Method and device for rapid particle removal using organic film

Abstract

The present disclosure provides a method and apparatus for rapidly removing particles using an organic film. The method comprises: S1, applying an organic solution to the surface of a material substrate containing particles to be removed, the organic solution comprising at least a polymer and a solvent; S2, baking the material substrate to make the organic solution viscous so as to wrap around the particles, the baking temperature being higher than the glass transition temperature of the polymer; S3, after the temperature is lowered, the organic solution in S2 solidifies into an organic film; and the organic film is peeled off, and the particles are simultaneously removed. The method disclosed herein can remove particles from the surface of a material substrate of any thickness and size in one go, with high particle removal efficiency and a particle removal rate exceeding 93%. It does not require the use of large amounts of high-purity chemical reagents and does not damage the surface of the material substrate. The method is applicable to the removal of particles from the surfaces of material substrates such as silicon wafers, silicon wafers covered with dielectrics and / or metals and / or photosensitive materials, silicon wafers containing graphic structures, and masks.

Description

Technical Field

[0001] The present disclosure relates to the field of semiconductor manufacturing technology, and in particular to a method and device for rapidly removing particles using an organic film. Background Art

[0002] In the semiconductor industry, particles are usually cleaned using wet cleaning technology (Wet Clean Technology) based on chemical reagents. This technology uses a large amount of high-purity chemical reagents, which not only pollutes the environment, but also increases additional technical costs for the treatment of chemical waste liquid after cleaning.

[0003] To address these issues, technicians have developed an alternative cleaning technology, namely dry cleaning technology (DryClean Technology). Existing dry cleaning technologies include plasma cleaning technology, photochemical cleaning technology, and supercritical CO2 fluid cleaning technology. Among them, plasma cleaning technology can easily damage the surface of the material substrate; photochemical cleaning technology has low removal efficiency, leaving ash residue after treatment, and ultraviolet rays can easily harm the health of process operators; in supercritical CO2 fluid cleaning technology, the van der Waals force between CO2 molecules is weaker than that of hydrocarbon solvent molecules, and the solubility of inorganic or organic substances is relatively small, resulting in a narrow range of applications.

[0004] In addition, the mature cleaning technologies in the above-mentioned semiconductor industry are mainly for bare wafers and wafers coated with photoresist. For wafers covered with dielectrics, metals or multi-layer films, targeted development of chemical cleaning reagents is required, which has a long development cycle and poor compatibility. For the cleaning of patterned wafers, specialized technologies such as megasonic waves are required, and the cleaning equipment is expensive. Summary of the Invention

[0005] (1) Technical issues to be resolved

[0006] In response to the above problems, the present disclosure provides a method and device for quickly removing particles using organic films, which are used to solve technical problems such as the narrow application range, low removal efficiency, easy surface damage, and severe environmental pollution of traditional methods.

[0007] (2) Technical solution

[0008] On the one hand, the present disclosure provides a method for quickly removing particles using an organic film, comprising: S1, applying an organic solution to the surface of a material substrate containing particles to be removed; wherein the organic solution includes at least a polymer and a solvent; S2, baking the material substrate to make the organic solution viscous so as to wrap the particles; wherein the baking temperature is higher than the glass transition temperature of the polymer; S3, after the temperature is lowered, the organic solution in S2 solidifies into an organic film; and peeling off the organic film, and the particles are removed at the same time.

[0009] Furthermore, the coating method in S1 includes one of spin coating, scraping coating, and drop coating; the material substrate in S1 includes one of a silicon wafer, a silicon wafer covered with a dielectric and / or metal and / or photosensitive material, a silicon wafer containing a graphic structure, and a mask.

[0010] Furthermore, the mass percentage of the high molecular weight polymer in S1 is 1 to 30%, and the high molecular weight polymer includes one or more of polyethylene terephthalate, epoxy acrylate resin, polyurethane acrylate, unsaturated polyester resin, polyester acrylate, polyether acrylate, polymethyl methacrylate, polyvinyl alcohol, and hyaluronic acid; the solvent in S1 includes one or more of water, anisole, chlorophenol, cresol, carbon tetrachloride, benzene, toluene, dichloroethane, chloroform, and acetone.

[0011] Furthermore, the organic solution in S1 also includes additives, and the mass percentage of the additives is 0.1-1%; the additives include one or more of 1,4-butanediol, glycerol, triethanolamine, trimethylolethane, ethanol, ethylene glycol, polyvinyl alcohol, dipentaerythritol, tripentaerythritol, and polyvinyl pyrrolidone.

[0012] Furthermore, the viscosity of the organic solution in S1 ranges from 1 MPa.s to 25 Pa.s.

[0013] Furthermore, the baking temperature range in S2 is 50°C to 100°C; the method of stripping the organic film in S3 includes one of automatic film stripping and tearing stripping; the thickness of the organic film in S3 is 1μm to 10μm; the particle size of the particles to be removed is above 30nm, and the particle removal rate is above 93%.

[0014] On the other hand, the present disclosure provides a device for quickly removing particles using an organic film, comprising: a coating unit for coating an organic solution on the surface of a material substrate from which the particles are to be removed; wherein the organic solution comprises at least a polymer and a solvent; a baking unit for baking the material substrate to make the organic solution viscous so as to wrap around the particles; wherein the baking temperature is higher than the glass transition temperature of the polymer; a stripping unit for solidifying the viscous organic solution into an organic film after the temperature is lowered; and stripping the organic film, and the particles are removed at the same time.

[0015] Furthermore, the coating unit includes: a coating wafer table, including a partition and a vacuum adsorption chamber, the partition is used to divide the vacuum adsorption chamber into areas; a vacuum control module, connected to the vacuum adsorption chamber, used to form a vacuum in the vacuum adsorption chamber; a rotation control module, connected to the coating wafer table, used to drive the coating wafer table to rotate; a clean module, arranged on the upper part of the coating wafer table, used to provide filtered clean air; a liquid supply module, used to provide organic solution, degumming liquid and pipeline flushing liquid; a coating module, used to coat the organic solution; an edge glue removal module, used to remove the edge glue formed after the organic solution is coated; and a drainage module, used to directionally extract the exhaust gas.

[0016] Furthermore, the baking unit includes: a baking and peeling wafer carrier for supporting the material base; a heating element for baking the material base; a vacuum adsorption element, which is alternately distributed with the heating element and is used for vacuum adsorption of the material base to facilitate subsequent peeling of the organic film.

[0017] Furthermore, the peeling unit includes: an adhesive film, which has adhesive force on the side facing the organic film, and the adhesive force between the adhesive film and the organic film is greater than the adhesive force between the organic film and the material substrate; a pressure measuring element, which is used to press the adhesive film down so that it contacts the organic film and measures the pressure value applied to the organic film; an active roller, which is combined with one end of the adhesive film and is used to drive the adhesive film to separate the organic film from the material substrate when the pressure value reaches a set value; and a passive roller, which is combined with the other end of the adhesive film and moves synchronously with the active roller under the drive of the adhesive film and provides a new adhesive film.

[0018] (3) Beneficial effects

[0019] The method and device disclosed herein for rapidly removing particles using an organic film utilize the pore structure and volume phase change characteristics of the organic film itself. During baking, the temperature is higher than the glass transition temperature of the high-molecular polymer in the organic solution, the organic solution is converted into a high-viscosity state, and the particles are wrapped by the high-viscosity organic solution; after cooling, the temperature is lower than the glass transition temperature of the high-molecular polymer, the high-viscosity organic solution further solidifies, and an organic film is formed; the mechanical interlocking force between the organic film and the particles is enhanced, the particles are fixed in the organic film, and the particles are removed while the organic film is peeled off.

[0020] The method disclosed herein is simple to operate and can remove particles on the surface of a material substrate of any thickness and any size at one time. It has a high particle removal efficiency, with a particle removal rate of over 93%. It does not require the use of a large amount of high-purity chemical reagents and does not damage the surface of the material substrate. It is particularly suitable for removing particles below 100 nm and can be applied to the removal of particles on the surface of material substrates such as silicon wafers, silicon wafers covered with dielectrics and / or metals and / or photosensitive materials, silicon wafers containing graphic structures, and masks. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] Figure 1 A flow chart schematically illustrates a method for rapidly removing particles using an organic film according to an embodiment of the present disclosure;

[0022] Figure 2 The following schematically shows a structural diagram of a device for rapidly removing particles using an organic film according to an embodiment of the present disclosure;

[0023] Figure 3 Schematically shows a structural diagram of a coating unit in a device for rapidly removing particles using an organic thin film according to an embodiment of the present disclosure;

[0024] Figure 4 The structure diagram of the baking and stripping unit in the device for rapidly removing particles using an organic film according to an embodiment of the present disclosure is schematically shown;

[0025] Figure 5 Schematically shows a structural diagram of peeling of an organic thin film from a material substrate according to Example 1 of the present disclosure;

[0026] Figure 6 Schematically shows a structural diagram of peeling of an organic thin film from a material substrate according to Example 2 of the present disclosure;

[0027] Figure 7 Schematically shows a structural diagram of peeling of an organic thin film from a material substrate according to Example 3 of the present disclosure;

[0028] Figure 8 Schematically showing a photograph of the organic film after demoulding and SEM images before and after particle removal according to Example 1 of the present disclosure;

[0029] Figure 9 Schematically showing a photograph of the organic film after demolding and SEM images before and after particle removal according to Example 2 of the present disclosure;

[0030] Figure 10 Schematically shows the natural dust distribution on the surface of the material substrate before and after particle removal according to Example 3 of the present disclosure;

[0031] Figure 11 Schematically shows a flow chart of peeling an organic thin film from a mask according to Example 4 of the present disclosure and SEM images of the mask surface before and after particle removal;

[0032] Description of reference numerals:

[0033] 1. Material substrate; 2. Organic film; 3. Warped portion; 4. Organic solution; 5. First functional layer; 6. Second functional layer; 7. Wafer; 101. Loading and unloading unit; 102. Electronic control unit; 103. Transmission unit; 104. Coating unit; 105. Baking and stripping unit; 201. Cleaning module; 202. Pressure pipe; 203. Coating module; 204. First nozzle; 205. Pipeline flushing waste liquid nozzle; 206. Second nozzle; 207. First guide member; 208. Auxiliary chamber; 209. Partition member; 210. Vacuum adsorption chamber; 211. Rotation control module; 212, vacuum control module; 213, second guide member; 214, third nozzle; 215, valve; 216, first storage bottle; 217, third storage bottle; 218, second storage bottle; 301, pressure measuring element; 302, suspension component; 303, active roller; 304, passive roller; 305, power component; 306, support component; 307, baking and peeling wafer carrier; 308, vacuum adsorption element; 309, heating element; 310, ejector pin; 311, adhesive film; 312, support cavity; 313, vacuum pump. DETAILED DESCRIPTION

[0034] In order to make the objectives, technical solutions and advantages of the present disclosure more clearly understood, the present disclosure is further described in detail below in conjunction with specific embodiments and with reference to the accompanying drawings.

[0035] The terms used herein are only for describing specific embodiments and are not intended to limit the present disclosure. The terms "comprise," "include," etc. used herein indicate the presence of the features, steps, operations, and / or components, but do not exclude the presence or addition of one or more other features, steps, operations, or components.

[0036] This disclosure provides a method for rapidly removing particles using an organic film. Figure 1 , including: S1, applying an organic solution to the surface of a material substrate containing particles to be removed; wherein the organic solution includes at least a polymer and a solvent; S2, baking the material substrate to make the organic solution viscous so as to wrap the particles; wherein the baking temperature is higher than the glass transition temperature of the polymer; S3, after the temperature is lowered, the organic solution in S2 solidifies into an organic film; peeling off the organic film, and the particles are removed at the same time.

[0037] The method first applies an organic solution to the surface of the material substrate, covering the particles to be removed at the same time; then the material substrate is baked, and the baking temperature is higher than the glass transition temperature of the high molecular polymer in the organic solution, so that the organic solution is transformed into a high viscosity state, and the particles are trapped in the organic solution in the high viscosity state and are wrapped by the organic solution in the high viscosity state; after cooling, the temperature is reduced and lower than the glass transition temperature of the high molecular polymer, and the organic solution in the high viscosity state is further solidified and transformed into a solid state, forming an organic film, and the mechanical interlocking force between the organic film and the particles is enhanced, and the particles are fixed in the organic film. When the organic film is peeled off, the particles are also removed, and the material substrate is cleaned. The particles in this disclosure refer to particulate pollutants, and the size of the particles is generally below 100nm.

[0038] On the one hand, the present disclosure utilizes the pore structure and volume phase change characteristics of the organic film itself, and the method for removing particles is simple to operate. It has significant advantages over traditional dry cleaning technology and wet cleaning technology. Without applying external energy to the material substrate, the particles can be trapped in the organic film, and particles on material substrates of any thickness and any size can be removed at one time; the organic solution can coat the entire area of ​​the material substrate, so the particle removal efficiency is high and the speed is fast. On the other hand, in the particle removal process, only a small amount of high-molecular organic solution is needed, and there is no need to use a large amount of high-purity chemical reagents such as strong acids and strong bases. Therefore, a large amount of waste liquid will not be generated, and there is no need to use expensive cleaning equipment, which reduces the pollution to the environment. Finally, the stripping method of the organic film is simple, does not require a special stripping solution, and there is no residue after treatment. It will not cause damage to the surface of the material substrate and has a wide range of applications.

[0039] Based on the above embodiment, the coating method in S1 includes one of spin coating, scraping coating, and drop coating; the material substrate in S1 includes one of a silicon wafer, a silicon wafer covered with a dielectric and / or metal and / or photosensitive material, a silicon wafer containing a graphic structure, and a mask.

[0040] The method of coating the organic solution in the present disclosure is not limited to the above three methods. Other methods that can make the organic solution form a uniform film on the surface of the material substrate can be applied to the present disclosure. It should be noted that when using the spin coating method, in order to avoid bubbles during the spin coating process, the spin coating speed adopts a low-speed and high-speed combination method. The low-speed spin coating speed range is 200rpm~500rpm, and the high-speed spin coating speed range is 1000rpm~4000rpm. The total spin coating time range of low-speed spin coating and high-speed spin coating is preferably 30s~60s, but can be adjusted as needed. After baking, the thickness of the organic solution film formed is 1μm~10μm.

[0041] The material substrate in S1 is the material substrate on which the particulate contaminants adsorbed on its surface need to be removed. The material substrate can be of any material, and there is no limit on its thickness and size, including but not limited to the following three types of silicon wafers, or a silicon wafer containing a multi-layer thin film structure, or a silicon wafer that has undergone chemical mechanical polishing (CMP), ion implantation and other processes; wherein, the characteristic size of the silicon wafer containing a graphic structure is ≤100nm, and the aspect ratio is ≥3:1. Since the method disclosed in the present invention does not cause damage to the surface of the material substrate, it is particularly suitable for cleaning silicon wafers covered with dielectrics, metals or multi-layer films, and silicon wafers containing graphic structures.

[0042] Based on the above embodiment, the mass percentage of the high molecular weight polymer in S1 is 1 to 30%, and the high molecular weight polymer includes one or more of polyethylene glycol terephthalate (PET), epoxy acrylate resin (EA), polyurethane acrylate (PUA), unsaturated polyester resin (UPE), polyester acrylate (PEA), polyether acrylate (Polyether acrylate), polymethyl methacrylate (PMMA), polyvinyl alcohol (PVA), and hyaluronic acid (HA); the solvent in S1 includes one or more of water, anisole, chlorophenol, cresol, carbon tetrachloride, benzene, toluene, dichloroethane, chloroform, and acetone.

[0043] The organic solution used in S1 comprises at least a polymer and a solvent, wherein the polymer comprises 1 to 30% by weight, with the remainder being the solvent. The organic film subsequently formed is a thermosetting or thermoplastic polymer having a well-defined pore structure, volume phase transition, and mechanical properties such as tensile strength and elongation at break.

[0044] Based on the above embodiment, the organic solution in S1 further includes an additive, and the mass percentage of the additive is 0.1-1%; the additive includes one or more of 1,4-butanediol, glycerol, triethanolamine, trimethylolethane, ethanol, ethylene glycol, polyethylene glycol, dipentaerythritol, tripentaerythritol, and polyvinyl pyrrolidone.

[0045] The organic solution may also include additives, with the polymer comprising 1-30% by weight, the additive comprising 0.1-1% by weight, and the remainder being solvent. The additives are used to control the adhesion between the organic film and the substrate, thereby enabling particle removal from various substrates. If the adhesion between the organic film and the substrate is adequate, additives may not be required.

[0046] It should also be noted that if the surface of the material substrate contains a photosensitive material, the components in the organic solution (which may include additives) must not dissolve or react with the photosensitive material, and the glass transition temperature of the organic solution must be lower than the pre-drying temperature of the photosensitive material, which is ≤100°C.

[0047] Based on the above embodiment, the viscosity of the organic solution in S1 ranges from 1 MPa.s to 25 Pa.s.

[0048] The organic solution viscosity being within the above range is beneficial for regulating the film-forming properties of the organic thin film formed in the subsequent process.

[0049] Based on the above embodiment, the baking temperature range in S2 is 50°C to 100°C.

[0050] In addition to regulating the adhesion between the organic film and the material substrate by adding additives, the baking temperature during the process can also be used to control it. In order to achieve effective particle removal by the organic film while maintaining the integrity of the multi-layer film structure on the material substrate, the glass transition temperature of the organic film must be less than or equal to the baking temperature, and the solvent content within the organic film after baking must be greater than or equal to 40%. This is to regulate the adhesion between the organic film and the material substrate and ensure that the subsequent stripping process does not affect the integrity of the multi-layer film structure on the material substrate. Therefore, the baking temperature range in the process is preferably 50°C to 100°C.

[0051] Based on the above embodiment, the method of stripping the organic film in S3 includes one of automatic film stripping and tearing stripping; the thickness of the organic film in S3 is 1μm~10μm; the particle size of the particles to be removed is above 30nm, and the particle removal rate can reach above 93%.

[0052] Depending on the type of organic film, the peeling process can be automatic or tear-off. Automatic peeling relies on the principle that, under external heating, pressure, or other mechanical conditions, some of the polymer chains are broken, causing the organic film to shrink. Tear-off peeling utilizes an adhesive roller structure, where the adhesion between the roller and the organic film must be greater than the adhesion between the organic film and the substrate.

[0053] The thickness of the organic film in S3 is the thickness of the cured film. This thickness within the aforementioned range helps ensure that the organic film does not break during the stripping process. Furthermore, the post-coating curing time of the organic film is controlled within 10 minutes to ensure the efficiency of the particle removal method. The particle removal capability of the organic film and the damage to the substrate can be adjusted by adding additives to the organic film and controlling the baking process conditions. This allows for the effective removal of particles of various sizes, and is particularly suitable for the removal of particles under 100 nm.

[0054] The present disclosure also provides a device for quickly removing particles using an organic film, comprising: a coating unit for coating an organic solution on the surface of a material substrate from which particles are to be removed; wherein the organic solution comprises at least a polymer and a solvent; a baking unit for baking the material substrate to make the organic solution viscous so as to wrap around the particles; wherein the baking temperature is higher than the glass transition temperature of the polymer; a stripping unit for solidifying the viscous organic solution into an organic film after the temperature is lowered; and stripping the organic film, and the particles are removed at the same time.

[0055] like Figure 2 As shown, the coating unit 104 covers the organic solution onto the material substrate by spin coating, drip coating, scraping, etc., and is mainly used for uniform coating of the organic solution on the material substrate; the coating unit 104 also includes a liquid supply module, which is used to supply the organic solution to the solution nozzle. The organic solution includes but is not limited to pipeline cleaning liquid, organic solution that can be solidified into an organic film, and degumming liquid that can dissolve the organic film; that is, the coating unit 104 also has the function of removing edge glue.

[0056] The baking and stripping unit 105, consisting of a baking unit and a stripping unit, is primarily used to coat the particles with the organic solution and remove the organic film. The baking unit provides vacuum suction and heating functions, solidifying the organic solution on the substrate. Once cooled and solidified into an organic film, the substrate is secured by vacuum suction, preparing for the organic film stripping process. The stripping unit incorporates a roller structure and a pressure sensor for stripping the organic film.

[0057] like Figure 2As shown, the particle removal device also includes a loading and unloading unit 101, an electronic control unit 102, and a transmission unit 103. The loading and unloading unit 101 is used to transport the material substrate storage box; the electronic control unit 102 is used to realize the automated control of the organic dry cleaning process and flow; and the transmission unit 103 is used to transport the material substrate during the organic dry cleaning process. The process flow of the particle removal device includes: the material substrate to be removed from the particles is placed in the storage box of the loading and unloading unit 101, and is transferred to the coating unit 104 by the mechanical transfer arm in the transmission unit 103 for the coating process of the organic solution; then, the mechanical transfer arm in the transmission unit 103 transfers the material substrate to the baking and stripping unit 105 for baking the organic solution and stripping the organic film; after the cleaning, the material substrate is placed into another clean storage box in the loading and unloading unit 101 by the mechanical transfer arm in the transmission unit 103, and the material substrate is cleaned.

[0058] Based on the above embodiments, the coating unit includes: a coating wafer table, including a partition and a vacuum adsorption chamber, the partition is used to divide the vacuum adsorption chamber into areas; a vacuum control module, connected to the vacuum adsorption chamber, for forming a vacuum in the vacuum adsorption chamber; a rotation control module, connected to the coating wafer table, for driving the coating wafer table to rotate; a clean module, arranged on the upper part of the coating wafer table, for providing filtered clean air for the coating unit, which can be filtered by a fan filter unit (FFU); a liquid supply module, for providing organic solution, degumming liquid and pipeline flushing liquid; a coating module, for coating the organic solution; an edge glue removal module, for removing the edge glue formed after the organic solution is coated; and a drainage module, for directionally extracting the exhaust gas.

[0059] The specific structure of the coating unit 104 is as follows Figure 3 As shown. The material substrate 1 is adsorbed on the coating wafer stage, which is composed of a partition 209 and a vacuum adsorption chamber 210. The partition 209 divides the vacuum adsorption chamber 210 into regions to accommodate the adsorption of material substrates of different sizes. The partition 209 can be retracted into the auxiliary chamber 208 as needed, thereby achieving regional division of the vacuum adsorption chamber 210. Specifically, the partition 209 is, for example, a latch. The adsorption vacuum is generated by the vacuum control module 212, which is connected to the vacuum adsorption chamber 210 through the rotation control module 211. Specifically, the rotation control module 211 is, for example, a bearing, and the vacuum control module 212 is, for example, a vacuum pump.

[0060] The liquid supply module includes a first storage bottle 216, a second storage bottle 218, a third storage bottle 217, a pressure pipe 202, and a valve 215. The organic solution placed in the first storage bottle 216 is pressure-fed to the first nozzle 204 via the pressure pipe 202, where it is dripped onto the material substrate 1. The pressure pipe 202 is retractable and, in combination with the rotation control module 211, can achieve spin coating, drip coating, etc. of the organic solution 4 on the material substrate 1. In combination with the coating module 203, the organic solution 4 can also be scraped. One side of the coating module 203 can be retracted to accommodate scraping processes for material substrates of various sizes. Specifically, the coating module 203 is, for example, a scraping component. The edge glue removal module includes a second nozzle 206 and a third nozzle 214. After the organic solution 4 completes the coating process, the glue removal liquid placed in the second storage bottle 218 can be passed through the second nozzle 206 and the third nozzle 214 to remove the edge glue after the organic solution 4 is coated, facilitating the subsequent demolding and peeling of the organic film. This part of the degumming liquid can be selectively sprayed through the valve 215. The third storage bottle 217 stores the pipeline flushing liquid, which can be used to clean the pressure pipeline 202 when replacing the solution or solvent. The waste liquid after pipeline flushing is discharged from the pipeline flushing waste liquid nozzle 205. At this time, the pressure pipeline 202 shrinks to the position above the pipeline flushing waste liquid nozzle 205 and is separated from the material base 1. The drainage module includes a first drainage member 207 and a second drainage member 213 arranged on both sides of the coating wafer table. The waste gas generated by the organic solution coating process is orderly and directionally exhausted by the first drainage member 207 and the second drainage member 213. The coating unit 104 and the baking and stripping unit 105 also include a clean module 201, which is used to provide clean air filtered by the FFU.

[0061] On the basis of the above embodiment, the baking unit includes: a baking and peeling table for supporting the material base; a heating element for baking the material base; a vacuum adsorption element, which is alternately distributed with the heating element and is used to vacuum adsorb the material base to facilitate the subsequent peeling of the organic film; the peeling unit includes: an adhesive film, which has adhesion on the side facing the organic film, and the adhesion between the adhesive film and the organic film is greater than the adhesion between the organic film and the material base; a pressure measuring element, which is used to press the adhesive film down so that it contacts the organic film and measures the pressure value applied by the adhesive film to the organic film through the suspension component 302; an active roller, which is combined with one end of the adhesive film, and is used to drive the adhesive film to separate the organic film from the material base when the pressure value reaches a set value; a passive roller, which is combined with the other end of the adhesive film, and is driven by the adhesive film and moves synchronously with the active roller and provides a new adhesive film.

[0062] The specific structure of the baking and peeling unit 105 is as follows: Figure 4As shown, the material substrate 1 is placed on ejector pins 310, approximately 5 cm above the baking and stripping stage 307. This ensures uniform heating of the material substrate 1 coated with the organic solution 4. Considering that the baking and stripping stage 307 needs to simultaneously perform both heating and vacuum adsorption functions, heating elements 309 (e.g., resistance wires) and vacuum adsorption elements 308 (e.g., vacuum adsorption rings) are arranged in a cross-pattern. The adsorption vacuum is generated by a vacuum pump 313, which is connected to the baking and stripping stage 307 via a support cavity 312. After the baking and curing process is completed, the ejector pins 310 retract into the baking and stripping stage 307, bringing the material substrate 1 into contact with the baking and stripping stage 307. Vacuum adsorption then occurs to facilitate the stripping of the organic film. The stripping unit consists of a passive roller 304, an active roller 303, an adhesive film 311, and a pressure sensor 301. The pressure sensor 301 is movable in the x- and z-directions via a suspension component 302. The adhesive film 311 has adhesive force on the side facing the organic film. The adhesive force between the adhesive film 311 and the organic film is greater than the adhesive force between the organic film and the material substrate 1. The active roller 303 is driven by the power component 305 to move. The passive roller 304 moves along with the active roller 303 via the adhesive film 311. The passive roller 304 is supported by the support component 306.

[0063] First, the pressure measuring element 301 moves to the edge of the organic film, then moves downward, contacts the adhesive film 311, and then continues to move downward to contact the organic film. At this time, the pressure measuring element 301 continues to move downward to measure the pressure value. When the pressure value reaches the set value, the pressure measuring element 301 is allowed to move upward quickly under the action of the suspension component 302, and the organic film can be adjusted as shown in FIG. Figure 5 The active roller 303 then moves in the x-direction, causing the adhesive film 311 to drive the organic film to continue peeling in the x-direction, and finally completely detach from the material base 1, thereby removing particles from the material base 1.

[0064] The present disclosure applies organic thin film materials to the surface cleaning of material substrates in the semiconductor industry, breaking the drawbacks of the original wet cleaning technology that uses a large amount of chemical liquids, avoiding the problem of handling chemical waste liquids, saving cleaning costs and reducing pollution to the environment. At the same time, the method disclosed in the present disclosure also has the advantages of high cleaning efficiency, no damage to the surface of the material substrate, and no residue after treatment. By wrapping the organic thin film, it can achieve the removal of particles of different sizes; without applying external energy to the material substrate, the particles can be trapped in the organic thin film, and can achieve a one-time rapid removal of particles of 100nm and below on material substrates of any thickness and any size. The demolding method is simple, does not require special stripping liquid, and there is no residue after treatment. It is especially suitable for cleaning particles of dielectric or metal or multi-layer film-covered material substrates and material substrates containing graphic structures. Finally, the present disclosure only requires a simple modification on the glue coating equipment to achieve rapid removal of particles, without relying on expensive cleaning equipment, and has a wide range of applications.

[0065] The present disclosure is further described below through specific embodiments. The following examples specifically illustrate the method and apparatus for rapidly removing particles using an organic film. However, the following examples are merely illustrative of the present disclosure and are not intended to limit the scope of the present disclosure.

[0066] The method disclosed herein for rapidly removing particles using an organic film comprises performing the following steps in sequence:

[0067] Step 1: Applying an organic solution to a material substrate from which particles need to be removed; methods for applying the organic solution to the material substrate include, but are not limited to, spin coating, scraping, drip coating, etc.; equivalent to the above-mentioned step S1.

[0068] Step 2: Bake the material base covered with the organic solution, and the organic solution becomes viscous so as to wrap the particles on the surface of the material base; the glass transition temperature of the organic film must be less than or equal to the baking temperature, and the solvent content inside the organic film after baking must be greater than or equal to 40%. The baking temperature range in the process is preferably 50°C to 100°C; this is equivalent to the above-mentioned step S2.

[0069] Step 3: After cooling, the viscous organic solution further solidifies to form an organic film. The organic film is then peeled from the substrate, simultaneously removing the particles. Peeling methods include automatic peeling or tearing. The tearing process must be performed in a clean environment (ISO Class 5 or higher). The tearing process uses a rolling motion to ensure uniform tearing force, effectively controlling the amount of organic film remaining on the substrate. This is equivalent to step S3 above.

[0070] According to the above steps 1 to 3, four specific embodiments are provided below.

[0071] Example 1:

[0072] This embodiment is described by taking the removal of particles on a bare wafer as an example. The implementation steps are as follows:

[0073] Step 11: SiO2 particles with a particle size of 100 nm were coated on the bare wafer to investigate the ability of the organic thin film HA to remove SiO2 particles;

[0074] Step 12: Apply the HA organic solution on a bare wafer with a thickness of 725 μm and a diameter of 30 mm, first spin-coating at a low speed of 500 rpm for 10 seconds, and then spin-coating at a high speed of 2000 rpm for 50 seconds. The HA organic solution consists of hyaluronic acid HA and solvent water, with the mass percentage of HA being 3% and the rest being water. The viscosity of the HA organic solution is 2.0 mPa.s.

[0075] Step 13: Figure 5 As shown, an organic solution is coated on a wafer 7, and the organic solution solidifies to form an organic film 2. During the solidification process, a warped portion 3 is formed at the edge of the organic film 2. In this embodiment, the wafer 7 is a material substrate, and the HA film is the organic film 2. Specifically, the bare wafer coated with the HA organic solution is placed on a hot plate, and baked at 80°C for 4 minutes. The temperature is then adjusted to 90°C and the baking is continued to solidify the HA film layer. Finally, the baking is continued at 100°C for 1 minute. Due to the strong dehydration of HA, the HA at the edge of the bare wafer will naturally warp during the baking process, and the HA film will automatically peel off. Figure 8 As shown in (a);

[0076] Step 14: Separate the naturally warped HA organic film from the bare wafer, thereby removing the 100nm SiO2 particles on the bare wafer. The SEM image of the bare wafer surface before removing the particles is as follows: Figure 8 As shown in (b), the white bright spots in the figure are the SiO2 particles on the spin coating. The SEM image of the bare wafer surface after removing the particles is as follows Figure 8 As shown in (c), the original Figure 8 The white bright spots in (b) disappear, indicating that the SiO2 particles are removed. According to statistics, the particle removal rate of this embodiment reaches 95.6%.

[0077] Example 2:

[0078] This embodiment is described by taking the removal of particles on a wafer containing a metallic silver layer as an example. The implementation steps are as follows:

[0079] Step 21: Depositing a layer of metallic silver with a thickness of 40 nm on an 8-inch bare wafer with a thickness of 725 μm and a diameter of 200 mm by magnetron sputtering;

[0080] Step 22: Spin-coating SiO2 particles with a particle size of 60 nm on the silver film layer to examine the ability of the organic thin film PVA to remove particles on the silver film layer;

[0081] Step 23: Figure 6 As shown, a first functional layer 5 is prepared on a wafer 7, and an organic solution is coated on the first functional layer 5. The organic solution solidifies to form an organic film 2, and a warped portion 3 is formed at the edge of the organic film 2 during the solidification process. In this embodiment, the wafer 7 and the first functional layer 5 constitute the material substrate, and the PVA film is the organic film 2. Specifically, the PVA organic solution is spin-coated on a silver film covered with SiO2 particles with a particle size of 60 nm, first at a low speed of 400 rpm for 20 seconds, and then at a high speed of 3000 rpm for 30 seconds; wherein, the alcoholysis degree of PVA is 88%, the PVA organic solution is composed of a high molecular polymer PVA, an additive glycerol, and a solvent water, and has a viscosity of 10.0 mPa.s. The mass percentage of PVA in the PVA organic solution is 25%, the mass percentage of glycerol is 3%, and the rest is water;

[0082] Step 24: Place the material substrate coated with the PVA organic solution on a hot plate, bake at a temperature of 65° C. for 3 to 8 minutes;

[0083] Step 25: After the material base is naturally cooled to room temperature, the PVA organic film is peeled off from the silver film layer by tearing. Figures 2 to 4 In the device shown, the pressure element 301 first moves to the edge of the PVA film, then moves downward, making contact with the adhesive film 311, and then continues downward to contact the PVA film. At this point, the downward movement continues, and the pressure element 301 measures the pressure value. When the pressure value reaches the set value of 40N, the pressure element 301 is quickly moved upward by the suspension component 302, and the PVA film is partially peeled off from the material substrate. Subsequently, the active roller 303 moves in the x-direction, causing the adhesive film 311 to continue peeling the organic film in the x-direction, and finally completely detaching from the material substrate. Figure 9 As shown in (a), the particles on the wafer containing the metallic silver layer are removed. The SEM image of the material substrate surface before the particles are removed is shown in FIG. Figure 9 As shown in (b), the SEM image of the material substrate surface after removing the particles is as follows Figure 9 As shown in (c), it can be seen that most of the SiO2 particles are removed. According to statistics, the particle removal rate of this embodiment reaches 93.8%.

[0084] Example 3:

[0085] This embodiment is described by taking the removal of particles on a wafer having a multi-layer film structure as an example. The implementation steps are as follows:

[0086] Step 31: Spin-coat a 1 μm thick layer of photoresist on an 8-inch bare wafer with a thickness of 725 μm and a diameter of 200 mm;

[0087] Step 32: Depositing a silver film with a thickness of 20 nm on the photoresist by thermal evaporation;

[0088] Step 33: Place the silver film in an atmospheric environment for 1 hour to allow enough dust to fall onto the silver film.

[0089] Step 34: Spin-coating a PVA organic solution on the silver film covered with naturally fallen dust, first at a low speed of 200 rpm for 30 seconds, followed by a high speed of 4000 rpm for 20 seconds; wherein the alcoholysis degree of the PVA is 88%, the PVA organic solution is composed of a high molecular weight polymer PVA, an additive triethanolamine, and a solvent water, and has a viscosity of 5.0 mPa·s, wherein the mass percentage of PVA in the PVA organic solution is 24%, the mass percentage of triethanolamine is 1%, and the remainder is water;

[0090] Step 35: placing the material substrate coated with the PVA organic solution in an oven at a baking temperature of 60° C. to 80° C. for 10 min to 30 min;

[0091] Step 36: After the material base is naturally cooled to room temperature, the PVA organic film is peeled off from the silver film layer by tearing. Figures 2 to 4 In the device shown, the pressure measuring element 301 first moves to the edge of the PVA organic film, then moves downward, contacts the adhesive film 311, and then continues to move downward to contact the PVA organic film. At this time, it continues to move downward, and the pressure measuring element 301 measures the pressure value. When the pressure value reaches the set value of 25N, the pressure measuring element 301 is allowed to move upward rapidly under the action of the suspension component 302, and the PVA organic film can be partially peeled off from the material base. The pressure setting value here is smaller than that in Example 2 because it is considered that the particles removed here are not SiO2 particles but natural dust. The adhesion of the two is different from that of silver. The former is chemical adsorption and the latter is physical adsorption. Subsequently, the active roller 303 will move along the x-direction, so that the adhesive film 311 drives the organic film to continue to peel off in the x-direction, and finally completely separates from the material base, thereby achieving the removal of particles on the wafer containing the multi-layer film structure. The distribution diagram of natural dust on the surface of the material base before removing the particles is shown in FIG. Figure 10 As shown in (a), the number of natural dust particles with a diameter range of 50nm to 200μm is 127,778, and the number of natural dust particles with a diameter of more than 200μm is 141. The distribution of natural dust particles on the surface of the material substrate after removing particles is shown in Figure 10As shown in (b), the number of naturally fallen dust particles with a diameter of 50nm to 200μm is 6892, and the number of naturally fallen dust particles with a diameter of 200μm is 18. 95% of the naturally fallen dust particles are removed.

[0092] Example 4:

[0093] This embodiment takes the removal of naturally fallen dust particles on a mask as an example for illustration, and the implementation steps are as follows:

[0094] Step 41: The particles on the mask are naturally fallen dust.

[0095] Step 41: A PMMA organic solution is drop-coated on a mask having a line width of 100 nm and an aspect ratio of 3:1. The PMMA organic solution is composed of a high molecular weight polymer PMMA and a solvent anisole. The mass percentage of PMMA in the PMMA organic solution is 11%, and the remainder is the solvent anisole. The viscosity of the PMMA organic solution is 24.5 Pa.s at 25°C. In this embodiment, the mask is the material substrate.

[0096] Step 42: Place the PMMA-coated mask on a hot plate at 80° C. and bake for 10 minutes with the lid closed.

[0097] Step 43: After the sample is cooled and solidified, the PMMA organic film layer is peeled off from the mask by tearing. Figures 2 to 4 In the device shown, pressure element 301 first moves to the edge of the PMMA film, then moves downward, making contact with adhesive film 311, and then continues downward to contact the PMMA film. At this point, while continuing downward, pressure element 301 measures the pressure. When the pressure reaches the set value of 100N (the PMMA solution enters the gaps in the nanopattern of the mask, so the required pressure is greater than the pressure on the flat silver film), pressure element 301 is rapidly moved upward by suspension component 302, allowing the PMMA film to partially peel away from the substrate. Subsequently, active roller 303 moves in the x-direction, allowing adhesive film 311 to drive the organic film to continue peeling in the x-direction, ultimately completely detaching from the mask. Figure 11 As shown in (a), the particles on the mask are removed. The SEM image of the mask surface before removing the particles is shown in Figure 11 As shown in (b), the SEM image of the mask surface after removing the particles is as follows Figure 11 As shown in (c), it can be seen that most of the particles are removed. According to statistics, the particle removal rate of this embodiment reaches 93.2%.

[0098] The present invention discloses a method and apparatus for rapidly removing particles using an organic film. By utilizing the pore structure and volume phase change characteristics of the organic film itself, particles on the surface of a material substrate of any thickness and any size can be removed at one time. The particle removal efficiency is high, and the use of a large amount of high-purity chemical reagents is not required. There is no damage to the surface of the material substrate, and the application range is wide.

[0099] The specific embodiments described above further illustrate the purpose, technical solutions and beneficial effects of the present disclosure. It should be understood that the above are only specific embodiments of the present disclosure and are not intended to limit the present disclosure. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present disclosure should be included in the scope of protection of the present disclosure.

Claims

1. A method for rapidly removing particles using an organic film, characterized in that: include: S1, applying an organic solution to the surface of a material substrate containing particles to be removed; wherein the organic solution comprises at least a polymer and a solvent; S2, baking the material substrate to make the organic solution viscous so as to wrap the particles; wherein the baking temperature is higher than the glass transition temperature of the polymer; the baking temperature range is 50° C. to 100° C.; S3, after the temperature is lowered, the organic solution in S2 solidifies into an organic film; the organic film is peeled off, and the particles are removed at the same time; the method for peeling off the organic film includes tearing peeling, and the tearing peeling is performed using a roller structure with adhesive force, and the structure includes: an adhesive film having adhesive force on a side facing the organic film, wherein the adhesive force between the adhesive film and the organic film is greater than the adhesive force between the organic film and the material substrate; a pressure measuring element for pressing the adhesive film downward to make it contact the organic film and measuring the pressure value applied to the organic film; an active roller, coupled to one end of the adhesive film, for driving the adhesive film to separate the organic film from the material substrate when the pressure value reaches a set value; The passive roller is combined with the other end of the adhesive film, and moves synchronously with the active roller under the drive of the adhesive film to provide a new adhesive film.

2. The method for rapidly removing particles using an organic film according to claim 1, wherein: The coating method in S1 includes one of spin coating, blade coating, and drop coating; The material substrate in S1 includes one of a silicon wafer, a silicon wafer covered with a dielectric and / or metal and / or photosensitive material, a silicon wafer with a pattern structure, and a mask.

3. The method for rapidly removing particles using an organic film according to claim 1, wherein: The mass percentage of the high molecular weight polymer in S1 is 1-30%, and the high molecular weight polymer includes one or more of polyethylene terephthalate, epoxy acrylate resin, polyurethane acrylate, unsaturated polyester resin, polyester acrylate, polyether acrylate, polymethyl methacrylate, polyvinyl alcohol, and hyaluronic acid; The solvent in S1 includes one or more of water, anisole, chlorophenol, cresol, carbon tetrachloride, benzene, toluene, dichloroethane, chloroform, and acetone.

4. The method for rapidly removing particles using an organic film according to claim 3, wherein: The organic solution in S1 further includes an additive, and the mass percentage of the additive is 0.1-1%; The additives include one or more of 1,4-butanediol, glycerol, triethanolamine, trimethylolethane, ethanol, ethylene glycol, polyvinyl alcohol, dipentaerythritol, tripentaerythritol, and polyvinyl pyrrolidone.

5. The method for rapidly removing particles using an organic film according to claim 1, wherein: The viscosity of the organic solution in S1 is in the range of 1 mPa.s to 25 Pa.s.

6. The method for rapidly removing particles using an organic film according to claim 1, wherein: The thickness of the organic film in S3 is 1 μm to 10 μm; The particle size of the particles to be removed is greater than 30 nm.

7. A device for rapidly removing particles using an organic film, characterized in that: include: A coating unit, configured to coat an organic solution on a surface of a material substrate from which particles are to be removed; wherein the organic solution comprises at least a high molecular weight polymer and a solvent; A baking unit, configured to bake the material substrate to make the organic solution viscous so as to wrap the particles; wherein the baking temperature is higher than the glass transition temperature of the high molecular weight polymer; and the baking temperature range is 50° C. to 100° C.; A stripping unit is used to solidify the viscous organic solution into an organic film after the temperature is lowered; and to strip the organic film, and the particles are removed at the same time; the stripping unit includes: an adhesive film having adhesive force on a side facing the organic film, wherein the adhesive force between the adhesive film and the organic film is greater than the adhesive force between the organic film and the material substrate; a pressure measuring element for pressing the adhesive film downward to make it contact the organic film and measuring the pressure value applied to the organic film; an active roller, coupled to one end of the adhesive film, for driving the adhesive film to separate the organic film from the material substrate when the pressure value reaches a set value; The passive roller is combined with the other end of the adhesive film, and moves synchronously with the active roller under the drive of the adhesive film to provide a new adhesive film.

8. The device for rapidly removing particles using an organic film according to claim 7, characterized in that: The coating unit comprises: The coating wafer stage comprises a separator and a vacuum adsorption chamber, wherein the separator is used to divide the vacuum adsorption chamber into regions; A vacuum control module connected to the vacuum adsorption chamber and used to form a vacuum in the vacuum adsorption chamber; A rotation control module, connected to the coating wafer stage, and configured to drive the coating wafer stage to rotate; A clean module is provided on the upper portion of the coating substrate platform and is used to provide filtered clean air; A liquid supply module, used for providing the organic solution, degumming solution and pipeline flushing solution; A coating module, used for coating the organic solution; An edge bead removal module, used for removing the edge bead formed after the organic solution is applied; Diversion module for targeted exhaust air extraction.

9. The device for rapidly removing particles using an organic film according to claim 7, characterized in that: The baking unit comprises: A baking and peeling wafer carrier, used for supporting the material substrate; A heating element, used for baking the material substrate; The vacuum adsorption elements are alternately distributed with the heating elements and are used to perform vacuum adsorption on the material substrate to facilitate the subsequent peeling of the organic film.

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