WO2024000740A1

WO2024000740A1 - Photoresist cleaning solution, as well as preparation method therefor and cleaning method thereof

Info

Publication number: WO2024000740A1
Application number: PCT/CN2022/111340
Authority: WO
Inventors: 杜秀彤; 张恺
Original assignee: 北京华卓精科科技股份有限公司; 北京优微精密测控技术研究有限公司
Priority date: 2022-06-27
Filing date: 2022-08-10
Publication date: 2024-01-04
Also published as: CN115097703A

Abstract

A photoresist cleaning solution, as well as a preparation method therefor and a cleaning method thereof in the technical field of photoresist cleaning. The photoresist cleaning solution comprises: a cleaning agent, a metal corrosion inhibitor and water; the cleaning agent comprises a first cleaning agent and/or a second cleaning agent, the first cleaning agent comprising a pyrrolidinone compound; the second cleaning agent comprises alkyl ammonium hydroxide; the metal corrosion inhibitor comprises benzotriazole and a derivative thereof. The photoresist cleaning solution can completely remove a photoresist without corroding a metal film, especially a chromium film, and may achieve repeated photoresist coating and utilization of a chromium-plated substrate, thus having remarkable economic benefits.

Description

Photoresist cleaning solution and preparation method and cleaning method thereof

Cross-references to related applications

This application claims priority to the Chinese patent application with application number 2022107378218 and titled "Photoresist Cleaning Liquid and Preparation Method and Cleaning Method" submitted to the China Patent Office on June 27, 2022, the entire content of which is incorporated by reference. in this application.

Technical field

The application belongs to the technical field of photoresist cleaning, and specifically relates to a photoresist cleaning liquid and its preparation method and cleaning method.

Background technique

In the field of semiconductor manufacturing, photolithography processes are often used. Photolithography is a technology that uses exposure and development to create micro-nano patterns on a photoresist layer. It is often configured to make a photoresist mask. In order to obtain products that meet the demand, it is usually necessary to plate a metal film on the surface of the photoresist mask substrate. For example, chromium-plated substrates are usually used in the manufacturing process of chips and gratings.

When the photoresist layer or photoresist mask pattern does not meet the technical requirements, the original photoresist layer needs to be removed with a cleaning solution for secondary coating. Or pattern transfer is performed after forming a photoresist mask and exposure. After obtaining the desired pattern, cleaning fluid needs to be used to peel off the remaining photoresist. It is worth noting that during the process of removing photoresist, it is very necessary to avoid damage to the metal film.

At present, photoresist cleaning solutions are mainly composed of polar organic solvents, strong alkali and deionized water, and remove the photoresist on the surface of the substrate by soaking or rinsing. However, the existing photoresist cleaning solution has a mediocre cleaning effect on the photoresist, and it is easy to cause corrosion to the metal substrate or metal film, and the damage to the metal substrate or metal film is relatively high.

Therefore, the metal corrosion problem of photoresist cleaning solutions and cleaning methods in the related art needs to be improved.

Application content

In view of the above-mentioned problems, this application aims to solve one of the technical problems in the related art, at least to a certain extent. To this end, the present application provides a photoresist cleaning solution and its preparation method and cleaning method, which can improve the cleaning effect of the photoresist, avoid or reduce corrosion of the metal film, and overcome the shortcomings of the existing technology. .

In order to solve the above technical problems, this application is implemented as follows:

According to one aspect of the present application, an embodiment of the present application provides a photoresist cleaning liquid. The photoresist cleaning liquid includes: a cleaning agent, a metal corrosion inhibitor and water; wherein the cleaning agent includes a first cleaning agent. agent and/or second cleaning agent;

The first cleaning agent includes pyrrolidone compounds, the second cleaning agent includes alkyl ammonium hydroxide, and the metal corrosion inhibitor includes benzotriazole and its derivatives.

Optionally, the photoresist cleaning liquid includes a first photoresist cleaning liquid and a second photoresist cleaning liquid;

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.

Optionally, the first photoresist cleaning solution includes the following mass percentage components: 45%-95% of the first cleaning agent, 0.01%-10% of the metal corrosion inhibitor and the balance of water.

Optionally, the second photoresist cleaning solution includes the following mass percentage components: 50%-95% of the second cleaning agent, 0.01%-10% of the metal corrosion inhibitor and the balance of water.

Optionally, the first photoresist cleaning solution includes the following mass percentage components: 60%-95% of the first cleaning agent, 0.01%-5% of the metal corrosion inhibitor and the balance of water.

Optionally, the second photoresist cleaning solution includes the following mass percentage components: 60%-95% of the second cleaning agent, 0.01%-5% of the metal corrosion inhibitor and the balance of water.

Optionally, the photoresist cleaning solution includes the following mass percentage components: 35%-55% first cleaning agent, 20%-40% second cleaning agent, 0.01%-10% metal corrosion inhibition agent and remaining water.

Optionally, the pyrrolidone compound includes at least one of N-methylpyrrolidone, N-ethylpyrrolidone, N-hydroxyethylpyrrolidone, N-propylpyrrolidone, N-butylpyrrolidone or N-cyclohexylpyrrolidone. kind.

Alternatively, the alkyl ammonium hydroxide includes tetramethyl ammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, methyltriethylammonium hydroxide, benzyl triethylammonium hydroxide At least one of methylammonium hydroxide or benzyltriethylammonium hydroxide.

Optionally, the benzotriazole and its derivatives include at least one of benzotriazole, hydroxybenzotriazole, alkylbenzotriazole or carboxybenzotriazole.

According to another aspect of the present application, embodiments of the present application also provide a method for preparing a photoresist cleaning solution as described above. The preparation method includes: mixing a cleaning agent, a metal corrosion inhibitor and water evenly, The photoresist cleaning liquid is obtained.

In some embodiments, the preparation method includes:

Mix the first cleaning agent, metal corrosion inhibitor and water evenly to obtain a first photoresist cleaning solution;

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

According to another aspect of the present application, an embodiment of the present application also provides a cleaning method for cleaning the photoresist using the photoresist cleaning liquid as described above. The photoresist cleaning liquid includes a first photoresist cleaning method. liquid and a second photoresist cleaning liquid, the cleaning method includes:

(a) Place the device to be cleaned containing photoresist in the second photoresist cleaning solution and perform immersion cleaning;

(b) Rinse the device to be cleaned with water after cleaning in step (a);

(c) Place the device to be cleaned after flushing in step (b) into the first photoresist cleaning solution for cleaning;

(d) Rinse the device to be cleaned after cleaning in step (c) with water and then dry it.

Wherein, the temperature range for cleaning using the second photoresist cleaning liquid or the first photoresist cleaning liquid is 25°C-60°C;

And/or, the cleaning time using the second photoresist cleaning solution or the first photoresist cleaning solution is 5 minutes to 40 minutes.

Optionally, step (c) specifically includes:

Place the device to be cleaned after rinsing in step (b) into the first photoresist cleaning solution and perform ultrasonic cleaning. The temperature of ultrasonic cleaning is 25°C-35°C, and the time of ultrasonic cleaning is 5min-20min;

After the ultrasonic cleaning is completed, the first photoresist cleaning solution is heated to a predetermined temperature and soaked for cleaning. The predetermined temperature is 45°C-55°C, and the soaking and cleaning time is 5min-20min;

And/or, the step (d) specifically includes:

The device to be cleaned after cleaning in step (c) is first rinsed with water, then ultrasonic cleaned with an alcohol solvent, and then rinsed with water; the ultrasonic cleaning temperature is 25°C-35°C, and the ultrasonic cleaning time is 15 minutes -30min;

Then dry it using nitrogen blow drying and hot stage drying.

Embodiments of the present application also provide a cleaning method for cleaning photoresist using the photoresist cleaning liquid as described above. The photoresist cleaning liquid includes a first cleaning agent, a second cleaning agent, and a metal corrosion inhibitor. and water; the cleaning method includes:

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

(b) Rinse the device to be cleaned with water after cleaning in step (a);

(c) Place the device to be cleaned after flushing in step (b) into an alcohol solvent for ultrasonic cleaning;

Implementing the technical solution of this application will at least have the following beneficial effects:

In the embodiment of the present application, the photoresist cleaning solution provided includes a first cleaning agent and/or a second cleaning agent, a metal corrosion inhibitor, and water. The first cleaning agent includes a pyrrolidone compound, and the second cleaning agent Including alkyl ammonium hydroxides, metal corrosion inhibitors include benzotriazole and its derivatives. Therefore, one or more of pyrrolidone compounds and alkyl ammonium hydroxide can be used to effectively remove the photoresist on the surface of the substrate, and benzotriazole and its derivatives can be used as metal corrosion inhibitors to effectively remove the photoresist on the metal surface. A protective film is formed to inhibit the corrosion of the metal film by the cleaning agent, preferably the corrosion of the chromium film. Therefore, the photoresist cleaning solution can completely remove the photoresist without corroding the metal film, and more preferably does not corrode the chromium film, and can realize the repeated coating and utilization of the chromium-plated substrate.

The preparation method of the photoresist cleaning solution provided by the embodiment of the present application is simple, easy and easy to operate, and only requires that the raw material components are mixed evenly. The cleaning method of the photoresist cleaning solution provided by the embodiment of the present application can completely remove the photoresist on the surface of the substrate without corroding the metal film on the surface of the substrate. The metal film includes a metal chromium film, which can realize the repeated use of chromium plating substrates. The use of glue has obvious economic benefits.

Description of drawings

Figure 1 is a schematic flow chart of a cleaning method for a photoresist cleaning solution provided by some exemplary embodiments of the present application;

Figure 2 is a schematic flow chart of a cleaning method for a photoresist cleaning solution provided by other exemplary embodiments of the present application;

Figure 3 is a picture of the results of cleaning the photoresist on the surface of the chromium-plated substrate with the photoresist cleaning solution provided in Example 1 of the present application;

Figure 4 is a picture of the results of cleaning the photoresist on the surface of the chromium-plated substrate with the photoresist cleaning solution provided in Comparative Example 1;

Figure 5 is a picture of the surface morphology of the marked part in Figure 3 under a 100x optical microscope;

Figure 6 is a picture of the surface morphology of the marked part in Figure 4 under a 100x optical microscope.

Detailed ways

The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present application. Obviously, the described embodiments are part of the embodiments of the present application, rather than all of the embodiments. Based on the embodiments in this application, all other embodiments obtained by those of ordinary skill in the art without creative efforts fall within the scope of protection of this application. If the specific conditions are not specified in the examples, the conditions should be carried out according to the conventional conditions or the conditions recommended by the manufacturer.

The endpoints of ranges and any values disclosed herein are not limited to the precise range or value, but these ranges or values are to be understood to include values approaching such ranges or values. For numerical ranges, the endpoint values of each range, the endpoint values of each range or individual point values, and the individual point values can be combined with each other to obtain one or more new numerical ranges.

It should be noted that the terms "and/or" or "/" used in this article are only an association relationship describing associated objects, indicating that there can be three relationships, for example, A and/or B, which can mean: existing alone A, A and B exist at the same time, and B alone exists. As used in the embodiments and the appended claims, the singular forms "a," "the" and "the" are intended to include the plural forms as well, unless the context clearly dictates otherwise.

In the description of this application, use of the terms "at least one of," "at least one of," or other similar terms connected to a list of items may mean any combination of the listed items. For example, if the items A, B are listed, then 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, then the phrase "at least one of A, B, C" means only A; or only B; only C; A and B (excluding C); A and C (excluding B); B and C (excluding A); or all of A, B and C. Item A may contain a single component or multiple components. Item B may contain a single component or multiple components. Item C may contain a single component or multiple components.

Those skilled in the art understand that, as mentioned in the background art, existing photoresist cleaning solutions still have more or less defects, and there is still a need for improvement. For example, Chinese patent CN105527803A discloses a cleaning solution containing water, alcoholamines, alcohol ethers, pyrogallol and its derivatives, and C3-C6 polyols, and the cleaning solution does not contain fluoride, hydroxylamine, cyclic alcohols, etc. amines and quaternary amine hydroxides; however, after repeated cleaning with this cleaning solution, it is more corrosive to metal chromium. For another example, Japanese patent JP1998239865 discloses an alkaline cleaning solution composed of tetramethyl ammonium hydroxide, dimethyl sulfoxide, 1,3-dimethyl-2-imidazolidinone and water. Similarly, this The cleaning solution is corrosive to the metal film and cannot completely remove the photoresist on the substrate. Therefore, how to make the photoresist cleaning solution have good photoresist removal capabilities and reduce or avoid corrosion of the metal film has become an urgent problem that the industry needs to solve.

Based on this, the technical solution of the embodiment of the present application provides a photoresist cleaning solution that can effectively inhibit corrosion of the metal film and effectively improve the photoresist removal capability, its preparation method and cleaning method, which can improve the photoresist in related technologies. The etching cleaning solution has poor cleaning effect and causes great damage to the metal film, which can improve the device yield. See below for a description of specific technical solutions.

In some embodiments of the present application, a photoresist cleaning liquid is provided. The photoresist cleaning liquid includes: a cleaning agent, a metal corrosion inhibitor and water; wherein the cleaning agent includes a first cleaning agent and/or a third cleaning agent. 2. Cleaning agent;

According to the technical solution provided by the embodiments of the present application, due to the special composition of the photoresist cleaning solution of the present application, the photoresist on the surface of the substrate can be completely removed, improving the removal ability of the photoresist without corroding the surface of the substrate. Metal films, especially metal chromium films, are more effective in inhibiting corrosion. Based on the analysis of this phenomenon, the inventor believes that it may be that the photoresist cleaning solution of the present application synergizes with each other through a suitable and appropriate amount of pyrrolidone compounds and/or alkyl ammonium hydroxide, benzotriazole and its derivatives, and water. With the mutual cooperation and support of the functions of each raw material component, as well as the mutual restriction and matching of the proportions, the photoresist removal ability of the photoresist cleaning solution is improved, and the photoresist cleaning effect is strong, while making the photo The resist cleaning solution has low damage to metal films such as metal chromium films, and effectively solves the problem of poor cleaning effect of photoresist cleaning solutions in the prior art and large damage to metal films.

It can be understood that the cleaning agent includes a first cleaning agent and/or a second cleaning agent means that the cleaning agent can be a first cleaning agent, a second cleaning agent, or a first cleaning agent and a second cleaning agent.

The first cleaning agent or the second cleaning agent in the photoresist cleaning solution can be configured to remove the photoresist on the surface of the substrate; and the mixture of the first cleaning agent and the second cleaning agent can also be configured to remove the photoresist on the surface of the substrate. of photoresist. Therefore, the photoresist cleaning solution may be composed of one or more of the first cleaning agent and the second cleaning agent, a 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 composed of a second cleaning agent, a metal corrosion inhibitor, and water. In some cases, the photoresist cleaning solution is composed of a first cleaning agent, a second cleaning agent, a metal corrosion inhibitor and water.

According to the embodiment of the present application, the metal corrosion inhibitor is selected from benzotriazole and its derivatives, because both N heteroatoms in benzotriazole and its derivatives can have weak interactions with metal atoms. , which is more conducive to its adsorption and coordination on the surface of metal materials, thereby conducive to the anti-corrosion of metal materials and effective protection of metal films. That is to say, using benzotriazole and its derivatives as corrosion inhibitors, a dense protective film can be formed on the metal surface to inhibit the corrosion of the metal film by the cleaning agent, thereby reducing or avoiding the corrosion of the photoresist cleaning solution on the metal. Membrane damage. Moreover, benzotriazole and its derivatives have good compatibility with pyrrolidone compounds and alkyl ammonium hydroxide, are easy to prepare, and are conducive to improving the stability of the system. They have good anti-corrosion effects and are easy to prepare. , Therefore, it is preferred to use benzotriazole and its derivatives as corrosion inhibitors. In addition, benzotriazole and its derivatives can have an anti-corrosion effect on a variety of metals (such as metal copper, metal chromium, etc.). In particular, it can inhibit corrosion of metal chromium films and achieve the best performance of chromium-plated substrates. Apply glue repeatedly for use.

According to the embodiment of the present application, the first cleaning agent is selected from pyrrolidone compounds, and the second cleaning agent is selected from alkyl ammonium hydroxide. Alkyl ammonium hydroxide can be configured to decompose the polymer chain segments in the photoresist, dissolve the photoresist, and improve the cleaning effect of the photoresist. Pyrrolidone compounds can not only fully dissolve and mix the components in the cleaning solution, but also dissolve the photoresist when used in photoresist cleaning and have a certain photoresist removal ability. Pyrrolidone compounds can assist alkyl ammonium hydroxide, and the two work together to further improve the cleaning effect of photoresist.

It should be noted that the embodiments of the present application have no restrictions on the source of raw materials for the photoresist cleaning solution. Those skilled in the art can flexibly choose according to actual needs, as long as it does not limit the purpose of the present application. For example, pyrrolidone compounds, alkyl ammonium hydroxides, benzotriazoles and their derivatives can be obtained commercially, or can be prepared by oneself by referring to methods known in the relevant fields.

In some embodiments, the photoresist cleaning solution or the water used in preparing the photoresist cleaning solution 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 remove the photoresist more thoroughly during cleaning, the photoresist cleaning solution is divided into a first photoresist cleaning solution and a second photoresist cleaning solution. In this way, through the cooperation of the two during cleaning, the first photoresist cleaning solution and the second photoresist cleaning solution are respectively used to clean the device to be cleaned multiple times, which can not only improve the cleaning effect of the photoresist, but also completely remove the substrate The photoresist on the surface can also avoid corrosion of the metal film and reduce damage to the metal film during cleaning.

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

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

In this document, unless otherwise stated, the percentages, proportions or parts referred to are by mass. For example, the first cleaning agent 45%-95% can be expressed as the first cleaning agent 45wt%-95wt% or 45 mass%-95 mass%. In this article, unless otherwise stated, percentage (%) refers to the mass percentage relative to the composition. For example, the first photoresist cleaning solution includes the following components by mass: 45%-95% of the first cleaning agent, 0.01%-10% of the metal corrosion inhibitor and the balance of water, based on the first photolithography The total mass of the above components in the glue cleaning solution is the basis, and the sum of the contents of each component is 100%.

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

Specifically, in the second photoresist cleaning solution, the content of the second cleaning agent is 60%-95% by mass, further can be 65%-90%, and further can be 68%-88%; typical but not limiting For example, it can be 60%, 62%, 65%, 68%, 70%, 72%, 75%, 78%, 80%, 85%, 88%, 90%, 95%, and any of these point values. Any value in the range formed by the two. In the second photoresist cleaning solution, the content of the metal corrosion inhibitor is 0.01%-10% by mass, further may be 0.01%-5%, and further may be 0.01%-3%; typical but non-limiting examples include Can be 0.01%, 0.05%, 0.1%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 5%, 6%, 8%, 10% and any of these point values Any value in the range formed by the two.

According to some embodiments of the present application, the photoresist cleaning liquid includes a first photoresist cleaning liquid and a second photoresist cleaning liquid, and the first photoresist cleaning liquid and the second photoresist cleaning liquid are prepared by adjusting each raw material. The types and proportions of the components work synergistically with other components, and the contribution of each component to the performance indicators of the photoresist cleaning solution such as cleaning effect, anti-corrosion effect or synergy of the entire system is comprehensively considered. By making each component When the components are within the above range, the prepared photoresist cleaning solution can have stable performance, good photoresist cleaning effect, and strong anti-corrosion effect. Furthermore, by rationally adjusting and optimizing the content of each component in the photoresist cleaning solution, making it within the optimal range, giving full play to the synergistic effect between the components, further improving the comprehensive performance of the photoresist cleaning solution, while reducing Cleaning fluid production costs.

As mentioned above, in some cases, the photoresist cleaning solution may be composed of a first photoresist cleaning solution and a second photoresist cleaning solution, where the first photoresist cleaning solution includes a first cleaning agent, metal corrosion Inhibitor and water, the second photoresist cleaning solution includes a second cleaning agent, metal corrosion inhibitor and water. In other cases, the photoresist cleaning solution may 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 includes the following mass percentage components: 35%-55% first cleaning agent, 20%-40% second cleaning agent, 0.01%-10% Metal corrosion inhibitors and balance water. Preferably, in some embodiments, the photoresist cleaning solution includes the following mass percentage components: 40%-50% first cleaning agent, 25%-35% second cleaning agent, 0.01%-3% of metal corrosion inhibitors and balance water.

In order to meet the needs of improving the cleaning effect of the photoresist cleaning solution, the specific types of pyrrolidone compounds can be diverse. In order to optimize the cleaning effect of the photoresist cleaning solution, in some embodiments, the pyrrolidone compounds include N-methylpyrrolidone, N-ethylpyrrolidone, N-hydroxyethylpyrrolidone, N-propylpyrrolidone, N -At least one of butylpyrrolidone or N-cyclohexylpyrrolidone. Preferably, in some embodiments, the pyrrolidone compound includes at least one of N-methylpyrrolidone, N-ethylpyrrolidone or N-hydroxyethylpyrrolidone. Exemplarily, the pyrrolidone compound may be N-methylpyrrolidone, may be N-ethylpyrrolidone, may be N-hydroxyethylpyrrolidone, or may be any two or more of the above compounds in any ratio. mixture.

In addition, in other embodiments, the pyrrolidone compounds are not limited to the ones listed above. In order to meet the needs of improving the cleaning effect of the photoresist cleaning solution, other types of pyrrolidone compounds can be used, which are not mentioned here. Describe in detail one by one.

In order to meet the needs of improving the cleaning effect of the photoresist cleaning solution, the specific types of alkyl ammonium hydroxide can be diverse. In order to optimize the cleaning effect of the photoresist cleaning solution, in some embodiments, the alkyl ammonium hydroxide includes tetramethyl ammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, and tetrabutylammonium hydroxide. At least one of ammonium, methyltriethylammonium hydroxide, benzyltrimethylammonium hydroxide or benzyltriethylammonium hydroxide. Preferably, in some embodiments, the alkyl ammonium hydroxide includes at least one of tetramethyl ammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide or tetrabutylammonium hydroxide. Exemplarily, the alkyl ammonium hydroxide may be tetramethyl ammonium hydroxide, may be tetraethylammonium hydroxide, may be tetrapropylammonium hydroxide, may be tetrabutylammonium hydroxide, or may be the above alkyl ammonium hydroxide A mixture of any two or more ammonium oxides in any proportion.

In order to meet the needs of improving the cleaning effect of the photoresist cleaning solution and reducing damage to the metal film, the specific types of benzotriazole and its derivatives can be diverse. In order to optimize the anti-corrosion effect of the photoresist cleaning solution, in some embodiments, the benzotriazole and its derivatives include benzotriazole, hydroxybenzotriazole, alkylbenzotriazole At least one of azole or carboxybenzotriazole. Preferably, in some embodiments, the benzotriazole and its derivatives include benzotriazole or hydroxybenzotriazole.

To sum up, as an example, the photoresist cleaning liquid provided by the embodiment of the present application may include a first photoresist cleaning liquid and a second photoresist cleaning liquid, wherein the first photoresist cleaning liquid includes the following mass percentage Components: 45%-90% first cleaning agent, 0.01%-3% metal corrosion inhibitor and 7%-54.99% water; the second photoresist cleaning solution includes the following mass percentage components: 65 %-90% secondary cleaning agent, 0.01%-3% metal corrosion inhibitor and 7%-34.99% water. The pyrrolidone compound is selected from one or more of N-methylpyrrolidone, N-ethylpyrrolidone or N-hydroxyethylpyrrolidone; the alkyl ammonium hydroxide is selected from tetramethylammonium hydroxide, tetraethyl hydroxide One or more of ammonium, tetrapropylammonium hydroxide or tetrabutylammonium hydroxide.

As another example, the photoresist cleaning solution provided by the embodiment of the present application includes the following mass percentage components: 40%-50% of the first cleaning agent, 25%-35% of the second cleaning agent, 0.01%- 3% metal corrosion inhibitor and 22%-24.99% water. The pyrrolidone compound is selected from one or more of N-methylpyrrolidone, N-ethylpyrrolidone or N-hydroxyethylpyrrolidone; the alkyl ammonium hydroxide is selected from tetramethylammonium hydroxide, tetraethyl hydroxide One or more of ammonium, tetrapropylammonium hydroxide or tetrabutylammonium hydroxide.

In some embodiments, the present application also provides a method for preparing a photoresist cleaning solution as described above. The preparation method includes: uniformly mixing a cleaning agent, a metal corrosion inhibitor and water to obtain the photoresist cleaning solution. Resin cleaning fluid.

The preparation method of the photoresist cleaning solution only requires mixing the components with appropriate contents evenly. The process is simple and easy to operate, and is suitable for industrial-scale production.

In some embodiments, the preparation method includes:

Wherein, the mixing temperature may be room temperature.

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

The photoresist cleaning liquid can be used in a temperature range of 25°C-60°C; further, the photoresist cleaning liquid can be used in a temperature range of 25°C-50°C;

And/or, the cleaning time using the photoresist cleaning liquid may be 5 min-40 min; further, the cleaning time using the photoresist cleaning liquid may be 10 min-30 min.

Referring to Figure 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) Rinse the device to be cleaned with water after cleaning in step (a);

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

In some embodiments, in step (b), the device to be cleaned can be repeatedly rinsed with deionized water several times. The number of rinses can be 10-15 times, and the rinse time can be 8 minutes-15 minutes, and further can be 10 minutes.

In some embodiments, step (c) specifically includes:

After the ultrasonic cleaning is completed, the first photoresist cleaning solution is heated to a predetermined temperature and soaked for cleaning. The predetermined temperature is 45°C-55°C, and the soaking and cleaning time is 5min-20min.

In some embodiments, step (d) specifically includes:

Then dry it using nitrogen blow drying and hot stage drying.

In summary, as an example, with reference to Figure 2, the embodiment of the present application provides a photoresist cleaning solution and a cleaning method that is extremely low corrosive to metal films, preferably to chromium films, and specifically includes the following steps. :

Add deionized water to the mixture of the second cleaning agent and the metal corrosion inhibitor to prepare a second photoresist cleaning solution; the mass percentage of the second cleaning agent in the second photoresist cleaning solution is 65%-90% , the percentage of metal corrosion inhibitors is 0.01%-3%, and the mass percentage of deionized water is 7%-34.99%.

The device to be cleaned (substrate to be cleaned) is placed in the second photoresist cleaning solution, and soaked and cleaned at room temperature for a period of time, which period of time may be 5 min to 20 min, or further may be 10 min.

Take out the substrate to be cleaned from the second photoresist cleaning solution, repeatedly rinse it with deionized water several times, and rinse it for a period of time. The number of rinses may be 10-15 times, and the rinse time may be 8 min-15 min. , further can be 10min.

Add deionized water to the mixture of the first cleaning agent and the metal corrosion inhibitor to form a first photoresist cleaning solution; the mass percentage of the first cleaning agent in the first photoresist cleaning solution is 45%-90% , the percentage of metal corrosion inhibitor is 0.01%-3%, the mass percentage of deionized water is 7%-54.99%, and the first photoresist cleaning solution is poured into the ultrasonic cleaning tank.

Place the substrate to be cleaned after being rinsed with deionized water into the substrate clamping tool, put it into the first photoresist cleaning solution, and ultrasonically clean it for a period of time at a specified temperature. The specified temperature may be 25°C. -35°C, further may be 25°C, and the period of time may be 5min-20min, further may be 10min.

After the above-mentioned ultrasonic cleaning is completed, the first photoresist cleaning solution is heated to a predetermined temperature and soaked for cleaning for a period of time. The predetermined temperature may be 45°C-55°C, or further may be 50°C, and the period of time may be 5 minutes. -20min, further can be 10min.

Take out the soaked and cleaned substrate, repeatedly rinse it with deionized water several times, and rinse it for a period of time. The number of rinse times can be 10-15 times, and the rinse time can be 8 min-15 min. Further, the period of time can be is 10min.

After being rinsed with deionized water, the substrate is ultrasonically cleaned with an alcoholic solvent such as anhydrous ethanol at a specified temperature for a period of time. The specified temperature may be 25°C-35°C, and further may be 25°C. The specified period of time may be It is 15min-30min, and further it can be 20min.

Take out the ultrasonic cleaned substrate and repeatedly rinse it with deionized water several times for a period of time. The number of rinses may be 10-15 times, and the rinse time may be 8 min-15 min. Further, the rinse time It can be 10 minutes.

Blow dry the remaining deionized water on the surface of the substrate with nitrogen.

The substrate dried by nitrogen gas is placed on a hot stage and dried for a period of time. The drying time may be 1 min-10 min, further may be 2 min-5 min, further may be 2 min or 5 min.

In the embodiment of the present application, the temperature of the hot stage drying can be selected from 50°C to 60°C, and further can be 55°C, and the time can be selected from 2min to 5min, and further can be 3min.

The photoresist cleaning method provided by the embodiments of the present application not only has excellent cleaning effect on the photoresist, but can completely remove the photoresist on the surface of the substrate without corroding the metal on the surface of the substrate. Films, especially metallic chromium films, enable repeated coating and utilization of chromium-plated substrates, which has obvious economic benefits.

In order to fully explain the relevant performance of the photoresist cleaning solution provided by this application and facilitate the understanding of this application, this application has conducted multiple sets of experimental verifications. The present application will be further described below in conjunction with specific examples and comparative examples.

Example 1

1. The photoresist cleaning liquid of this embodiment includes a first photoresist cleaning liquid and a second photoresist cleaning liquid, wherein the first photoresist cleaning liquid includes the following mass percentage components: 60% of the first photoresist cleaning liquid. Cleaning agent, 0.1% metal corrosion inhibitor and 39.9% deionized water; the second photoresist cleaning solution includes the following mass percentage components: 67% second cleaning agent, 0.1% metal corrosion inhibitor and 32.9 % deionized water. The pyrrolidone compound is N-methylpyrrolidone, the alkyl ammonium hydroxide is tetramethylammonium hydroxide, and the metal corrosion inhibitor is benzotriazole.

2. A cleaning method for cleaning photoresist using the photoresist cleaning solution. The cleaning method includes:

Add deionized water to the mixture of the second cleaning agent and the metal corrosion inhibitor to prepare a second photoresist cleaning solution; the mass percentage of the second cleaning agent in the second photoresist cleaning solution is 67%, and the metal corrosion inhibitor content is 67%. The percentage of inhibitor is 0.1% and the mass percentage of deionized water is 32.9%.

Place the device to be cleaned (substrate to be cleaned) in the second photoresist cleaning solution, and soak and clean at 25°C for 10 minutes.

Take out the substrate to be cleaned from the second photoresist cleaning solution and repeatedly rinse it with deionized water 10 times. The total time for rinsing 10 times with deionized water is 10 minutes.

Add deionized water to the mixture of the first cleaning agent and the metal corrosion inhibitor to prepare the first photoresist cleaning solution; the mass percentage of the first cleaning agent in the first photoresist cleaning solution is 60%, and the metal corrosion inhibitor is 60%. The percentage of inhibitor is 0.1%, the mass percentage of deionized water is 39.9%, and the first photoresist cleaning solution is poured into the ultrasonic cleaning tank.

Place the substrate to be cleaned after being rinsed with deionized water into the substrate clamping tool, put it into the first photoresist cleaning solution, and perform ultrasonic cleaning at 25° C. for 10 minutes.

After the ultrasonic cleaning is completed, the first photoresist cleaning solution is heated to 50°C and soaked for 10 minutes.

Take out the substrate soaked and cleaned at 50°C and rinse it repeatedly with deionized water 10 times. The total time of rinsing 10 times with deionized water is 10 minutes.

Take 5000 mL of absolute ethanol in the ultrasonic cleaning tank, place the substrate cleaned with deionized water into the substrate holding tool, put it into absolute ethanol, and clean at 25°C for 20 minutes.

Take out the substrate that has been ultrasonically cleaned with absolute ethanol and repeatedly rinse it with deionized water 10 times. The total time for rinsing 10 times with deionized water is 10 minutes.

Blow dry the substrate cleaned with deionized water using ultrapure nitrogen for 2 minutes.

Place the nitrogen-dried substrate on a hot stage and bake it at 55°C for 3 minutes.

Comparative example 1

In Comparative Example 1, the existing photoresist cleaning solution and cleaning method (such as using the cleaning solution with patent publication number JP10239865A) are used to clean the photoresist on the surface of the chromium-plated substrate.

Compare the photoresist cleaning solution and cleaning method of Example 1 with the photoresist cleaning solution and cleaning method of Comparative Example 1.

Figure 3 shows the result of using the photoresist cleaning solution provided in Example 1 to clean the photoresist on the surface of the chromium-plated substrate. Figure 4 shows the photoresist on the surface of the chromium-plated substrate using the photoresist cleaning solution provided in Comparative Example 1. Result picture. As can be seen from Figures 3 and 4, when the technical solution of Example 1 of the present application is used for cleaning, the chromium film on the surface of the substrate has no macroscopic signs of corrosion; while after cleaning using the solution of Comparative Example 1, the chromium film on the surface of the substrate has There is obvious corrosion.

Figure 5 shows the surface morphology of the marked part (circled part) in Figure 3 under a 100x optical microscope, and Figure 6 shows the marked part (circled part) in Figure 4 under a 100x optical microscope. The surface morphology picture below. It can be seen from Figures 5 and 6 that the photoresist cleaning solution and cleaning method provided in Example 1 of the present application do not damage the chromium film on the surface of the substrate; while the photoresist cleaning solution and cleaning method in Comparative Example 1 do no damage to the substrate surface. The chromium film on the surface of the film is severely damaged.

Example 2

The cleaning method of Embodiment 2 is basically the same as that of Embodiment 1, and the similarities will not be repeated. The differences are:

The photoresist cleaning solution in this embodiment includes a first photoresist cleaning solution and a second photoresist cleaning solution, wherein the first photoresist cleaning solution includes the following mass percentage components: 50% of the first cleaning agent , 0.01% metal corrosion inhibitor and 49.99% deionized water; the second photoresist cleaning solution includes the following mass percentage components: 60% second cleaning agent, 0.01% metal corrosion inhibitor and 39.99% Deionized water. The pyrrolidone compound is N-methylpyrrolidone, the alkyl ammonium hydroxide is tetramethylammonium 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 similarities will not be repeated. The differences are:

The photoresist cleaning solution in this embodiment includes a first photoresist cleaning solution and a second photoresist cleaning solution, wherein the first photoresist cleaning solution includes the following mass percentage components: 72% of the first cleaning agent , 1% metal corrosion inhibitor and 27% deionized water; the second photoresist cleaning solution includes the following mass percentage components: 84% second cleaning agent, 0.5% metal corrosion inhibitor and 15.5% Deionized water. The pyrrolidone compound is N-methylpyrrolidone, the alkyl ammonium hydroxide is tetramethylammonium 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 similarities will not be repeated. The differences are:

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

The main difference between Example 2, Example 3, Example 4 and Example 1 lies in the different component ratios in the first photoresist cleaning solution and the second photoresist cleaning solution. The technical solutions of Example 2, Example 3, and Example 4 of the present application are respectively used to clean the chromium-plated substrate, and a good cleaning effect can be achieved. There is no sign of corrosion on the chromium film on the surface of the substrate macroscopically; and the examples are observed under a microscope. 2. The photoresist cleaning liquid and cleaning method provided in Example 3 and Example 4 will not damage the chromium film on the surface of the substrate. This shows that under the same other operating conditions, within the appropriate ratio range of the first photoresist cleaning solution and the second photoresist cleaning solution provided by this application, Example 4, Example 3, and Example 2 has no significant difference from the cleaning effect of Example 1.

Example 5

The cleaning method of Embodiment 5 is basically the same as that of Embodiment 1, and the similarities will not be repeated. The difference is that: the pyrrolidone compound in this embodiment is N-ethylpyrrolidone, and the alkyl ammonium hydroxide is tetrapropyl hydroxide. ammonium.

Example 6

The cleaning method of Example 6 is basically the same as that of Example 1, and the similarities will not be repeated. The difference is that the alkyl ammonium hydroxide in this example is methyltriethylammonium hydroxide.

Example 7

The cleaning method of Embodiment 7 is basically the same as that of Embodiment 1, and the similarities will not be repeated. The difference is that the pyrrolidone compound in this embodiment is N-hydroxyethylpyrrolidone, and the alkyl ammonium hydroxide is tetraethyl hydrogen. Ammonium oxide.

Example 8

The cleaning method of Embodiment 8 is basically the same as that of Embodiment 1, and the similarities will not be repeated. The difference is that the pyrrolidone compound in this embodiment is N-butylpyrrolidone, and the alkyl ammonium hydroxide is benzyltrimethyl. Ammonium hydroxide.

Example 9

The cleaning method of Embodiment 9 is basically the same as that of Embodiment 1, and the similarities will not be repeated. The difference is that: the pyrrolidone compound in this embodiment is N-cyclohexylpyrrolidone, and the alkyl ammonium hydroxide is benzyl triethyl. Ammonium hydroxide, metal corrosion inhibitor is alkylbenzotriazole.

Example 10

The cleaning method of Embodiment 10 is basically the same as that of Embodiment 1, and the similarities will not be repeated. The difference is that: the pyrrolidone compound in this embodiment is N-propylpyrrolidone, and the alkyl ammonium hydroxide is tetrabutylammonium hydroxide. Metal corrosion inhibitor is hydroxybenzotriazole.

The main difference between Example 5, Example 6, Example 7, Example 8, Example 9, Example 10 and Example 1 lies in the different types of components in the photoresist cleaning solution. The technical solutions of Examples 5 to 10 of the present application are respectively used to clean the chromium-plated substrate, and good cleaning effects can be achieved. There is no sign of corrosion on the chromium film on the surface of the substrate macroscopically; and the observations under the microscope are carried out using Examples 5 to 10. The photoresist cleaning fluid and cleaning method provided by 10 will not damage the chromium film on the surface of the substrate. This shows that under the same other operating conditions, within the specific types of pyrrolidone compounds, alkyl ammonium hydroxides and metal corrosion inhibitors provided in this application, Examples 5, 6, 7, There is basically no significant difference in the cleaning effects between Example 8, Example 9, Example 10 and Example 1, and good cleaning effects can all be achieved.

Example 11

The cleaning method of Embodiment 11 is basically the same as that of Embodiment 1, and the similarities will not be repeated. The differences are:

The photoresist cleaning solution in this embodiment includes a first photoresist cleaning solution and a second photoresist cleaning solution, wherein the first photoresist cleaning solution includes the following mass percentage components: 45% of the first cleaning agent , 10% metal corrosion inhibitor and 45% deionized water; the second photoresist cleaning solution includes the following mass percentage components: 80% second cleaning agent, 10% metal corrosion inhibitor and 10% Deionized water. The pyrrolidone compound is N-hydroxyethylpyrrolidone, the alkyl ammonium hydroxide is tetraethylammonium 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 similarities will not be repeated. The differences are:

The photoresist cleaning solution in this embodiment includes a first photoresist cleaning solution and a second photoresist cleaning solution, wherein the first photoresist cleaning solution includes the following mass percentage components: 82% of the first cleaning agent , 6% metal corrosion inhibitor and 12% deionized water; the second photoresist cleaning solution includes the following mass percentage components: 77% second cleaning agent, 7% metal corrosion inhibitor and 16% Deionized water. The pyrrolidone compound is N-cyclohexylpyrrolidone, the alkyl ammonium hydroxide is tetrabutylammonium hydroxide, and the metal corrosion inhibitor is carboxybenzotriazole.

The main difference between Example 11, Example 12 and Example 1 is that the types and proportions of each component in the photoresist cleaning solution are different. The technical solutions of Examples 11 to 12 of the present application are respectively used to clean the chromium-plated substrate, and good cleaning effects can be achieved. There is no sign of corrosion on the chromium film on the surface of the substrate macroscopically; and the observations under the microscope are carried out using Examples 11 to 12. The photoresist cleaning fluid and cleaning method provided by 12 will not damage the chromium film on the surface of the substrate. This shows that, under the same operating conditions, within the specific types of pyrrolidone compounds, alkyl ammonium hydroxide and metal corrosion inhibitors provided by this application, and within the proportion range provided by this application, the implementation There is little difference in the cleaning effects between Example 11, Example 12 and Example 1, and good cleaning effects can be achieved.

Example 13

Embodiment 13 is the same as Embodiment 1 in using photoresist cleaning, and the similarities will not be repeated. The difference lies in the operating parameters in the cleaning method; the cleaning method includes:

Place the device to be cleaned (substrate to be cleaned) in the above-mentioned second photoresist cleaning solution, and soak and clean at 25°C for 20 minutes.

Take out the substrate to be cleaned from the second photoresist cleaning solution and repeatedly rinse it with deionized water 15 times. The total time for rinsing 15 times with deionized water is 15 minutes.

Place the substrate to be cleaned after being rinsed with deionized water into the substrate clamping tool, put it into the first photoresist cleaning solution, and conduct ultrasonic cleaning at 25° C. for 15 minutes.

After the ultrasonic cleaning is completed, the first photoresist cleaning solution is heated to 50°C and soaked for 5 minutes.

Take out the substrate soaked and cleaned at 50°C and rinse it repeatedly with deionized water 15 times. The total time of rinsing 15 times with deionized water is 15 minutes.

Take out the substrate that has been ultrasonically cleaned with absolute ethanol and rinse it with deionized water 15 times for a total of 15 minutes.

Blow dry the substrate cleaned with deionized water using ultrapure nitrogen for 5 minutes.

Place the nitrogen-dried substrate on a hot stage and bake it at 55°C for 2 minutes.

Example 14

Embodiment 14 is the same as Embodiment 1 in using photoresist cleaning, and the similarities will not be repeated. The difference lies in the operating parameters in the cleaning method; the cleaning method includes:

Place the device to be cleaned (substrate to be cleaned) in the second photoresist cleaning solution, and soak and clean at 25°C for 30 minutes.

Take out the substrate to be cleaned from the second photoresist cleaning solution and repeatedly rinse it with deionized water 10 times. The total time for rinsing 10 times with deionized water is 8 minutes.

Place the substrate to be cleaned after being rinsed with deionized water into the substrate clamping tool, put it into the first photoresist cleaning solution, and perform ultrasonic cleaning at 25° C. for 20 minutes.

After the ultrasonic cleaning is completed, the first photoresist cleaning solution is heated to 50°C and soaked for 20 minutes.

Take out the substrate soaked and cleaned at 50°C and rinse it repeatedly with deionized water 10 times. The total time for rinsing 10 times with deionized water is 8 minutes.

Take 5000 mL of absolute ethanol in the ultrasonic cleaning tank, place the substrate cleaned with deionized water into the substrate holding tool, put it into absolute ethanol, and clean at 25°C for 15 minutes.

Take out the substrate that has been ultrasonically cleaned with absolute ethanol and repeatedly rinse it with deionized water 10 times. The total time for rinsing 10 times with deionized water is 8 minutes.

Use ultrapure nitrogen to blow dry the substrate cleaned with deionized water for 10 minutes.

Place the nitrogen-dried substrate on a hot stage and bake it at 55°C for 5 minutes.

Example 15

Embodiment 15 is the same as the photoresist cleaning method used in Embodiment 1, and the similarities will not be repeated. The difference lies in the operating parameters in the cleaning method; the cleaning method includes:

Place the device to be cleaned (substrate to be cleaned) in the above-mentioned second photoresist cleaning solution, and soak and clean at 25°C for 40 minutes.

Place the substrate to be cleaned after being rinsed with deionized water into the substrate clamping tool, put it into the first photoresist cleaning solution, and perform ultrasonic cleaning at 25° C. for 5 minutes.

After the ultrasonic cleaning is completed, the first photoresist cleaning solution is heated to 50°C and soaked for 15 minutes.

Take 5000 mL of absolute ethanol in the ultrasonic cleaning tank, place the substrate cleaned with deionized water into the substrate holding tool, put it into absolute ethanol, and clean at 25°C for 30 minutes.

Place the nitrogen-dried substrate on a hot stage and bake it at 50°C for 3 minutes.

Example 16

Embodiment 16 is the same as the photoresist cleaning method used in Embodiment 1, and the similarities will not be repeated. The difference lies in the operating parameters in the cleaning method; the cleaning method includes:

Place the device to be cleaned (substrate to be cleaned) in the second photoresist cleaning solution, and soak and clean at 30°C for 10 minutes.

Place the substrate to be cleaned after being rinsed with deionized water into the substrate clamping tool, put it into the first photoresist cleaning solution, and perform ultrasonic cleaning at 30° C. for 10 minutes.

After the ultrasonic cleaning is completed, the first photoresist cleaning solution is heated to 45°C and soaked for 20 minutes.

Take out the substrate soaked and cleaned at 45°C and rinse it repeatedly with deionized water 10 times. The total time of rinsing 10 times with deionized water is 10 minutes.

Take 5000 mL of absolute ethanol in the ultrasonic cleaning tank, place the substrate cleaned with deionized water into the substrate holding tool, put it into absolute ethanol, and clean at 30°C for 15 minutes.

Example 17

Embodiment 17 is the same as the photoresist cleaning method used in Embodiment 1, and the similarities will not be repeated. The difference lies in the operating parameters in the cleaning method; the cleaning method includes:

Place the device to be cleaned (substrate to be cleaned) in the above-mentioned second photoresist cleaning solution, and soak and clean at 30°C for 15 minutes.

Place the substrate to be cleaned after being rinsed with deionized water into the substrate clamping tool, put it into the first photoresist cleaning solution, and perform ultrasonic cleaning at 30° C. for 15 minutes.

After the ultrasonic cleaning is completed, the first photoresist cleaning solution is heated to 45°C and soaked for 15 minutes.

Take 5000 mL of absolute ethanol in the ultrasonic cleaning tank, place the substrate cleaned with deionized water into the substrate holding tool, put it into absolute ethanol, and clean at 30°C for 20 minutes.

Example 18

Embodiment 18 is the same as the photoresist cleaning used in Embodiment 1, and the similarities will not be repeated. The difference lies in the operating parameters in the cleaning method; the cleaning method includes:

Place the device to be cleaned (substrate to be cleaned) in the second photoresist cleaning solution, and soak and clean at 35°C for 10 minutes.

Place the substrate to be cleaned after being rinsed with deionized water into the substrate clamping tool, put it into the first photoresist cleaning solution, and perform ultrasonic cleaning at 35° C. for 10 minutes.

After the ultrasonic cleaning is completed, the first photoresist cleaning solution is heated to 45°C and soaked for 10 minutes.

Place the nitrogen-dried substrate on a hot stage, bake it at 60°C for 3 minutes.

Example 19

Embodiment 19 is the same as the photoresist cleaning method used in Embodiment 1, and the similarities will not be repeated. The difference lies in the operating parameters in the cleaning method; the cleaning method includes:

Place the device to be cleaned (substrate to be cleaned) in the above-mentioned second photoresist cleaning solution, and soak and clean at 50°C for 8 minutes.

Place the substrate to be cleaned after being rinsed with deionized water into the substrate clamping tool, put it into the first photoresist cleaning solution, and perform ultrasonic cleaning at 35° C. for 8 minutes.

After the ultrasonic cleaning is completed, the first photoresist cleaning solution is heated to 55°C and soaked for 10 minutes.

Take out the substrate soaked and cleaned at 55°C and rinse it repeatedly with deionized water 10 times. The total time of rinsing 10 times with deionized water is 10 minutes.

Take 5000 mL of absolute ethanol in the ultrasonic cleaning tank, place the substrate cleaned with deionized water into the substrate holding tool, put it into absolute ethanol, and clean at 35°C for 20 minutes.

Place the nitrogen-dried substrate on the hot stage, dry it at 60°C, and bake it for 3 minutes.

Example 20

Embodiment 20 is the same as Embodiment 1 in using photoresist cleaning, and the similarities will not be repeated. The difference lies in the operating parameters in the cleaning method; the cleaning method includes:

Place the device to be cleaned (the substrate to be cleaned) in the second photoresist cleaning solution, and soak and clean it at 60°C for 5 minutes.

Place the substrate to be cleaned after being rinsed with deionized water into the substrate clamping tool, put it into the first photoresist cleaning solution, and conduct ultrasonic cleaning at 35° C. for 5 minutes.

After the ultrasonic cleaning is completed, the first photoresist cleaning solution is heated to 55°C and soaked for 5 minutes.

Take 5000 mL of absolute ethanol in the ultrasonic cleaning tank, place the substrate cleaned with deionized water into the substrate holding tool, put it into absolute ethanol, and clean at 35°C for 15 minutes.

The main difference between Embodiment 13 to Embodiment 20 and Embodiment 1 is that the temperature and time of cleaning by the second photoresist cleaning liquid or the first photoresist cleaning liquid are different. The technical solutions of Examples 13 to 20 of the present application are respectively used to clean the chromium-plated substrate, and a good cleaning effect can be achieved. There is no sign of corrosion on the chromium film on the surface of the substrate macroscopically; and when observed under a microscope, Examples 13 to 20 are used. The photoresist cleaning fluid and cleaning method provided by 20 will not damage the chromium film on the surface of the substrate. This shows that under the same other operating conditions, within the appropriate cleaning temperature and cleaning time range provided in this application, there is little difference in the cleaning effect of each embodiment, and good cleaning effects can be achieved.

Example 21

The photoresist cleaning solution in this embodiment includes a first photoresist cleaning solution and a second photoresist cleaning solution. The cleaning method includes:

1) Take 1950mL of the second cleaning agent and 1mL of the metal corrosion inhibitor in a designated container, add 1749mL of deionized water to it, and stir the above mixture evenly to prepare the second photoresist cleaning solution; that is, the second photoresist cleaning solution The proportion of the second cleaning agent is 52.7%, the proportion of metal corrosion inhibitor is 0.03%, and the proportion of deionized water is 47.27%.

2) Place the substrate to be cleaned in the substrate clamping tool, put it into the above-mentioned second photoresist cleaning solution, and soak and clean at 25°C for 10 minutes;

3) Take out the substrate that has been soaked and cleaned in the mixed solution, and rinse it repeatedly with deionized water 10 times for a total time of 10 minutes;

4) Take 2500mL of the first cleaning agent and 1mL of the corrosion inhibitor in a designated container, and add 2499mL of deionized water to it, that is, the proportion of the first cleaning agent is 50% and the proportion of the metal corrosion inhibitor is 50%. The proportion of deionized water is 0.02%, and the proportion of deionized water is 49.98%; stir the above mixture evenly to prepare the first photoresist cleaning solution, and pour it into the ultrasonic cleaning tank;

5) Place the substrate rinsed with deionized water into the substrate clamping tool, put it into mixed solution 2, and ultrasonically clean it at 25°C for 10 minutes;

6) After the ultrasonic cleaning is completed, heat the mixed solution 2 to 50°C and soak for 10 minutes;

7) Take out the substrate after soaking and cleaning at 50°C, and rinse it repeatedly with deionized water 10 times. The total time of rinsing 10 times is 10 minutes;

8) Take 5000mL of absolute ethanol in the ultrasonic cleaning tank, place the substrate cleaned with deionized water into the substrate clamping tool, put it into absolute ethanol, and clean at 25°C for 20 minutes;

9) Take out the substrate that has been ultrasonically cleaned with absolute ethanol, and rinse it repeatedly with deionized water 10 times. The total time for rinsing 10 times is 10 minutes;

10) Use ultrapure nitrogen to dry the substrate cleaned with deionized water for 2 minutes;

11) Place the nitrogen-dried substrate on the hot stage, dry it at 55°C, and bake for 3 minutes.

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

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

(b) Rinse the device to be cleaned with water after cleaning in step (a);

Example 22

1. The photoresist cleaning solution of this embodiment includes the following mass percentage components: 45% first cleaning agent, 30% second cleaning agent, 0.02% metal corrosion inhibitor and 24.98% deionization water. The pyrrolidone compound is N-methylpyrrolidone, the alkyl ammonium hydroxide is tetramethylammonium hydroxide, and the metal corrosion inhibitor is benzotriazole.

Take 2250mL of the first cleaning agent, 1500mL of the second cleaning agent and 1mL of metal corrosion inhibitor in a designated container, add 1249mL of deionized water to it, stir the above mixture evenly to prepare a mixed solution and pour it into the ultrasonic Clean the tank.

Place the substrate to be cleaned in the substrate clamping tool, put it into the above mixed solution, and ultrasonically clean it at 25°C for 30 minutes.

Take out the substrate after ultrasonic cleaning and rinse it repeatedly with deionized water 10 times. The total time of rinsing 10 times is 10 minutes.

Take 5000mL of ethylene glycol in the ultrasonic cleaning tank, place the substrate cleaned with deionized water into the substrate holding tool, put it into the ethylene glycol, and clean at 25°C for 20 minutes.

Take out the substrate that has been ultrasonically cleaned with ethylene glycol and rinse it repeatedly with deionized water 10 times. The total time for rinsing 10 times is 10 minutes.

Example 23

The cleaning methods of Embodiment 23 are basically the same as those of Embodiment 22, and the similarities will not be repeated. The differences are:

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

Example 24

The cleaning methods of Embodiment 24 are basically the same as those of Embodiment 22, and the similarities will not be repeated. The differences are:

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

Example 25

The cleaning methods of Embodiment 25 are basically the same as those of Embodiment 22, and the similarities will not be repeated. The differences are:

The photoresist cleaning solution in this embodiment includes the following mass percentage components: 35% first cleaning agent, 40% second cleaning agent, 10% metal corrosion inhibitor, and 15% deionized water. The pyrrolidone compound is N-propylpyrrolidone, the alkyl ammonium hydroxide is methyltriethylammonium hydroxide, and the metal corrosion inhibitor is hydroxybenzotriazole.

Example 26

The cleaning methods of Embodiment 26 are basically the same as those of Embodiment 22, and the similarities will not be repeated. The differences are:

The photoresist cleaning solution in this embodiment includes the following mass percentage components: 55% first cleaning agent, 20% second cleaning agent, 5% metal corrosion inhibitor, and 20% deionized water. The pyrrolidone compound is N-cycloethylpyrrolidone, the alkyl ammonium hydroxide is benzyltrimethylammonium hydroxide, and the metal corrosion inhibitor is hydroxybenzotriazole.

In Examples 22 to 26, the first cleaning agent and the second cleaning agent are directly mixed to form a photoresist cleaning liquid and then cleaned. The cleaning method is simpler and the operating steps are simplified. The technical solutions of Examples 22 to 26 of the present application are respectively used to clean the chromium-plated substrate, and good cleaning effects can also be achieved. There is no sign of corrosion on the chromium film on the surface of the substrate macroscopically; and the observations under the microscope are carried out using Examples 22 to 26. The photoresist cleaning solution and cleaning method provided in Example 26 will not damage the chromium film on the surface of the substrate.

The embodiments of the present application have been described above in conjunction with the accompanying drawings. However, the present application is not limited to the above-mentioned specific implementations. The above-mentioned specific implementations are only illustrative and not restrictive. Those of ordinary skill in the art will Inspired by this application, many forms can be made without departing from the purpose of this application and the scope protected by the claims, all of which fall within the protection of this application.

Industrial applicability

The photoresist cleaning solution and its preparation method and cleaning method provided in the embodiments of the present application can completely remove the photoresist without corroding the metal film, especially without corroding the chromium film, and can realize repeated coating of chromium-plated substrates. Utilization has significant economic benefits.

Claims

A photoresist cleaning liquid, characterized in that the photoresist cleaning liquid includes: a cleaning agent, a metal corrosion inhibitor and water; wherein the cleaning agent includes a first cleaning agent and/or a second cleaning agent;

The first cleaning agent includes pyrrolidone compounds, the second cleaning agent includes alkyl ammonium hydroxide, and the metal corrosion inhibitor includes benzotriazole and its derivatives.
The photoresist cleaning solution according to claim 1, wherein the photoresist cleaning solution includes 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.
The photoresist cleaning solution according to claim 2, wherein the first photoresist cleaning solution includes the following mass percentage components: 45%-95% of the first cleaning agent, 0.01%-10% of metal corrosion inhibitors and balance water.
The photoresist cleaning solution according to claim 3, characterized in that the first photoresist cleaning solution includes the following mass percentage components: 60%-90% of the first cleaning agent, 0.01%-5% of metal corrosion inhibitors and balance water.
The photoresist cleaning solution according to claim 2, wherein the second photoresist cleaning solution includes the following mass percentage components: 50%-95% second cleaning agent, 0.01%-10% of metal corrosion inhibitors and balance water.
The photoresist cleaning solution according to claim 5, characterized in that the second photoresist cleaning solution includes the following mass percentage components: 60%-95% second cleaning agent, 0.01%-5% of metal corrosion inhibitors and balance water.
The photoresist cleaning solution according to claim 1, characterized in that the photoresist cleaning solution includes the following mass percentage components: 35%-55% of the first cleaning agent, 20%-40% of the third cleaning agent 2. Cleaning agent, 0.01%-10% metal corrosion inhibitor and the balance water.
The photoresist cleaning solution according to any one of claims 1 to 7, characterized in that the pyrrolidone compounds include N-methylpyrrolidone, N-ethylpyrrolidone, N-hydroxyethylpyrrolidone, N-propylpyrrolidone At least one of N-butylpyrrolidone, N-butylpyrrolidone or N-cyclohexylpyrrolidone.
The photoresist cleaning solution according to any one of claims 1 to 7, wherein the alkyl ammonium hydroxide includes tetramethyl ammonium hydroxide, tetraethylammonium hydroxide, and tetrapropylammonium hydroxide. , at least one of tetrabutylammonium hydroxide, methyltriethylammonium hydroxide, benzyltrimethylammonium hydroxide or benzyltriethylammonium hydroxide.
The photoresist cleaning solution according to any one of claims 1 to 7, characterized in that the benzotriazole and its derivatives include benzotriazole, hydroxybenzotriazole, alkylbenzene At least one of benzotriazole or carboxybenzotriazole.
A method for preparing a photoresist cleaning solution according to any one of claims 1 to 10, characterized in that the preparation method includes: mixing a cleaning agent, a metal corrosion inhibitor and water evenly to obtain the photoresist cleaning solution. Resin cleaning fluid.
The preparation method of photoresist cleaning solution according to claim 11, characterized in that the preparation method includes:

Mix the first cleaning agent, metal corrosion inhibitor and water evenly to obtain a first photoresist cleaning solution;

Mix the second cleaning agent, metal corrosion inhibitor and water evenly to obtain a second photoresist cleaning solution.
A cleaning method for cleaning photoresist using the photoresist cleaning liquid according to any one of claims 1 to 10, characterized in that the photoresist cleaning liquid includes a first photoresist cleaning liquid and a second photoresist cleaning liquid. Photoresist cleaning solution, the cleaning method includes:

(a) Place the device to be cleaned containing photoresist in the second photoresist cleaning solution and perform immersion cleaning;

(b) Rinse the device to be cleaned with water after cleaning in step (a);

(c) Place the device to be cleaned after flushing in step (b) into the first photoresist cleaning solution for cleaning;

(d) Rinse the device to be cleaned after cleaning in step (c) with water and then dry;

Wherein, the temperature range for cleaning using the second photoresist cleaning liquid or the first photoresist cleaning liquid is 25°C-60°C;

And/or, the cleaning time using the second photoresist cleaning solution or the first photoresist cleaning solution is 5 minutes to 40 minutes.
The cleaning method according to claim 13, wherein step (c) specifically includes:

Place the device to be cleaned after rinsing in step (b) into the first photoresist cleaning solution and perform ultrasonic cleaning. The temperature of ultrasonic cleaning is 25°C-35°C, and the time of ultrasonic cleaning is 5min-20min;

After the ultrasonic cleaning is completed, the first photoresist cleaning solution is heated to a predetermined temperature and soaked for cleaning. The predetermined temperature is 45°C-55°C, and the soaking and cleaning time is 5min-20min.
The cleaning method according to claim 13, wherein step (d) specifically includes:

The device to be cleaned after cleaning in step (c) is first rinsed with water, then ultrasonic cleaned with an alcohol solvent, and then rinsed with water; the ultrasonic cleaning temperature is 25°C-35°C, and the ultrasonic cleaning time is 15 minutes -30min;

Then dry it using nitrogen blow drying and hot stage drying.
A cleaning method for cleaning photoresist using the photoresist cleaning liquid according to any one of claims 1 to 10, characterized in that the photoresist cleaning liquid includes a first cleaning agent, a second cleaning agent, Metal corrosion inhibitor and water; the cleaning method includes:

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

(b) Rinse the device to be cleaned with water after cleaning in step (a);

(c) Place the device to be cleaned after flushing in step (b) into an alcohol solvent for ultrasonic cleaning;

(d) Rinse the device to be cleaned after cleaning in step (c) with water and then dry it.