CN115097703A

CN115097703A - Photoresist cleaning solution and preparation method and cleaning method thereof

Info

Publication number: CN115097703A
Application number: CN202210737821.8A
Authority: CN
Inventors: 杜秀彤; 张恺
Original assignee: Beijing U Precision Tech Co Ltd
Current assignee: Beijing Youwei Precision Measurement And Control Technology Research Co ltd; Beijing U Precision Tech Co Ltd
Priority date: 2022-06-27
Filing date: 2022-06-27
Publication date: 2022-09-23
Also published as: WO2024000740A1

Abstract

The application discloses a photoresist cleaning solution, a preparation method thereof and a cleaning method, and belongs to the technical field of photoresist cleaning. A photoresist cleaning solution, comprising: cleaning agents, metal corrosion inhibitors and water; wherein the cleaning agent comprises a first cleaning agent and/or a second cleaning agent; the first cleaning agent comprises a pyrrolidone compound, the second cleaning agent comprises alkyl ammonium hydroxide, and the metal corrosion inhibitor comprises benzotriazole and derivatives thereof. The method can thoroughly remove the photoresist without corroding the metal film, especially the chromium film, can realize repeated gluing utilization of the chromium-plated substrate, and has remarkable economic benefit.

Description

Photoresist cleaning solution and preparation method and cleaning method thereof

Technical Field

The application belongs to the technical field of photoresist cleaning, and particularly relates to a photoresist cleaning solution, and a preparation method and a cleaning method thereof.

Background

In the field of semiconductor manufacturing, a photolithography process is commonly used. The photolithography process is a technique for fabricating a micro-nano pattern on a photoresist layer by exposure and development, and is commonly used for fabricating a photoresist mask. In order to obtain a satisfactory product, it is usually necessary to plate a metal film on the surface of the photoresist mask substrate, for example, a chrome-plated substrate is usually used in the chip and grating manufacturing process.

When the photoresist layer or the photoresist mask pattern does not meet the technical requirements, the original photoresist layer needs to be removed by using a cleaning solution so as to carry out secondary gluing. Alternatively, after a resist mask is formed and exposed, pattern transfer is performed, and after a desired pattern is obtained, the remaining resist needs to be stripped off with a cleaning solution. It is noted that it is necessary to avoid damage to the metal film during the process of removing the photoresist.

At present, a photoresist cleaning solution mainly comprises a polar organic solvent, a strong base, deionized water and the like, and removes the photoresist on the surface of a substrate in a soaking or rinsing manner. However, the conventional photoresist cleaning solution has a general cleaning effect on the photoresist, is likely to corrode a metal base material or a metal film, and has a high damage on the metal base material or the metal film.

Therefore, the photoresist cleaning solution and the method for cleaning the same in the related art need to be improved in terms of metal corrosion.

Disclosure of Invention

In view of the above-mentioned problems, the present invention is directed to solving, at least to some extent, one of the technical problems in the related art. Therefore, the invention provides the photoresist cleaning solution, and the preparation method and the cleaning method thereof, which can improve the cleaning effect on the photoresist, avoid or reduce the corrosion on a metal film and overcome the defects in the prior art.

In order to solve the technical problem, the present application is implemented as follows:

according to an aspect of the present application, embodiments of the present application provide a photoresist cleaning solution, including: cleaning agents, metal corrosion inhibitors and water; wherein the cleaning agent comprises a first cleaning agent and/or a second cleaning agent;

the first cleaning agent comprises a pyrrolidone compound, the second cleaning agent comprises alkyl ammonium hydroxide, and the metal corrosion inhibitor comprises benzotriazole and derivatives thereof.

In some embodiments thereof, the photoresist cleaning solution comprises a first photoresist cleaning solution and a second photoresist cleaning solution;

the first photoresist cleaning solution includes: the first cleaning agent, the metal corrosion inhibitor and water;

the second photoresist cleaning solution includes: the second cleaning agent, the metal corrosion inhibitor and water.

In some embodiments, the first photoresist cleaning solution comprises the following components in percentage by mass: 45-95% of first cleaning agent, 0.01-10% of metal corrosion inhibitor and the balance of water;

and/or the second photoresist cleaning solution comprises the following components in percentage by mass: 50 to 95 percent of second cleaning agent, 0.01 to 10 percent of metal corrosion inhibitor and the balance of water.

In some embodiments, the first photoresist cleaning solution comprises the following components in percentage by mass: 60 to 95 percent of first cleaning agent, 0.01 to 5 percent of metal corrosion inhibitor and the balance of water;

and/or the second photoresist cleaning solution comprises the following components in percentage by mass: 60 to 95 percent of second cleaning agent, 0.01 to 5 percent of metal corrosion inhibitor and the balance of water.

In some embodiments, the photoresist cleaning solution comprises the following components in percentage by mass: 35 to 55 percent of first cleaning agent, 20 to 40 percent of second cleaning agent, 0.01 to 10 percent of metal corrosion inhibitor and the balance of water.

In some embodiments, the pyrrolidone-based compound includes at least one of N-methylpyrrolidone, N-ethylpyrrolidone, N-hydroxyethylpyrrolidone, N-propylpyrrolidone, N-butylpyrrolidone, or N-cyclohexylpyrrolidone;

and/or the alkyl ammonium hydroxide comprises at least one of tetramethyl ammonium hydroxide, tetraethyl ammonium hydroxide, tetrapropyl ammonium hydroxide, tetrabutyl ammonium hydroxide, methyltriethyl ammonium hydroxide, benzyltrimethyl ammonium hydroxide, or benzyltriethylammonium hydroxide;

and/or the benzotriazole and the derivative thereof comprise at least one of benzotriazole, hydroxy benzotriazole, alkyl benzotriazole or carboxyl benzotriazole.

According to another aspect of the present application, there is also provided a method for preparing the photoresist cleaning solution, the method comprising: and uniformly mixing a cleaning agent, a metal corrosion inhibitor and water to obtain the photoresist cleaning solution.

In some embodiments thereof, the method of making comprises:

uniformly mixing a first cleaning agent, a metal corrosion inhibitor and water to obtain a first photoresist cleaning solution;

and uniformly mixing the second cleaning agent, the metal corrosion inhibitor and water to obtain a second photoresist cleaning solution.

According to still another aspect of the present application, there is also provided a cleaning method for cleaning a photoresist using the photoresist cleaning solution as described above, the photoresist cleaning solution including a first photoresist cleaning solution and a second photoresist cleaning solution, the cleaning method including:

(a) placing the device to be cleaned containing the photoresist in a second photoresist cleaning solution for soaking and cleaning;

(b) washing the device to be cleaned in the step (a) with water;

(c) placing the device to be cleaned after being washed in the step (b) in a first photoresist cleaning solution for cleaning;

(d) and (c) washing the to-be-cleaned device cleaned in the step (c) with water, and then drying.

Wherein the temperature range for cleaning by using the second photoresist cleaning solution or the first photoresist cleaning solution is 25-60 ℃;

and/or the time for cleaning by adopting the second photoresist cleaning solution or the first photoresist cleaning solution is 5min-40 min.

In some embodiments, the step (c) specifically comprises:

placing the device to be cleaned washed in the step (b) in a first photoresist cleaning solution, and carrying out ultrasonic cleaning at the temperature of 25-35 ℃ for 5-20 min;

after the ultrasonic cleaning is finished, heating the first photoresist cleaning solution to a preset temperature, and soaking and cleaning the first photoresist cleaning solution, wherein the preset temperature is 45-55 ℃, and the soaking and cleaning time is 5-20 min;

and/or, the step (d) specifically comprises:

washing the device to be cleaned in the step (c) with water, then ultrasonically cleaning the device with an alcohol solvent, and then washing the device with water; wherein the temperature of ultrasonic cleaning is 25-35 ℃, and the time of ultrasonic cleaning is 15-30 min;

then drying by nitrogen blow-drying and hot-plate drying.

The embodiment of the application also provides a cleaning method for cleaning photoresist by using the photoresist cleaning solution, wherein the photoresist cleaning solution comprises a first cleaning agent, a second cleaning agent, a metal corrosion inhibitor and water; the cleaning method comprises the following steps:

(a) mixing a first cleaning agent, a second cleaning agent, a metal corrosion inhibitor and water to obtain a photoresist cleaning solution, and placing a device to be cleaned containing photoresist in the photoresist cleaning solution for ultrasonic cleaning;

(b) washing the device to be washed in the step (a) with water;

(c) placing the device to be cleaned washed in the step (b) in an alcohol solvent for ultrasonic cleaning;

The technical scheme of the invention at least has the following beneficial effects:

in the embodiment of the application, the provided photoresist cleaning solution comprises a first cleaning agent and/or a second cleaning agent, a metal corrosion inhibitor and water, wherein the first cleaning agent comprises a pyrrolidone compound, the second cleaning agent comprises alkyl ammonium hydroxide, and the metal corrosion inhibitor comprises benzotriazole and derivatives thereof. Therefore, the photoresist on the surface of the substrate can be effectively removed by using one or more of the pyrrolidone compounds and the alkyl ammonium hydroxide, and a protective film can be formed on the surface of the metal by using the benzotriazole and the benzotriazole derivatives as metal corrosion inhibitors, so that the corrosion of the cleaning agent to the metal film is inhibited, and the corrosion to the chromium film is preferably inhibited. Therefore, the photoresist cleaning solution can thoroughly remove the photoresist without corroding a metal film, more preferably without corroding a chromium film, and can realize repeated gluing and utilization of the chromium-plated substrate.

The preparation method of the photoresist cleaning solution provided by the embodiment of the invention is simple, easy to implement and easy to operate, and only needs to uniformly mix all the raw material components. The cleaning method of the photoresist cleaning solution provided by the embodiment of the invention can completely remove the photoresist on the surface of the substrate and does not corrode the metal film on the surface of the substrate, and the metal film comprises the metal chromium film, so that the repeated gluing utilization of the chromium-plated substrate can be realized, and the cleaning method has obvious economic benefit.

Drawings

FIG. 1 is a schematic flow diagram of a method for cleaning a photoresist cleaning solution according to some exemplary embodiments of the present application;

FIG. 2 is a schematic flow diagram of a method for cleaning a photoresist cleaning solution according to still other exemplary embodiments of the present application;

FIG. 3 is a photograph showing the results of cleaning a photoresist on the surface of a chrome-plated substrate with the photoresist cleaning solution provided in example 1 of the present application;

FIG. 4 is a photograph showing the result of cleaning a resist on the surface of a chromium plated substrate with the resist cleaning solution provided in comparative example 1;

FIG. 5 is a 100 times optical microscope image of the surface topography of the marked part of FIG. 3;

FIG. 6 is a 100 times optical microscope image of the surface topography of the marked part of FIG. 4.

Detailed Description

The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application, and it is obvious that the described embodiments are some, but not all, embodiments of the present application. All other embodiments obtained by a person of ordinary skill in the art based on the embodiments in the present application without making any creative effort belong to the protection scope of the present application. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer.

The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For numerical ranges, one or more new numerical ranges may be obtained by combining the individual values, or by combining the individual values.

It should be noted that the term "and/or"/"used herein is only one kind of association relationship describing associated objects, and means that there may be three relationships, for example, a and/or B, and may mean: a exists alone, A and B exist simultaneously, and B exists alone. As used in the examples of this application and the appended claims, the singular forms "a", "an", and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise.

In the description of the present application, use of the term "at least one of," "at least one of," or other similar terms to connect lists of items may imply any combination of the listed items. For example, if item A, B is listed, the phrase "at least one of A, B" means only a; only B; or A and B. In another example, if the items A, B, C are listed, the phrase "at least one of A, B, C" means a only; or only B; only C; a and B (excluding C); a and C (excluding B); b and C (excluding A); or A, B and all of C. Item a may comprise a single element or multiple elements. Item B may comprise a single element or multiple elements. Item C may comprise a single element or multiple elements.

Those skilled in the art understand that, as background art suggests, existing photoresist cleaning solutions still suffer from more or less drawbacks and there is still a need for improvement. For example, chinese patent CN105527803A discloses a cleaning solution containing water, alcohol amine, alcohol ether, pyrogallol and its derivatives and C3-C6 polyol, and the cleaning solution does not contain fluoride, hydroxylamine, cyclic amine and quaternary amine hydroxide; however, after repeated cleaning for many times with this cleaning liquid, the metal chromium is highly corrosive. For another example, japanese patent JP1998239865 discloses an alkaline cleaning solution composed of tetramethylammonium hydroxide, dimethyl sulfoxide, 1, 3-dimethyl-2-imidazolidinone, water and the like, which is also corrosive to a metal film and cannot completely remove a photoresist on a substrate. Therefore, how to make the photoresist cleaning solution have good photoresist removing capability and reduce or avoid corrosion to the metal film becomes a problem which is urgently needed to be solved by the industry.

Based on this, the technical scheme of the embodiment of the application provides the photoresist cleaning solution, the preparation method thereof and the cleaning method thereof, which can effectively inhibit corrosion to the metal film and effectively improve the photoresist removal capability, so that the problems of poor cleaning effect and large damage to the metal film of the photoresist cleaning solution in the related art can be solved, and the yield of devices can be improved. See below for a description of specific embodiments.

In some embodiments of the present application, there is provided a photoresist cleaning solution, including: cleaning agents, metal corrosion inhibitors and water; wherein the cleaning agent comprises a first cleaning agent and/or a second cleaning agent;

According to the technical scheme provided by the embodiment of the invention, due to the special composition of the photoresist cleaning solution, the photoresist on the surface of the substrate can be completely removed, the removal capability of the photoresist is improved, the metal film on the surface of the substrate is not corroded, and particularly, the effect of inhibiting the corrosion of the metal chromium film is more remarkable. The inventors have analyzed based on this phenomenon and considered that it is possible to: according to the photoresist cleaning solution, through the mutual synergistic cooperation of a proper and appropriate amount of pyrrolidone compounds and/or alkyl ammonium hydroxide, benzotriazole and derivatives thereof and water, under the mutual restriction and collocation of the functions, the support and the proportion of the raw material components, the photoresist removing capability of the photoresist cleaning solution is improved, the photoresist cleaning effect is strong, meanwhile, the damage of the photoresist cleaning solution to a metal film such as a metal chromium film is low, and the problems of poor cleaning effect and large damage to the metal film of the photoresist cleaning solution in the prior art are effectively solved.

It is understood that the cleaning agent comprises a first cleaning agent and/or a second cleaning agent, meaning that the cleaning agent may be the first cleaning agent, the second cleaning agent, or both the first cleaning agent and the second cleaning agent.

The first cleaning agent or the second cleaning agent in the photoresist cleaning solution can be used for removing the photoresist on the surface of the substrate; and a mixture of the first cleaning agent and the second cleaning agent may also be used to remove the photoresist on the surface of the substrate. Thus, the photoresist cleaning solution may be composed of one or more of the first cleaning agent and the second cleaning agent, the metal corrosion inhibitor, and water. Specifically, in some cases, the photoresist cleaning solution may be composed of a first cleaning agent, a metal corrosion inhibitor, and water. In other cases, the photoresist cleaning solution is comprised of a second cleaning agent, a metal corrosion inhibitor, and water. In still other cases, the photoresist cleaning solution is comprised of a first cleaning agent, a second cleaning agent, a metal corrosion inhibitor, and water.

According to the embodiment of the application, the metal corrosion inhibitor is selected from benzotriazole and derivatives thereof, and because two N heteroatoms in the benzotriazole and the derivatives thereof can generate weak interaction with metal atoms, the metal corrosion inhibitor is more favorable for adsorption and coordination on the surface of a metal material, so that the metal material is favorably prevented from corrosion, and a metal film is effectively protected. Namely, benzotriazole and derivatives thereof are used as corrosion inhibitors, so that a compact protective film can be formed on the surface of metal, and the corrosion of the cleaning agent to the metal film is inhibited, thereby reducing or avoiding the damage of the photoresist cleaning solution to the metal film. And the benzotriazole and the derivative thereof have good compatibility with pyrrolidone compounds and alkyl ammonium hydroxide, are easy to prepare, are beneficial to improving the stability of a system, have good anti-corrosion effect and are easy to prepare, so that the benzotriazole and the derivative thereof are preferably selected as corrosion inhibitors. In addition, benzotriazole and derivatives thereof can play a role in corrosion prevention on various metals (such as metal copper, metal chromium and the like), particularly can inhibit corrosion on a metal chromium film, and realize repeated glue coating utilization of a chromium-plated substrate for many times.

According to the embodiment of the application, the first cleaning agent is selected from pyrrolidone compounds, and the second cleaning agent is selected from alkyl ammonium hydroxide. The alkyl ammonium hydroxide can be used for decomposing a polymer chain segment in the photoresist, dissolving the photoresist and improving the cleaning effect on the photoresist. The pyrrolidone compound can fully dissolve and uniformly mix all components in the cleaning solution, can dissolve the photoresist when being applied to cleaning of the photoresist, and has certain photoresist removal capacity. The pyrrolidone compound can assist alkyl ammonium hydroxide, and the alkyl ammonium hydroxide and the pyrrolidone compound are cooperated to further improve the cleaning effect of the photoresist.

It should be noted that, the embodiment of the present invention has no limitation on the source of the raw material of the photoresist cleaning solution, and those skilled in the art can flexibly select the raw material according to the actual requirement as long as the purpose of the present invention is not limited. Such as pyrrolidones, alkylammonium hydroxides and benzotriazoles and derivatives thereof, are commercially available or may be prepared by themselves in accordance with methods known in the relevant art.

In some embodiments, the photoresist rinse or water used in the preparation of the photoresist rinse may be deionized water.

In some embodiments, the photoresist cleaning solution includes a first photoresist cleaning solution and a second photoresist cleaning solution;

In order to improve the cleaning effect of the photoresist cleaning solution and to more thoroughly remove the photoresist during cleaning, the photoresist cleaning solution is divided into a first photoresist cleaning solution and a second photoresist cleaning solution. Therefore, the first photoresist cleaning solution and the second photoresist cleaning solution are respectively utilized to clean the device to be cleaned for multiple times through the matching of the first photoresist cleaning solution and the second photoresist cleaning solution, so that the cleaning effect of the photoresist can be improved, the photoresist on the surface of the substrate can be completely removed, the corrosion to the metal film can be avoided during cleaning, and the damage to the metal film is reduced.

In some embodiments, the first photoresist cleaning solution comprises the following components in percentage by mass: 45-95% of first cleaning agent, 0.01-10% of metal corrosion inhibitor and the balance of water. In some embodiments, the first photoresist cleaning solution comprises the following components in percentage by mass: 60 to 90 percent of first cleaning agent, 0.01 to 5 percent of metal corrosion inhibitor and the balance of water. Preferably, in some embodiments, the first photoresist cleaning solution comprises the following components in percentage by mass: 45% -90% of first cleaning agent, 0.01% -3% of metal corrosion inhibitor and 7% -54.99% of water. The total mass percentage of the first cleaning agent, the metal corrosion inhibitor and the water is 100 percent.

Specifically, in the first photoresist cleaning solution, the content of the first cleaning agent is 45 to 95 percent by mass, further 60 to 95 percent by mass, and further 60 to 90 percent by mass; typically but not by way of limitation, for example, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, and any two of these values may be included in the range. In the first photoresist cleaning solution, the content of the metal corrosion inhibitor is 0.01 to 10 percent by mass, further 0.01 to 5 percent by mass, and further 0.01 to 3 percent by mass; typical but non-limiting examples are 0.01%, 0.05%, 0.1%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 5%, 6%, 8%, 10%, and any value within the range of any two of these values.

Herein, percentages, ratios or parts referred to are by mass unless otherwise indicated. For example, the first cleaning agent may be 45% to 95%, which may be expressed as 45% to 95% by weight or 45% to 95% by mass of the first cleaning agent. Herein, the percentages (%) refer to the mass percentage relative to the composition, unless otherwise specified. For example, the first photoresist cleaning solution includes the following components in percentage by mass: 45 to 95 percent of first cleaning agent, 0.01 to 10 percent of metal corrosion inhibitor and the balance of water, based on the total mass of the components in the first photoresist cleaning solution, wherein the sum of the contents of the components is 100 percent.

In some embodiments, the second photoresist cleaning solution comprises the following components in percentage by mass: 50 to 95 percent of second cleaning agent, 0.01 to 10 percent of metal corrosion inhibitor and the balance of water. In some embodiments, the second photoresist cleaning solution comprises the following components in percentage by mass: 60 to 95 percent of second cleaning agent, 0.01 to 5 percent of metal corrosion inhibitor and the balance of water. Preferably, in some embodiments, the second photoresist cleaning solution comprises the following components in percentage by mass: 65-90% of second cleaning agent, 0.01-3% of metal corrosion inhibitor and 7-34.99% of water. The total mass percentage of the second cleaning agent, the metal corrosion inhibitor and the water is 100 percent.

Specifically, in the second photoresist cleaning solution, the content of the second cleaning agent is 60% to 95% by mass, further 65% to 90% by mass, and further 68% to 88% by mass; exemplary but non-limiting examples are 60%, 62%, 65%, 68%, 70%, 72%, 75%, 78%, 80%, 85%, 88%, 90%, 95%, and any value in the range of any two of these points. In the second photoresist cleaning solution, the content of the metal corrosion inhibitor is 0.01 to 10 percent by mass, further 0.01 to 5 percent by mass, and further 0.01 to 3 percent by mass; typical but non-limiting examples are 0.01%, 0.05%, 0.1%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 5%, 6%, 8%, 10%, and any value within the range of any two of these points.

According to some embodiments of the present invention, the photoresist cleaning solution includes a first photoresist cleaning solution and a second photoresist cleaning solution, and the first photoresist cleaning solution and the second photoresist cleaning solution cooperate with other components by adjusting the kind and ratio of each raw material component, and the contribution of each component to the performance index of the photoresist cleaning solution, such as cleaning effect, anti-corrosion effect or the cooperativity of the whole system, is comprehensively considered, and by making each component within the above range, the prepared photoresist cleaning solution can be stable in performance, good in photoresist cleaning effect and strong in anti-corrosion effect. Furthermore, the contents of all components in the photoresist cleaning solution are reasonably adjusted and optimized to be within an optimal range, so that the synergistic cooperation effect among all the components is fully exerted, the comprehensive performance of the photoresist cleaning solution is further improved, and the production cost of the cleaning solution is reduced.

As previously described, in some cases, the photoresist rinse may be composed of a first photoresist rinse including a first rinsing agent, a metal corrosion inhibitor and water and a second photoresist rinse including a second rinsing agent, a metal corrosion inhibitor and water. In other cases, the photoresist cleaning solution can also be composed of a first cleaning agent, a second cleaning agent, a metal corrosion inhibitor, and water. Specifically, in some embodiments, the photoresist cleaning solution comprises the following components in percentage by mass: 35 to 55 percent of first cleaning agent, 20 to 40 percent of second cleaning agent, 0.01 to 10 percent of metal corrosion inhibitor and the balance of water. Preferably, in some embodiments, the photoresist cleaning solution comprises the following components in percentage by mass: 40-50% of first cleaning agent, 25-35% of second cleaning agent, 0.01-3% of metal corrosion inhibitor and the balance of water.

The specific types of the pyrrolidone type compounds can be diversified under the condition of satisfying the requirements of improving the cleaning effect of the photoresist cleaning solution and the like. In order to optimize the cleaning effect of the photoresist cleaning solution, in some embodiments, the pyrrolidone-based compound includes at least one of N-methylpyrrolidone, N-ethylpyrrolidone, N-hydroxyethylpyrrolidone, N-propylpyrrolidone, N-butylpyrrolidone, or N-cyclohexylpyrrolidone. Preferably, in some embodiments, the pyrrolidone-based compound includes at least one of N-methylpyrrolidone, N-ethylpyrrolidone, or N-hydroxyethylpyrrolidone. The pyrrolidone type compound can be N-methyl pyrrolidone, N-ethyl pyrrolidone, N-hydroxyethyl pyrrolidone, or a mixture of any two or more of the above compounds in any proportion.

In addition, in other embodiments, the pyrrolidone-based compound is not limited to the above-mentioned ones, and other types of pyrrolidone-based compounds can be used in the case of satisfying the requirement of improving the cleaning effect of the photoresist cleaning solution, and the like, and will not be described in detail.

The specific type of the alkyl ammonium hydroxide may be various under the condition that the requirements for improving the cleaning effect of the photoresist cleaning solution and the like are satisfied. To optimize the cleaning effect of the photoresist cleaning solution, in some embodiments, the alkyl ammonium hydroxide includes at least one of tetramethyl ammonium hydroxide, tetraethyl ammonium hydroxide, tetrapropyl ammonium hydroxide, tetrabutyl ammonium hydroxide, methyltriethyl ammonium hydroxide, benzyltrimethyl ammonium hydroxide, or benzyltriethylammonium hydroxide. Preferably, in some embodiments, the alkyl ammonium hydroxide comprises at least one of tetramethyl ammonium hydroxide, tetraethyl ammonium hydroxide, tetrapropyl ammonium hydroxide, or tetrabutyl ammonium hydroxide. Illustratively, the alkyl ammonium hydroxide may be tetramethyl ammonium hydroxide, may be tetraethyl ammonium hydroxide, may be tetrapropyl ammonium hydroxide, may be tetrabutyl ammonium hydroxide, or may be a mixture of any two or more of the above alkyl ammonium hydroxides in any ratio.

The specific types of benzotriazole and its derivatives can be varied under the conditions of satisfying the requirements of improving the cleaning effect of the photoresist cleaning solution, reducing the damage to the metal film, and the like. In order to optimize the corrosion prevention effect of the photoresist cleaning solution, in some embodiments, the benzotriazole and the derivative thereof include at least one of benzotriazole, hydroxybenzotriazole, alkylbenzotriazol, or carboxybenzotriazol. Preferably, in some embodiments, the benzotriazole and derivatives thereof include benzotriazole or hydroxy benzotriazole.

In summary, as an example, the photoresist cleaning solution provided by the embodiments of the present invention may include a first photoresist cleaning solution and a second photoresist cleaning solution, wherein the first photoresist cleaning solution includes the following components by mass percent: 45% -90% of a first cleaning agent, 0.01% -3% of a metal corrosion inhibitor and 7% -54.99% of water; the second photoresist cleaning solution comprises the following components in percentage by mass: 65% -90% of second cleaning agent, 0.01% -3% of metal corrosion inhibitor and 7% -34.99% of water. The pyrrolidone compound is selected from one or more of N-methyl pyrrolidone, N-ethyl pyrrolidone or N-hydroxyethyl pyrrolidone; the alkyl ammonium hydroxide is selected from one or more of tetramethyl ammonium hydroxide, tetraethyl ammonium hydroxide, tetrapropyl ammonium hydroxide or tetrabutyl ammonium hydroxide.

As another example, the photoresist cleaning solution provided by the embodiment of the present invention includes the following components by mass: 40-50% of first cleaning agent, 25-35% of second cleaning agent, 0.01-3% of metal corrosion inhibitor and 22-24.99% of water. The pyrrolidone compound is selected from one or more of N-methyl pyrrolidone, N-ethyl pyrrolidone or N-hydroxyethyl pyrrolidone; the alkyl ammonium hydroxide is selected from one or more of tetramethyl ammonium hydroxide, tetraethyl ammonium hydroxide, tetrapropyl ammonium hydroxide or tetrabutyl ammonium hydroxide.

In some embodiments, the present application also provides a method of preparing the photoresist cleaning solution as described above, the method comprising: and uniformly mixing a cleaning agent, a metal corrosion inhibitor and water to obtain the photoresist cleaning solution.

The preparation method of the photoresist cleaning solution can be used for uniformly mixing the components with proper content, has simple process and easy operation, and is suitable for industrial mass production.

In some embodiments, the method of making comprises:

Wherein, the temperature of the mixing can be room temperature.

In some embodiments, the present application also provides a cleaning method for cleaning a photoresist using the photoresist cleaning solution as described above, the cleaning method including:

the use temperature range of the photoresist cleaning solution can be 25-60 ℃; further, the use temperature range of the photoresist cleaning solution can be 25-50 ℃;

and/or the time for cleaning by using the photoresist cleaning solution can be 5min-40 min; further, the time for cleaning by using the photoresist cleaning solution may be 10min to 30 min.

Referring to fig. 1, in some embodiments, the photoresist cleaning solution includes a first photoresist cleaning solution and a second photoresist cleaning solution, and the cleaning method includes:

(b) washing the device to be cleaned in the step (a) with water;

(c) placing the device to be cleaned washed in the step (b) in a first photoresist cleaning solution for cleaning;

In some embodiments, in the step (a), the soaking and cleaning may be performed at normal temperature, and the cleaning time may be 5min to 20min, and further may be 10 min.

In some embodiments, in the step (b), the device to be cleaned may be repeatedly rinsed with deionized water for several times, the number of rinsing may be 10 to 15 times, and the rinsing time may be 8min to 15min, and further may be 10 min.

In some embodiments, the step (c) specifically comprises:

after the ultrasonic cleaning is finished, heating the first photoresist cleaning solution to a preset temperature, and performing soaking cleaning, wherein the preset temperature is 45-55 ℃, and the soaking cleaning time is 5-20 min.

In some embodiments, the step (d) specifically comprises:

then drying by nitrogen blow-drying and hot-plate drying.

In summary, as an example, referring to fig. 2, the photoresist cleaning solution and the cleaning method thereof provided by the embodiment of the present invention have extremely low corrosivity to metal films, and preferably extremely low corrosivity to chromium films, and specifically include the following steps:

adding deionized water into a mixture of a second cleaning agent and a metal corrosion inhibitor to prepare a second photoresist cleaning solution; the second cleaning agent in the second photoresist cleaning solution comprises 65-90% by mass of a second cleaning agent, 0.01-3% by mass of a metal corrosion inhibitor and 7-34.99% by mass of deionized water.

And placing a device to be cleaned (a substrate to be cleaned) in the second photoresist cleaning solution, and soaking and cleaning for a period of time at normal temperature, wherein the period of time can be 5-20 min, and further can be 10 min.

And taking the substrate to be cleaned out of the mixed second photoresist cleaning solution, and repeatedly washing the substrate with deionized water for several times for a period of time, wherein the washing times can be 10-15 times, and the washing time can be 8-15 min, and further can be 10 min.

Adding deionized water into a mixture of the first cleaning agent and the metal corrosion inhibitor to prepare a first photoresist cleaning solution; the first photoresist cleaning solution comprises, by mass, 45% -90% of a first cleaning agent, 0.01% -3% of a metal corrosion inhibitor and 7% -54.99% of deionized water, and is poured into an ultrasonic cleaning tank.

And placing the substrate to be cleaned, which is washed by the deionized water, in a substrate clamping tool, placing the substrate into the first photoresist cleaning solution, and ultrasonically cleaning the substrate at a specified temperature for a period of time, wherein the specified temperature can be 25-35 ℃, further can be 25 ℃, and the period of time can be 5-20 min, further can be 10 min.

After the ultrasonic cleaning is finished, the first photoresist cleaning solution is heated to a predetermined temperature, and is soaked and cleaned for a period of time, wherein the predetermined temperature can be 45-55 ℃, further can be 50 ℃, and the period of time can be 5-20 min, further can be 10 min.

And taking out the substrate which is soaked and cleaned, and repeatedly washing the substrate with deionized water for a plurality of times for a period of time, wherein the washing times can be 10-15 times, the washing time can be 8min-15min, and further the period of time can be 10 min.

And ultrasonically cleaning the substrate washed by the deionized water by using an alcohol solvent such as absolute ethyl alcohol at a specified temperature for a period of time, wherein the specified temperature can be 25-35 ℃, further can be 25 ℃, and the period of time can be 15-30 min, further can be 20 min.

Taking out the substrate subjected to ultrasonic cleaning, and repeatedly washing the substrate with deionized water for several times, wherein the washing times can be 10-15 times, the washing time can be 8min-15min, and further the washing time can be 10 min.

And blowing the residual deionized water on the surface of the substrate by using nitrogen.

And placing the substrate dried by the nitrogen on a hot table for drying for a period of time, wherein the drying time can be 1min-10min, further can be 2min-5min, further can be 2min or 5 min.

In the embodiment of the invention, the temperature for drying the hot plate can be selected to be 50-60 ℃, further can be 55 ℃, and the time can be selected to be 2-5 min, further can be 3 min.

The method for cleaning the photoresist by using the photoresist cleaning solution provided by the embodiment of the invention has an excellent cleaning effect on the photoresist, can completely remove the photoresist on the surface of the substrate, does not corrode a metal film on the surface of the substrate, especially a metal chromium film, realizes repeated gluing utilization of a chromium-plated substrate, and has obvious economic benefits.

In order to fully illustrate the relevant performance of the photoresist cleaning solution provided by the application and facilitate understanding of the invention, multiple sets of experimental verification are performed in the application. The present invention will be further described with reference to specific examples and comparative examples.

Example 1

1. The photoresist cleaning solution of the embodiment comprises a first photoresist cleaning solution and a second photoresist cleaning solution, wherein the first photoresist cleaning solution comprises the following components in percentage by mass: 60% of a first cleaning agent, 0.1% of a metal corrosion inhibitor and 39.9% of deionized water; the second photoresist cleaning solution comprises the following components in percentage by mass: 67% of a second cleaning agent, 0.1% of a metal corrosion inhibitor and 32.9% of deionized water. The pyrrolidone compound is N-methyl pyrrolidone, the alkyl ammonium hydroxide is tetramethyl ammonium hydroxide, and the metal corrosion inhibitor is benzotriazole.

2. The cleaning method for cleaning the photoresist by using the photoresist cleaning solution comprises the following steps:

adding deionized water into the mixture of the second cleaning agent and the metal corrosion inhibitor to prepare a second photoresist cleaning solution; the second cleaning agent in the second photoresist cleaning solution comprises 67% by mass of a second cleaning agent, 0.1% by mass of a metal corrosion inhibitor and 32.9% by mass of deionized water.

The device to be cleaned (substrate to be cleaned) was placed in the above-mentioned second photoresist cleaning solution, and immersion-cleaned at 25 ℃ for 10 min.

And taking the substrate to be cleaned out of the mixed second photoresist cleaning solution, repeatedly washing the substrate with deionized water for 10 times, and washing the substrate with the deionized water for 10 times for 10 min.

Adding deionized water into a mixture of the first cleaning agent and the metal corrosion inhibitor to prepare a first photoresist cleaning solution; the first photoresist cleaning solution comprises 60% by mass of a first cleaning agent, 0.1% by mass of a metal corrosion inhibitor and 39.9% by mass of deionized water, and is poured into the ultrasonic cleaning tank.

And placing the substrate to be cleaned, which is washed by the deionized water, in a substrate clamping tool, placing the substrate into the first photoresist cleaning solution, and ultrasonically cleaning the substrate for 10min at 25 ℃.

And after the ultrasonic cleaning is finished, heating the first photoresist cleaning solution to 50 ℃, and soaking and cleaning for 10 min.

Taking out the substrate soaked and cleaned at 50 ℃, repeatedly washing the substrate with deionized water for 10 times, and washing the substrate with the deionized water for 10 times for 10 min.

And (3) taking 5000mL of absolute ethyl alcohol into an ultrasonic cleaning tank, placing the substrate cleaned by the deionized water into a substrate clamping tool, placing the substrate into the absolute ethyl alcohol, and cleaning for 20min at 25 ℃.

And taking out the substrate subjected to the ultrasonic cleaning by the absolute ethyl alcohol, repeatedly washing the substrate by deionized water for 10 times, and washing the substrate by the deionized water for 10 times for 10 min.

And blowing the substrate cleaned by the deionized water for 2min by adopting ultra-pure nitrogen.

And (3) placing the substrate dried by nitrogen on a hot bench, drying at 55 ℃, and baking for 3 min.

Comparative example 1

Comparative example 1 this example uses a conventional resist cleaning solution and cleaning method (e.g., a cleaning solution disclosed in JP 10239865A) to clean a resist on the surface of a chromium-plated substrate.

The photoresist cleaning solution and cleaning method of example 1 were compared with those of comparative example 1.

FIG. 3 is a photograph showing the results of cleaning a photoresist on the surface of a chrome-plated substrate using the photoresist cleaning solution provided in example 1, and FIG. 4 is a photograph showing the results of cleaning a photoresist on the surface of a chrome-plated substrate using the photoresist cleaning solution provided in comparative example 1. As can be seen from fig. 3 and 4, when the technical scheme of the embodiment 1 of the invention is adopted for cleaning, the chromium film on the surface of the substrate has no macroscopic corrosion signs; after the cleaning by adopting the scheme of the comparative example 1, the chromium film on the surface of the substrate obviously has corrosion phenomenon.

Fig. 5 shows a surface topography picture of the marked part (circled square part) in fig. 3 under a 100-fold optical microscope, and fig. 6 shows a surface topography picture of the marked part (circled circular part) in fig. 4 under a 100-fold optical microscope. As can be seen from fig. 5 and 6, the photoresist cleaning solution and the cleaning method provided in embodiment 1 of the present invention have no damage to the chromium film on the surface of the substrate; the photoresist cleaning solution and the cleaning method of comparative example 1 had severe damage to the chromium film on the substrate surface.

Example 2

The cleaning method of embodiment 2 is basically the same as that of embodiment 1, and the description of the same parts is omitted, except that:

the photoresist cleaning solution of the embodiment includes a first photoresist cleaning solution and a second photoresist cleaning solution, wherein the first photoresist cleaning solution includes the following components by mass percent: 50% of a first cleaning agent, 0.01% of a metal corrosion inhibitor and 49.99% of deionized water; the second photoresist cleaning solution comprises the following components in percentage by mass: 60% of second cleaning agent, 0.01% of metal corrosion inhibitor and 39.99% of deionized water. The pyrrolidone compound is N-methyl pyrrolidone, the alkyl ammonium hydroxide is tetramethyl ammonium hydroxide, and the metal corrosion inhibitor is benzotriazole.

Example 3

The cleaning method of embodiment 3 is basically the same as that of embodiment 1, and the description of the same parts is omitted, except that:

the photoresist cleaning solution of the embodiment includes a first photoresist cleaning solution and a second photoresist cleaning solution, wherein the first photoresist cleaning solution includes the following components by mass percent: 72% of a first cleaning agent, 1% of a metal corrosion inhibitor and 27% of deionized water; the second photoresist cleaning solution comprises the following components in percentage by mass: 84% of second cleaning agent, 0.5% of metal corrosion inhibitor and 15.5% of deionized water. The pyrrolidone compound is N-methyl pyrrolidone, the alkyl ammonium hydroxide is tetramethyl ammonium hydroxide, and the metal corrosion inhibitor is benzotriazole.

Example 4

The cleaning method of embodiment 4 is basically the same as that of embodiment 1, and the description of the same parts is omitted, except that:

the photoresist cleaning solution of the embodiment includes a first photoresist cleaning solution and a second photoresist cleaning solution, wherein the first photoresist cleaning solution includes the following components by mass percent: 90% of a first cleaning agent, 5% of a metal corrosion inhibitor and 5% of deionized water; the second photoresist cleaning solution comprises the following components in percentage by mass: 95% of second cleaning agent, 3% of metal corrosion inhibitor and 2% of deionized water. The pyrrolidone compound is N-methyl pyrrolidone, the alkyl ammonium hydroxide is tetramethyl ammonium hydroxide, and the metal corrosion inhibitor is benzotriazole.

The main difference between example 2, example 3, and example 4 and example 1 is that the component ratios in the first and second photoresist cleaning solutions are different. The technical schemes of the embodiment 2, the embodiment 3 and the embodiment 4 of the invention are respectively adopted to clean the chromium-plated substrate, so that a good cleaning effect can be realized, and the chromium film on the surface of the substrate has no corrosion sign macroscopically; and the photoresist cleaning solution and the cleaning method provided in examples 2, 3 and 4 were used to observe the damage of the chromium film on the surface of the substrate under a microscope. It is thus demonstrated that the cleaning effects of examples 4, 3 and 2 are not significantly different from those of example 1 in the range of the proper mixture ratio of the first and second photoresist cleaning solutions provided by the present invention under the same other operating conditions.

Example 5

The cleaning method of embodiment 5 is basically the same as that of embodiment 1, and the description of the same parts is omitted, except that: the pyrrolidone compound in this example is N-ethyl pyrrolidone, and the alkylammonium hydroxide is tetrapropylammonium hydroxide.

Example 6

The cleaning method of embodiment 6 is basically the same as that of embodiment 1, and the description of the same parts is omitted, except that: the alkylammonium hydroxide of this example was methyltriethylammonium hydroxide.

Example 7

The cleaning method of embodiment 7 is basically the same as that of embodiment 1, and the description of the same parts is omitted, except that: the pyrrolidone compound in this example is N-hydroxyethyl pyrrolidone, and the alkylammonium hydroxide is tetraethylammonium hydroxide.

Example 8

The cleaning method of embodiment 8 is basically the same as that of embodiment 1, and the description of the same parts is omitted, except that: the pyrrolidone compound in this example is N-butyl pyrrolidone, and the alkyl ammonium hydroxide is benzyl trimethyl ammonium hydroxide.

Example 9

The cleaning method of embodiment 9 is basically the same as that of embodiment 1, and the description of the same parts is omitted, except that: the pyrrolidone compound in this example is N-cyclohexyl pyrrolidone, the alkyl ammonium hydroxide is benzyl triethyl ammonium hydroxide, and the metal corrosion inhibitor is alkyl benzotriazole.

Example 10

The cleaning method of embodiment 10 is basically the same as that of embodiment 1, and the description of the same parts is omitted, except that: the pyrrolidone compound in this example is N-propyl pyrrolidone, the alkyl ammonium hydroxide is tetrabutyl ammonium hydroxide, and the metal corrosion inhibitor is hydroxybenzotriazole.

The main difference between example 5, example 6, example 7, example 8, example 9, and example 10 and example 1 is the type of each component in the photoresist cleaning solution. The technical schemes of the embodiment 5 to the embodiment 10 of the invention are respectively adopted to clean the chromium-plated substrate, so that a good cleaning effect can be realized, and the chromium film on the surface of the substrate has no corrosion sign in a macroscopic view; and the photoresist cleaning solution and the cleaning method provided in examples 5 to 10 were used to observe the damage of the chromium film on the surface of the substrate under a microscope. It is thus demonstrated that, under the same operating conditions, the specific types of the pyrrolidone-based compound, the alkylammonium hydroxide and the metal corrosion inhibitor provided by the present invention are within the range, and that the cleaning effects of examples 5, 6, 7, 8, 9, 10 and 1 are substantially not significantly different, and that a good cleaning effect can be achieved.

Example 11

The cleaning method of embodiment 11 is basically the same as that of embodiment 1, and the description of the same parts is omitted, except that:

the photoresist cleaning solution of the embodiment includes a first photoresist cleaning solution and a second photoresist cleaning solution, wherein the first photoresist cleaning solution includes the following components by mass percent: 45% of a first cleaning agent, 10% of a metal corrosion inhibitor and 45% of deionized water; the second photoresist cleaning solution comprises the following components in percentage by mass: 80% of a second cleaning agent, 10% of a metal corrosion inhibitor and 10% of deionized water. The pyrrolidone compound is N-hydroxyethyl pyrrolidone, the alkyl ammonium hydroxide is tetraethyl ammonium hydroxide, and the metal corrosion inhibitor is hydroxybenzotriazole.

Example 12

The cleaning method of embodiment 12 is basically the same as that of embodiment 1, and the description of the same parts is omitted, except that:

the photoresist cleaning solution of the embodiment includes a first photoresist cleaning solution and a second photoresist cleaning solution, wherein the first photoresist cleaning solution includes the following components by mass percent: 82% of a first cleaning agent, 6% of a metal corrosion inhibitor and 12% of deionized water; the second photoresist cleaning solution comprises the following components in percentage by mass: 77% of second cleaning agent, 7% of metal corrosion inhibitor and 16% of deionized water. The pyrrolidone compound is N-cyclohexyl pyrrolidone, the alkyl ammonium hydroxide is tetrabutyl ammonium hydroxide, and the metal corrosion inhibitor is carboxyl benzotriazole.

The main difference between the cleaning solutions of the embodiments 11 and 12 and the embodiment 1 is the different types and ratios of the components in the photoresist cleaning solution. The technical schemes of the embodiment 11 to the embodiment 12 of the invention are respectively adopted to clean the chromium-plated substrate, so that a good cleaning effect can be realized, and the chromium film on the surface of the substrate has no corrosion signs macroscopically; and the photoresist cleaning solution and the cleaning method provided in examples 11 to 12 were used to observe the damage of the chromium film on the surface of the substrate under a microscope. It is thus demonstrated that under the same operating conditions, the cleaning effects of examples 11 and 12 are not much different from those of example 1 in the specific types of the pyrrolidone-based compound, the alkylammonium hydroxide and the metal corrosion inhibitor provided by the present invention and in the compounding ratio provided by the present invention, and that a good cleaning effect can be achieved.

Example 13

The embodiment 13 is the same as the embodiment 1 in terms of cleaning by using a photoresist, and details of the same parts are omitted, except for operation parameters in the cleaning method; the cleaning method comprises the following steps:

the device to be cleaned (substrate to be cleaned) was placed in the above-mentioned second photoresist cleaning solution, and immersion-cleaned at 25 ℃ for 20 min.

And taking the substrate to be cleaned out of the mixed second photoresist cleaning solution, repeatedly washing the substrate with deionized water for 15 times, and washing the substrate with the deionized water for 15 times for 15 min.

And placing the substrate to be cleaned after being washed by the deionized water into a substrate clamping tool, placing the substrate into the first photoresist cleaning solution, and ultrasonically cleaning the substrate for 15min at 25 ℃.

And after the ultrasonic cleaning is finished, heating the first photoresist cleaning solution to 50 ℃, and soaking and cleaning for 5 min.

Taking out the substrate soaked and cleaned at 50 ℃, repeatedly washing the substrate with deionized water for 15 times, wherein the total time of washing the substrate with deionized water for 15 times is 15 min.

And (3) putting 5000mL of absolute ethyl alcohol into an ultrasonic cleaning tank, putting the substrate cleaned by the deionized water into a substrate clamping tool, putting the substrate into the absolute ethyl alcohol, and cleaning for 20min at 25 ℃.

And taking out the substrate subjected to the ultrasonic cleaning by the absolute ethyl alcohol, repeatedly washing the substrate by the deionized water for 15 times, and washing the substrate by the deionized water for 15 times for 15 min.

And blowing the substrate cleaned by the deionized water for 5min by adopting ultra-pure nitrogen.

And (3) placing the substrate dried by nitrogen on a hot bench, drying at 55 ℃, and baking for 2 min.

Example 14

The embodiment 14 is the same as the embodiment 1 in terms of cleaning by using a photoresist, and details of the same parts are omitted, except for operation parameters in the cleaning method; the cleaning method comprises the following steps:

the device to be cleaned (substrate to be cleaned) was placed in the above-mentioned second photoresist cleaning solution, and immersion-cleaned at 25 ℃ for 30 min.

And taking the substrate to be cleaned out of the mixed second photoresist cleaning solution, repeatedly washing the substrate with deionized water for 10 times, and washing the substrate with the deionized water for 10 times for 8 min.

And placing the substrate to be cleaned, which is washed by the deionized water, in a substrate clamping tool, placing the substrate into the first photoresist cleaning solution, and ultrasonically cleaning the substrate for 20min at 25 ℃.

And after the ultrasonic cleaning is finished, heating the first photoresist cleaning solution to 50 ℃, and soaking and cleaning for 20 min.

Taking out the substrate soaked and cleaned at 50 ℃, repeatedly washing the substrate with deionized water for 10 times, and washing the substrate with deionized water for 10 times for 8 min.

And (3) taking 5000mL of absolute ethyl alcohol into an ultrasonic cleaning tank, placing the substrate cleaned by the deionized water into a substrate clamping tool, placing the substrate into the absolute ethyl alcohol, and cleaning for 15min at 25 ℃.

And taking out the substrate subjected to the ultrasonic cleaning by the absolute ethyl alcohol, repeatedly washing the substrate by deionized water for 10 times, and washing the substrate by the deionized water for 10 times for 8 min.

And blowing the substrate cleaned by the deionized water for 10min by adopting ultra-pure nitrogen.

And (3) placing the substrate dried by nitrogen on a hot bench, drying at 55 ℃, and baking for 5 min.

Example 15

The embodiment 15 is the same as the embodiment 1 in terms of cleaning by using a photoresist, and details of the same parts are omitted, except for operation parameters in the cleaning method; the cleaning method comprises the following steps:

the device to be cleaned (substrate to be cleaned) was placed in the above-mentioned second photoresist cleaning solution, and immersion-cleaned at 25 ℃ for 40 min.

And taking the substrate to be cleaned out of the mixed second photoresist cleaning solution, repeatedly washing the substrate with deionized water for 10 times, and washing the substrate with deionized water for 10 times for 10 min.

And placing the substrate to be cleaned, which is washed by the deionized water, in a substrate clamping tool, placing the substrate into the first photoresist cleaning solution, and ultrasonically cleaning the substrate for 5min at 25 ℃.

And after the ultrasonic cleaning is finished, heating the first photoresist cleaning solution to 50 ℃, and soaking and cleaning for 15 min.

And (3) taking 5000mL of absolute ethyl alcohol into an ultrasonic cleaning tank, placing the substrate cleaned by the deionized water into a substrate clamping tool, placing the substrate into the absolute ethyl alcohol, and cleaning for 30min at 25 ℃.

Taking out the substrate subjected to the ultrasonic cleaning by the absolute ethyl alcohol, repeatedly washing the substrate by deionized water for 10 times, and washing the substrate by the deionized water for 10 times for 10 min.

And blowing the substrate cleaned by the deionized water for 5min by using ultra-pure nitrogen.

And (3) placing the substrate dried by nitrogen on a hot table, drying at 50 ℃, and baking for 3 min.

Example 16

The embodiment 16 is the same as the embodiment 1 in terms of cleaning by using a photoresist, and details of the same parts are omitted, except for operation parameters in the cleaning method; the cleaning method comprises the following steps:

the device to be cleaned (substrate to be cleaned) was placed in the above-mentioned second photoresist cleaning solution, and immersion-cleaned at 30 ℃ for 10 min.

And placing the substrate to be cleaned after being washed by the deionized water into a substrate clamping tool, placing the substrate into the first photoresist cleaning solution, and ultrasonically cleaning the substrate for 10min at the temperature of 30 ℃.

And after the ultrasonic cleaning is finished, heating the first photoresist cleaning solution to 45 ℃, and soaking and cleaning for 20 min.

Taking out the substrate soaked and cleaned at the temperature of 45 ℃, repeatedly washing the substrate with deionized water for 10 times, and washing the substrate with the deionized water for 10 times for 10 min.

And (3) taking 5000mL of absolute ethyl alcohol into an ultrasonic cleaning tank, placing the substrate cleaned by the deionized water into a substrate clamping tool, placing the substrate into the absolute ethyl alcohol, and cleaning for 15min at the temperature of 30 ℃.

And (3) placing the substrate dried by nitrogen on a hot bench, drying at 50 ℃, and baking for 3 min.

Example 17

The embodiment 17 is the same as the embodiment 1 in terms of cleaning by using a photoresist, and details of the same parts are omitted, except for operation parameters in the cleaning method; the cleaning method comprises the following steps:

the device to be cleaned (substrate to be cleaned) was placed in the above-mentioned second photoresist cleaning solution, and immersion-cleaned at 30 ℃ for 15 min.

And placing the substrate to be cleaned after being washed by the deionized water into a substrate clamping tool, placing the substrate into the first photoresist cleaning solution, and ultrasonically cleaning for 15min at 30 ℃.

And after the ultrasonic cleaning is finished, heating the first photoresist cleaning solution to 45 ℃, and soaking and cleaning for 15 min.

And (3) putting 5000mL of absolute ethyl alcohol into an ultrasonic cleaning tank, putting the substrate cleaned by the deionized water into a substrate clamping tool, putting the substrate into the absolute ethyl alcohol, and cleaning for 20min at the temperature of 30 ℃.

And blowing the substrate cleaned by the deionized water for 2min by using ultra-pure nitrogen.

Example 18

The embodiment 18 is the same as the embodiment 1 in terms of cleaning by using a photoresist, and details of the same parts are omitted, except for operation parameters in the cleaning method; the cleaning method comprises the following steps:

the device to be cleaned (substrate to be cleaned) was placed in the above-mentioned second photoresist cleaning solution, and immersion-cleaned at 35 ℃ for 10 min.

And placing the substrate to be cleaned, which is washed by the deionized water, in a substrate clamping tool, placing the substrate into the first photoresist cleaning solution, and ultrasonically cleaning the substrate for 10min at the temperature of 35 ℃.

And after the ultrasonic cleaning is finished, heating the first photoresist cleaning solution to 45 ℃, and soaking and cleaning for 10 min.

Taking out the substrate soaked and cleaned at the temperature of 45 ℃, repeatedly washing the substrate with deionized water for 10 times, and washing the substrate with deionized water for 10 times for 10 min.

And (3) placing the substrate dried by nitrogen on a hot bench, drying at 60 ℃, and baking for 3 min.

Example 19

The embodiment 19 is the same as the embodiment 1 in terms of cleaning by using a photoresist, and details of the same parts are omitted, except for operation parameters in the cleaning method; the cleaning method comprises the following steps:

the device to be cleaned (substrate to be cleaned) was placed in the above-mentioned second photoresist cleaning solution, and immersion-cleaned at 50 ℃ for 8 min.

And placing the substrate to be cleaned, which is washed by the deionized water, in a substrate clamping tool, placing the substrate into the first photoresist cleaning solution, and ultrasonically cleaning the substrate for 8min at the temperature of 35 ℃.

And after the ultrasonic cleaning is finished, heating the first photoresist cleaning solution to 55 ℃, and soaking and cleaning for 10 min.

Taking out the substrate soaked and cleaned at the temperature of 55 ℃, repeatedly washing the substrate with deionized water for 10 times, and washing the substrate with the deionized water for 10 times for 10 min.

And (3) putting 5000mL of absolute ethyl alcohol into an ultrasonic cleaning tank, putting the substrate cleaned by the deionized water into a substrate clamping tool, putting the substrate into the absolute ethyl alcohol, and cleaning for 20min at 35 ℃.

Example 20

The embodiment 20 is the same as the embodiment 1 in terms of cleaning by using photoresist, and the same parts are not described again, except for the operating parameters in the cleaning method; the cleaning method comprises the following steps:

and (4) placing a device to be cleaned (a substrate to be cleaned) in the second photoresist cleaning solution, and soaking and cleaning for 5min at 60 ℃.

And placing the substrate to be cleaned, which is washed by the deionized water, in a substrate clamping tool, placing the substrate into the first photoresist cleaning solution, and ultrasonically cleaning the substrate for 5min at the temperature of 35 ℃.

And after the ultrasonic cleaning is finished, heating the first photoresist cleaning solution to 55 ℃, and soaking and cleaning for 5 min.

And (3) putting 5000mL of absolute ethyl alcohol into an ultrasonic cleaning tank, putting the substrate cleaned by the deionized water into a substrate clamping tool, putting the substrate into the absolute ethyl alcohol, and cleaning for 15min at 35 ℃.

Examples 13 to 20 are different from example 1 mainly in the temperature and time at which the second photoresist cleaning solution or the first photoresist cleaning solution is cleaned. The technical schemes of the embodiment 13 to the embodiment 20 of the invention are respectively adopted to clean the chromium-plated substrate, so that a good cleaning effect can be realized, and the chromium film on the surface of the substrate has no corrosion sign in a macroscopic view; and no damage was observed on the surface of the substrate under a microscope using the photoresist cleaning solution and the cleaning method provided in examples 13 to 20. Therefore, under the same other operating conditions, the cleaning effects of the embodiments are not greatly different within the proper cleaning temperature and cleaning time range provided by the invention, and good cleaning effects can be realized.

Example 21

The photoresist cleaning solution of the embodiment includes a first photoresist cleaning solution and a second photoresist cleaning solution, and the cleaning method includes:

1) 1950mL of second cleaning agent and 1mL of metal corrosion inhibitor are taken to be put in a specified container, 1749mL of deionized water is added into the second cleaning agent, and the mixture is stirred uniformly to prepare second photoresist cleaning solution; namely, the second cleaning agent was 52.7%, the metal corrosion inhibitor was 0.03%, and the deionized water was 47.27%.

2) Placing a substrate to be cleaned in a substrate clamping tool, putting the substrate into the second photoresist cleaning solution, and soaking and cleaning for 10min at 25 ℃;

3) taking out the substrate soaked and cleaned by the mixed solution, and repeatedly washing the substrate for 10 times by using deionized water, wherein the total time of washing for 10 times is 10 min;

4) 2500mL of first cleaning agent and 1mL of corrosion inhibitor are taken in a specified container, and 2499mL of deionized water is added into the container, namely, the proportion of the first cleaning agent is 50%, the proportion of the metal corrosion inhibitor is 0.02%, and the proportion of the deionized water is 49.98%; uniformly stirring the mixture to prepare a first photoresist cleaning solution, and pouring the first photoresist cleaning solution into an ultrasonic cleaning tank;

5) placing the substrate washed by the deionized water into a substrate clamping tool, placing the substrate into the mixed solution II, and ultrasonically cleaning for 10min at 25 ℃;

6) after the ultrasonic cleaning is finished, heating the mixed solution II to 50 ℃, and soaking and cleaning for 10 min;

7) taking out the substrate soaked and cleaned at 50 ℃, and repeatedly washing the substrate for 10 times by using deionized water, wherein the total time of washing for 10 times is 10 min;

8) placing 5000mL of absolute ethyl alcohol into an ultrasonic cleaning tank, placing the substrate cleaned by deionized water into a substrate clamping tool, placing the substrate into the absolute ethyl alcohol, and cleaning for 20min at 25 ℃;

9) taking out the substrate subjected to the ultrasonic cleaning by the absolute ethyl alcohol, and repeatedly washing the substrate for 10 times by deionized water, wherein the total time of washing for 10 times is 10 min;

10) drying the substrate cleaned by the deionized water by adopting ultra-pure nitrogen, and blowing for 2 min;

11) and (3) placing the substrate dried by nitrogen on a hot table, drying at 55 ℃, and baking for 3 min.

In this embodiment, the pyrrolidone compound is N-methylpyrrolidone, the alkyl ammonium hydroxide is tetramethyl ammonium hydroxide, and the metal corrosion inhibitor is benzotriazole.

In other embodiments, the photoresist cleaning solution comprises a first cleaning agent, a second cleaning agent, a metal corrosion inhibitor and deionized water; the cleaning method comprises the following steps:

(b) washing the device to be cleaned in the step (a) with water;

Example 22

1. The photoresist cleaning solution of the present example comprises the following components in the following mass percentages: 45% of the first cleaning agent, 30% of the second cleaning agent, 0.02% of a metal corrosion inhibitor and 24.98% of deionized water. The pyrrolidone compound is N-methyl pyrrolidone, the alkyl ammonium hydroxide is tetramethyl ammonium hydroxide, and the metal corrosion inhibitor is benzotriazole.

2250mL of the first cleaning agent, 1500mL of the second cleaning agent and 1mL of the metal corrosion inhibitor are taken out of a designated container, 1249mL of deionized water is added into the container, and the mixture is uniformly stirred to prepare a mixed solution which is poured into an ultrasonic cleaning tank.

And (3) placing the substrate to be cleaned into a substrate clamping tool, putting the substrate into the mixed solution, and ultrasonically cleaning for 30min at 25 ℃.

And taking out the substrate subjected to ultrasonic cleaning, and repeatedly washing the substrate for 10 times by using deionized water, wherein the total time of washing for 10 times is 10 min.

5000mL of ethylene glycol is taken to be placed in an ultrasonic cleaning tank, the substrate cleaned by deionized water is placed in a substrate clamping tool and is placed in the ethylene glycol, and the substrate is cleaned for 20min at the temperature of 25 ℃.

And taking out the substrate subjected to the ultrasonic cleaning by the ethylene glycol, and repeatedly washing the substrate by deionized water for 10 times, wherein the total time of washing for 10 times is 10 min.

Example 23

The cleaning method of embodiment 23 is substantially the same as that of embodiment 22, and the description of the same parts is omitted, except that:

the photoresist cleaning solution of the embodiment comprises the following components in percentage by mass: 40% of first cleaning agent, 35% of second cleaning agent, 0.01% of metal corrosion inhibitor and 24.99% of deionized water. The pyrrolidone compound is N-ethyl pyrrolidone, the alkyl ammonium hydroxide is tetrabutyl ammonium hydroxide, and the metal corrosion inhibitor is alkyl benzotriazole.

Example 24

The cleaning method of the embodiment 24 is basically the same as that of the embodiment 22, and the description of the same parts is omitted, except that:

the photoresist cleaning solution of the embodiment comprises the following components in percentage by mass: 50% of the first cleaning agent, 25% of the second cleaning agent, 3% of the metal corrosion inhibitor and 22% of deionized water. The pyrrolidone compound is N-hydroxyethyl pyrrolidone, the alkyl ammonium hydroxide is tetraethyl ammonium hydroxide, and the metal corrosion inhibitor is benzotriazole.

Example 25

The cleaning method of embodiment 25 is substantially the same as that of embodiment 22, and the description of the same parts is omitted, except that:

the photoresist cleaning solution of the embodiment comprises the following components in percentage by mass: 35% of the first cleaning agent, 40% of the second cleaning agent, 10% of the metal corrosion inhibitor and 15% of deionized water. The pyrrolidone compound is N-propyl pyrrolidone, the alkyl ammonium hydroxide is methyl triethyl ammonium hydroxide, and the metal corrosion inhibitor is hydroxy benzotriazole.

Example 26

The cleaning method of embodiment 26 is substantially the same as that of embodiment 22, and the description of the same parts is omitted, except that:

the photoresist cleaning solution of the embodiment comprises the following components in percentage by mass: 55% of the first cleaning agent, 20% of the second cleaning agent, 5% of the metal corrosion inhibitor and 20% of deionized water. The pyrrolidone compound is N-cycloethyl pyrrolidone, the alkyl ammonium hydroxide is benzyl trimethyl ammonium hydroxide, and the metal corrosion inhibitor is hydroxy benzotriazole.

Examples 22 to 26 are the cleaning method in which the first cleaning agent and the second cleaning agent are directly mixed to form the resist cleaning solution and the resist is cleaned, and the cleaning method is simpler and the operation steps are simplified. The technical schemes of the embodiments 22 to 26 of the invention are respectively adopted to clean the chromium-plated substrate, so that the good cleaning effect can be realized, and the chromium film on the surface of the substrate has no corrosion sign macroscopically; and the photoresist cleaning solution and the cleaning method provided in examples 22 to 26 were used to observe the damage of the chromium film on the surface of the substrate under a microscope.

While the present embodiments have been described with reference to the accompanying drawings, it is to be understood that the invention is not limited to the precise embodiments described above, which are meant to be illustrative and not restrictive, and that various changes may be made therein by those skilled in the art without departing from the spirit and scope of the invention as defined by the appended claims.

Claims

1. A photoresist cleaning solution, characterized in that the photoresist cleaning solution comprises: cleaning agents, metal corrosion inhibitors and water; wherein the cleaning agent comprises a first cleaning agent and/or a second cleaning agent;

2. The photoresist cleaning solution according to claim 1, wherein the photoresist cleaning solution comprises a first photoresist cleaning solution and a second photoresist cleaning solution;

3. The photoresist cleaning solution according to claim 2, wherein the first photoresist cleaning solution comprises the following components in percentage by mass: 45-95% of first cleaning agent, 0.01-10% of metal corrosion inhibitor and the balance of water;

4. The photoresist cleaning solution according to claim 3, wherein the first photoresist cleaning solution comprises the following components in percentage by mass: 60 to 90 percent of first cleaning agent, 0.01 to 5 percent of metal corrosion inhibitor and the balance of water;

5. The photoresist cleaning solution according to claim 1, wherein the photoresist cleaning solution comprises the following components in percentage by mass: 35 to 55 percent of first cleaning agent, 20 to 40 percent of second cleaning agent, 0.01 to 10 percent of metal corrosion inhibitor and the balance of water.

6. The photoresist cleaning solution according to any one of claims 1 to 5, wherein the pyrrolidone-based compound comprises at least one of N-methylpyrrolidone, N-ethylpyrrolidone, N-hydroxyethylpyrrolidone, N-propylpyrrolidone, N-butylpyrrolidone or N-cyclohexylpyrrolidone;

7. A method for producing the photoresist cleaning solution according to any one of claims 1 to 6, comprising: and uniformly mixing a cleaning agent, a metal corrosion inhibitor and water to obtain the photoresist cleaning solution.

8. The method for producing the photoresist cleaning solution according to claim 7, characterized by comprising:

9. A cleaning method for cleaning a photoresist using the photoresist cleaning solution according to any one of claims 1 to 6, wherein the photoresist cleaning solution comprises a first photoresist cleaning solution and a second photoresist cleaning solution, the cleaning method comprising:

(b) washing the device to be cleaned in the step (a) with water;

(d) washing the cleaned device to be cleaned in the step (c) with water, and then drying;

10. The cleaning method according to claim 9, wherein the step (c) specifically comprises:

and/or, the step (d) specifically comprises:

then drying by nitrogen blow-drying and hot-plate drying.

11. A cleaning method for cleaning a photoresist using the photoresist cleaning solution according to any one of claims 1 to 6, wherein the photoresist cleaning solution comprises a first cleaning agent, a second cleaning agent, a metal corrosion inhibitor and water; the cleaning method comprises the following steps:

(b) washing the device to be cleaned in the step (a) with water;

(d) and (c) washing the device to be cleaned in the step (c) by using water, and then drying.