CN119340202A - Photoresist stripping method - Google Patents
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- CN119340202A CN119340202A CN202411886168.7A CN202411886168A CN119340202A CN 119340202 A CN119340202 A CN 119340202A CN 202411886168 A CN202411886168 A CN 202411886168A CN 119340202 A CN119340202 A CN 119340202A
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Abstract
The application discloses a photoresist stripping method, and relates to the technical field of semiconductors. The photoresist stripping method comprises the steps of annealing a wafer to alloy a metal coating, soaking the wafer in a first organic solvent to soften the photoresist on the wafer, spraying the wafer by sequentially using a second organic solvent and a third organic solvent, wherein the second organic solvent comprises N-methyl pyrrolidone, the third organic solvent has higher volatility than the second organic solvent, and drying the wafer. The photoresist stripping method provided by the application can effectively remove the photoresist on the wafer, and can relieve the corrosion of NMP on the metal coating, so that the yield of the product can be improved.
Description
Technical Field
The application relates to the technical field of semiconductors, in particular to a photoresist stripping method.
Background
The production of semiconductors relies on the use of photolithographic processes that pattern integrated circuits with a width of tens of nanometers linewidths or even less using photoresist in specialized manufacturing tools. Photolithography represents more than one third of the total production cost of microelectronic fabrication because defects are easily created at this stage. The photoresist stripping step must completely remove the unexposed photoresist and not adversely affect the material surface of the underlying wafer. One method of removing the photoresist is to use an organic solvent to dissolve the unexposed photoresist, thereby achieving the purpose of complete stripping.
In the related art, a method of stripping photoresist on a wafer is to sequentially soak and rinse the wafer with an organic solution. However, the organic solvents used in the prior art include N-methylpyrrolidone (NMP), and analysis shows that NMP reacts with transition metals to cause corrosion of the metal features. Therefore, the photoresist stripping method in the related art may cause a problem of low product yield.
In view of this, the present application has been made.
Disclosure of Invention
The application aims to provide a photoresist stripping method which can reduce corrosion of a metal coating and improve the yield of products.
The application is realized in the following way:
The application provides a photoresist stripping method, which is used for stripping photoresist on a wafer, wherein the wafer is provided with a metal plating layer and photoresist, the material of the metal plating layer comprises at least two metals, the at least two metals comprise transition metals, and the photoresist stripping method comprises the following steps:
Annealing the wafer to alloy the metal coating;
soaking the wafer in a first organic solvent to soften the photoresist on the wafer;
spraying the wafer by sequentially using a second organic solvent and a third organic solvent, wherein the second organic solvent comprises N-methyl pyrrolidone, and the third organic solvent has higher volatility than the second organic solvent;
and drying the wafer.
In an alternative embodiment, the annealing is performed at a holding temperature of 160-200 ℃ for 3-8 hours.
In an alternative embodiment, the temperature rise rate of the annealing is 8-12 ℃ per minute, and the temperature reduction rate is 3-6 ℃ per minute.
In an alternative embodiment, the first organic solvent is selected from at least one of dimethyl sulfoxide and dimethylformamide.
In an alternative embodiment, the third organic solvent is selected from at least one of isopropanol, ethanol, and acetone.
In an alternative embodiment, the wafer is controlled to rotate at a rotational speed of 800-1000 r/min during the process of spraying and drying the wafer.
In an alternative embodiment, the process of spraying the wafer with the second organic solvent is continued for 300-350 s, and the spraying pressure is 5-10 mpa.
In an alternative embodiment, the process of spraying the wafer with the third organic solvent is continued for 5-20 s, and the spraying pressure is 0.1-0.2 mpa.
In an alternative embodiment, the step of drying the wafer includes:
and continuously introducing a drying gas into a chamber where the wafer is located, wherein the temperature of the drying gas is 50-75 ℃.
In an alternative embodiment, the drying gas is nitrogen.
The application has the following beneficial effects:
The photoresist stripping method comprises the steps of annealing a wafer to alloy a metal coating, soaking the wafer in a first organic solvent to soften the photoresist on the wafer, spraying the wafer by sequentially using a second organic solvent and a third organic solvent, wherein the second organic solvent comprises N-methyl pyrrolidone, the third organic solvent has higher volatility than the second organic solvent, and drying the wafer. In the photoresist stripping method provided by the application, the metal coating is alloyed by the annealing process, so that two different metals (such as copper and aluminum) in the metal coating can form intermetallic compounds (such as CuAl 2, cuAl 3 and the like), the corrosion of an organic solvent can be effectively resisted, and the corrosion damage of the metal coating is reduced. Furthermore, after annealing, the wafer is soaked by the first organic solvent to soften the photoresist, and meanwhile, the photoresist can be roughened due to partial dissolution, so that the surface area is larger, the soaked photoresist is easier to dissolve and remove in the spraying process, the spraying duration is shortened, and the corrosion of N-methylpyrrolidone (NMP) to a metal coating in the spraying process is reduced. The spraying process comprises spraying by using a second organic solvent, wherein the second organic solvent contains NMP, and the spraying process is characterized in that the photoresist can be effectively dissolved and removed, and the cost is low. The spraying process further comprises the step of spraying the wafer by using a third organic solvent, wherein the third organic solvent has higher volatility than the second organic solvent, so that the second organic solvent remained on the wafer can be effectively removed by using the third organic solvent, the corrosion of the third organic solvent to the metal coating is avoided, and meanwhile, the subsequent drying is facilitated due to the high volatility of the third organic solvent. Therefore, by the photoresist stripping method, the photoresist on the wafer can be effectively removed, and simultaneously, the corrosion of NMP to the metal coating can be relieved, so that the yield of the product can be improved.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are needed in the embodiments will be briefly described below, it being understood that the following drawings only illustrate some embodiments of the present application and therefore should not be considered as limiting the scope, and other related drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a flow chart of a photoresist stripping method according to an embodiment of the application;
FIG. 2 is a scanning electron micrograph of a metal plating layer of a wafer obtained in example 1 of the present application;
FIG. 3 is a surface microscopic image of a wafer obtained in example 1 of the present application;
FIG. 4 is a surface microscopic image of a wafer obtained in comparative example 1 of the present application;
FIG. 5 is a graph showing a probe test of a wafer according to example 1 of the present application;
fig. 6 is a graph of a probe test of the wafer obtained in comparative example 1 of the present application.
Detailed Description
As described in the background art, in the related art, during the process of removing photoresist (particularly, photoresist to be removed, such as photoresist not exposed to light), NMP has a better dissolution and removal effect on photoresist, but it corrodes the metal coating, resulting in a decrease in the yield of the product. In some prior art, when deionized water is used to rinse the wafer to remove the residual NMP, the deionized water and the residual NMP form a new solvent system, which can have a solvation effect on the transition metal in the metal coating, thereby further exacerbating the problem of corrosion of the metal coating. Taking the example of a metal coating comprising copper, the solvent system formed by deionized water and residual NMP may solvate the copper ionic complex, thereby exacerbating copper corrosion. Corrosion of the metal plating can have a performance impact on the final fabricated device (e.g., saw filter) and even result in device failure.
In order to solve the problem that a metal coating is easy to corrode and damage when photoresist is stripped in the related art, the embodiment of the application provides the photoresist stripping method, which is used for relieving the corrosion and damage of NMP to the metal coating and improving the product yield by sequentially annealing, soaking and showering different solvents on a wafer.
In order to make the objects, technical solutions and advantages of the embodiments of the present application more clear, the technical solutions of the embodiments of the present application will be clearly and completely described below. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
FIG. 1 is a flow chart of a photoresist stripping method according to an embodiment of the application. The photoresist stripping method provided by the embodiment of the application is used for stripping the photoresist on the wafer, wherein the wafer is provided with a metal plating layer and the photoresist (particularly the photoresist to be removed, such as the photoresist which is not exposed), the material of the metal plating layer comprises at least two metals, and the at least two metals comprise transition metals. For example, the metal plating includes copper and aluminum. As shown in fig. 1, the photoresist stripping method includes the following steps.
In step S100, the wafer is annealed to alloy the metal plating.
By annealing, the transition metal in the metal coating can form intermetallic compounds, and the intermetallic compounds have better corrosion resistance, so that corrosion to the metal coating can be effectively reduced when the photoresist is washed by N-methyl pyrrolidone (NMP).
In an alternative embodiment, the material of the metal plating layer includes copper and aluminum. Copper and aluminum can form intermetallic compounds such as CuAl 2、Cu9Al4、Cu3 Al and CuAl 3 during annealing, which are better in corrosion resistance than copper, and thus can effectively improve the problem of copper corrosion.
Optionally, the annealing temperature is 160-200 ℃ and the heat preservation time is 3-8 hours. For example, the annealing temperature is any one point value or any two point values of 160 ℃, 170 ℃, 180 ℃, 190 ℃ and 200 ℃, and the heat preservation time is any one point value or any two point values of 3h, 4h, 5h, 6h, 7h and 8h.
Optionally, in the annealing process, the heating rate is 8-12 ℃ per minute, and the cooling rate is 3-6 ℃ per minute. The heating process in the annealing process refers to a process of heating from normal temperature to heat preservation temperature, and the cooling process in the annealing process refers to a process of cooling from heat preservation temperature to normal temperature.
It will be appreciated that parameters such as the holding temperature, holding time, heating rate and cooling rate will affect the alloying effect, i.e. will affect the amount and type of intermetallic compound produced, and may be set according to specific needs, for example, in one embodiment, the holding temperature is 180 ℃, the holding time is 6 hours, the heating rate is 10 ℃ per minute, and the cooling rate is 5 ℃ per minute.
In step S200, the wafer is soaked in a first organic solvent to soften the photoresist on the wafer.
Alternatively, the first organic solvent is selected from at least one of dimethyl sulfoxide (DMSO) and dimethylformamide. The first organic solvent is not easy to corrode the metal coating, can effectively soften the photoresist, and can also enable the photoresist to be roughened due to partial dissolution, so that the photoresist after soaking is easier to dissolve and remove in the subsequent spraying process, the spraying duration is shortened, and the corrosion of N-methylpyrrolidone (NMP) to the metal coating in the spraying process is reduced.
The wafer can be soaked in a soaking tank filled with the first organic solvent for 10-60 min.
And step S300, spraying the wafer by sequentially using a second organic solvent and a third organic solvent, wherein the second organic solvent comprises N-methylpyrrolidone, and the third organic solvent has higher volatility than the second organic solvent.
In the embodiment of the application, after the wafer is soaked, the wafer can be placed on a stage in a flushing groove to spray the wafer. In the spraying process, the wafer is controlled to rotate at a rotating speed of 800-1000 r/min, so that the sprayed organic solvent can be uniformly contacted with the wafer, and the photoresist can be completely cleaned. Optionally, the wafer is fixed by vacuum adsorption, and the front and back surfaces of the wafer are sprayed simultaneously by using a spray head. When the second organic solvent is used for spraying, the stepping track of the spray head covers the whole wafer.
It is understood that since the wafer is soaked in advance, the photoresist is easily dissolved and removed when the second organic solvent is used for spraying, and the spraying time can be shortened. Optionally, the process of spraying the wafer by using the second organic solvent lasts 300-350 s, and the spraying pressure is 5-10 MPa. The shorter spraying time is favorable for avoiding corrosion of the metal coating, and the spraying pressure is controlled to be 5-10 MPa, so that enough cleaning force can be ensured to clean the photoresist.
After the second organic solvent is used for spraying the wafer, the wafer can be kept in a centrifugal rotation state, and the sprayed organic solvent is changed into a third organic solvent. Optionally, the third organic solvent is selected from at least one of isopropyl alcohol (IPA), ethanol, and acetone. The third organic solvent serves to dissolve and remove the remaining second organic solvent and the remaining photoresist. It will be appreciated that, since the second organic solvent itself dissolves the photoresist, the photoresist on the wafer cannot be removed without removing the second organic solvent having the photoresist dissolved therein, and NMP in the remaining second organic solvent still corrodes the metal plating layer. The third organic solvent can dissolve the second organic solvent and the photoresist, and the volatility of the third organic solvent is higher than that of the second organic solvent, so that the third organic solvent can not only effectively remove the second organic solvent remained on the wafer, avoid the corrosion of the third organic solvent to the metal coating, but also facilitate the subsequent drying due to the high volatility of the third organic solvent. The third organic solvent does not form a solvent system with NMP that is more corrosive to the metal coating than if deionized water was used to rinse the second organic solvent, thus helping to protect the metal coating from damage.
Optionally, the process of spraying the wafer with the third organic solvent is continued for 5-20 s, and the spraying pressure is 0.1-0.2 MPa. Since the third organic solvent is used to remove the remaining second organic solvent (with a small amount of photoresist dissolved), this can be accomplished in a short time and at a low pressure.
Step S400, drying the wafer.
In the embodiment of the application, after stopping spraying, the drying gas can be continuously introduced into the chamber (such as a spraying chamber) where the wafer is located, and the temperature of the drying gas is 50-75 ℃. Optionally, the drying gas is nitrogen. In other embodiments, inert gases such as argon, helium, etc. may also be used. And in the drying process, the third organic solvent is thoroughly volatilized, and the dried wafer is obtained.
Optionally, during the drying process, the wafer still keeps rotating, for example, at a rotational speed of 800-1000 r/min. The drying time should be based on the principle of thoroughly drying the wafer. Optionally, the pressure of the drying gas is 0.1-0.2 MPa during drying.
The features and capabilities of the present application are described in further detail below in connection with the examples. The plating on the wafer in various embodiments includes a copper layer and an aluminum layer.
Example 1
And (3) placing the coated wafer in an oven for annealing treatment, wherein the annealing heat preservation temperature is 180 ℃, the heat preservation time is 6 hours, the heating rate is 10 ℃ per minute, and the cooling rate is 5 ℃ per minute. The annealed wafer was left to stand in DMSO (as a first organic solvent) for 30min to soften the photoresist. The wafer was placed in a rinse tank, the wafer was rotated at a rotational speed of 1000r/min, and NMP (as a second organic solvent) was used to spray the front and back surfaces of the wafer for 300 seconds at a spray pressure of 8MPa. Thereafter, the wafer was rotated and sprayed with IPA (as a third organic solvent) to the front and back surfaces of the wafer for 15 seconds at a spray pressure of 0.15MPa. And after stopping spraying, continuously introducing 70 ℃ nitrogen into the spraying chamber, wherein the pressure is 0.15MPa, and until the wafer is dried.
Example 2
And (3) placing the coated wafer in an oven for annealing treatment, wherein the annealing heat preservation temperature is 160 ℃, the heat preservation time is 8 hours, the heating rate is 12 ℃ per minute, and the cooling rate is 6 ℃ per minute. The annealed wafer was left to stand in dimethylformamide (as the first organic solvent) and immersed for 10min to soften the photoresist. The wafer was placed in a rinse tank, the wafer was rotated at 800r/min, and NMP (as a second organic solvent) was used to spray the front and back surfaces of the wafer for 350s at a spray pressure of 10MPa. Thereafter, the wafer was rotated and sprayed with IPA (as a third organic solvent) to the front and back surfaces of the wafer for 20 seconds at a spray pressure of 0.2MPa. And after stopping spraying, continuously introducing 75 ℃ nitrogen into the spraying chamber, wherein the pressure is 0.2MPa, and until the wafer is dried.
Example 3
And (3) placing the coated wafer in an oven for annealing treatment, wherein the annealing heat preservation temperature is 200 ℃, the heat preservation time is 3 hours, the heating rate is 8 ℃ per minute, and the cooling rate is 3 ℃ per minute. The annealed wafer was left to stand in DMSO (as a first organic solvent) for 20min to soften the photoresist. The wafer was placed in a rinse tank, the wafer was rotated at 900r/min, and NMP (as a second organic solvent) was used to spray the front and back surfaces of the wafer, the NMP spraying time was 330s, and the spraying pressure was 6MPa. And then the wafer is kept rotating, ethanol (used as a third organic solvent) is used for spraying to the front and the back of the wafer, the spraying time of the ethanol is 5s, and the spraying pressure is 0.1MPa. And after stopping spraying, continuously introducing 60 ℃ nitrogen into the spraying chamber, wherein the pressure is 0.1MPa, and until the wafer is dried.
Example 4
And (3) placing the coated wafer in an oven for annealing treatment, wherein the annealing heat preservation temperature is 170 ℃, the heat preservation time is 4 hours, the heating rate is 9 ℃ per minute, and the cooling rate is 4 ℃ per minute. The annealed wafer was left to stand in DMSO (as a first organic solvent) for 60min to soften the photoresist. The wafer was placed in a rinse tank, the wafer was rotated at 800r/min, and NMP (as a second organic solvent) was used to spray the front and back surfaces of the wafer for 300 seconds at a spray pressure of 5MPa. And then the wafer is kept rotating, acetone (used as a third organic solvent) is used for spraying to the front and the back of the wafer, the spraying time of the acetone is 10s, and the spraying pressure is 0.15MPa. And after stopping spraying, continuously introducing 50 ℃ nitrogen into the spraying chamber, wherein the pressure is 0.2MPa, and until the wafer is dried.
Comparative example 1
The only difference compared to example 1 is that the wafer was not annealed.
Fig. 2 is a scanning electron micrograph of a metal plating layer of a wafer obtained in example 1 of the present application. As shown in fig. 2, when the cross section of the metal plating layer is observed by a scanning electron microscope, it is seen that after annealing, strong alloying occurs between the copper layer and the aluminum layer, and copper atoms migrate to the aluminum layer, so that intermetallic compounds are generated, and corrosion can be effectively resisted. Fig. 3 is a surface microscopic image of a wafer obtained in example 1 of the present application, wherein the dark color is a metal plating layer, and the surface smoothness of the metal plating layer is high, and no obvious corrosion and photoresist residue are observed. Fig. 4 is a surface microscopic image of a wafer obtained in comparative example 1 of the present application. As can be seen from fig. 4, there is a copper corrosion condition in a partial region (circled region in fig. 4).
The embodiment of the application provides a photoresist stripping method which can be applied to a process for manufacturing a surface acoustic wave filter, wherein a metal plating layer is used for forming an interdigital electrode (IDT) of the surface acoustic wave filter. When the surface acoustic wave filter operates, the piezoelectric effect causes the IDT to vibrate at a certain frequency, and the IDT in which copper corrosion occurs is broken due to quality and continuity, so that the vibration mode thereof is changed, thereby affecting the performance of the surface acoustic wave filter.
Fig. 5 is a graph showing the probe test of the wafer obtained in example 1 of the present application, and fig. 6 is a graph showing the probe test of the wafer obtained in comparative example 1 of the present application. As shown in fig. 5 and fig. 6, in the test result of the wafer obtained by the process method of the embodiment, the passband is not collapsed, and the insertion loss is normal. However, the wafer in comparative example 1 affects the vibration of IDT due to copper corrosion, resulting in failure of piezoelectric effect, collapse of pass bands of RX and TX, and failure of the whole device due to failure of effective filtering of frequencies in pass bands.
In summary, the application provides a photoresist stripping method, which comprises annealing a wafer to alloy a metal coating, soaking the wafer in a first organic solvent to soften the photoresist on the wafer, spraying the wafer with a second organic solvent and a third organic solvent sequentially, wherein the second organic solvent contains N-methylpyrrolidone, the third organic solvent has higher volatility than the second organic solvent, and drying the wafer. In the photoresist stripping method provided by the application, the metal coating is alloyed by the annealing process, so that two different metals (such as copper and aluminum) in the metal coating can form intermetallic compounds, the corrosion of an organic solvent can be effectively resisted, and the corrosion damage of the metal coating is reduced. Furthermore, after annealing, the wafer is soaked by the first organic solvent to soften the photoresist, and meanwhile, the photoresist can be roughened due to partial dissolution, so that the surface area is larger, the soaked photoresist is easier to dissolve and remove in the spraying process, the spraying duration is shortened, and the corrosion of N-methylpyrrolidone (NMP) to a metal coating in the spraying process is reduced. The spraying process comprises spraying by using a second organic solvent, wherein the second organic solvent contains NMP, and the spraying process is characterized in that the photoresist can be effectively dissolved and removed, and the cost is low. The spraying process further comprises the step of spraying the wafer by using a third organic solvent, wherein the third organic solvent has higher volatility than the second organic solvent, so that the second organic solvent remained on the wafer can be effectively removed by using the third organic solvent, the corrosion of the third organic solvent to the metal coating is avoided, and meanwhile, the subsequent drying is facilitated due to the high volatility of the third organic solvent. Therefore, by the photoresist stripping method, the photoresist on the wafer can be effectively removed, and simultaneously, the corrosion of NMP to the metal coating can be relieved, so that the yield of the product can be improved.
The above is only a preferred embodiment of the present application, and is not intended to limit the present application, but various modifications and variations can be made to the present application by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application should be included in the protection scope of the present application.
Claims (10)
1. A photoresist stripping method for stripping photoresist on a wafer, the wafer having a metal plating layer and the photoresist, the material of the metal plating layer comprising at least two metals including a transition metal, the photoresist stripping method comprising:
annealing the wafer to alloy the metal coating;
Soaking the wafer in a first organic solvent to soften the photoresist on the wafer;
Spraying the wafer by sequentially using a second organic solvent and a third organic solvent, wherein the second organic solvent comprises N-methylpyrrolidone, and the third organic solvent has higher volatility than the second organic solvent;
And drying the wafer.
2. The photoresist stripping method according to claim 1, wherein the annealing is performed at a holding temperature of 160-200 ℃ for 3-8 hours.
3. The photoresist stripping method according to claim 1, wherein the annealing has a heating rate of 8-12 ℃ per minute and a cooling rate of 3-6 ℃ per minute.
4. The photoresist stripping method according to claim 1, wherein the first organic solvent is selected from at least one of dimethyl sulfoxide and dimethylformamide.
5. The photoresist stripping method according to claim 1, wherein the third organic solvent is selected from at least one of isopropanol, ethanol and acetone.
6. The photoresist stripping method according to any one of claims 1 to 5, wherein the wafer is controlled to rotate at a rotational speed of 800 to 1000r/min during the process of spraying and drying the wafer.
7. The photoresist stripping method according to any one of claims 1 to 5, wherein the process of spraying the wafer with the second organic solvent is continued for 300 to 350 seconds at a pressure of 5 to 10mpa.
8. The photoresist stripping method according to any one of claims 1 to 5, wherein the process of spraying the wafer with the third organic solvent is continued for 5 to 20 seconds at a pressure of 0.1 to 0.2mpa.
9. The photoresist stripping method according to any one of claims 1 to 5, wherein the step of baking the wafer comprises:
And continuously introducing drying gas into a chamber where the wafer is located, wherein the temperature of the drying gas is 50-75 ℃.
10. The photoresist stripping method according to claim 9, wherein the baking gas is nitrogen.
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