Chip photoresist cleaning solution as well as preparation method and application thereof
By using a composite corrosion inhibitor of phenyl phosphate derivatives and fluorinated dendritic polymers, a protective film is formed to isolate water molecules from contact with the metal, thus solving the corrosion problem of photoresist cleaning solution on active metals such as aluminum and copper, achieving efficient cleaning and improved yield.
Patent Information
- Application Number
- CN202510829895.8
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-06-20
- Publication Date
- 2025-11-07
AI Technical Summary
Existing photoresist cleaning solutions cause severe corrosion to reactive metals such as aluminum and copper during the removal process, affecting wafer yield. Moreover, as device geometry shrinks, the metal corrosion problem becomes increasingly serious.
A compound corrosion inhibitor consisting of phenyl phosphate derivatives and fluorinated dendritic polymers is used to form a micelle-film bilayer structure. This structure forms a protective film on the metal surface by adsorption, isolating water molecules from contacting the metal and reducing the corrosion rate.
This technology enables efficient cleaning of photoresist using a pure immersion process, resulting in virtually no corrosion, protecting the metal surface, and improving wafer yield.
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Figure CN120904971A_ABST
Abstract
Description
TECHNICAL FIELD
[0001] The present application relates to photoresist cleaning liquid technology, in particular to a chip photoresist cleaning liquid and a preparation method and application thereof. BACKGROUND
[0002] In the semiconductor manufacturing process, it is necessary to form a photoresist mask on the surface of the material. After the desired pattern is obtained through the exposure and pattern transfer process, the wafer surface will be left with photoresist used as a mask. These residual photoresist must be completely removed before the next process, and it is necessary to ensure that no corrosion occurs to any substrate during the cleaning process.
[0003] At present, the photoresist cleaning liquid mainly consists of polar organic solvents, strong alkalis and / or water, etc. Its cleaning method includes immersing the semiconductor wafer in the cleaning liquid or directly washing it. However, due to the presence of strong alkalis in the cleaning liquid, serious and widespread corrosion problems often occur during the chemical cleaning of photoresist, especially for active metals such as aluminum and copper, thereby significantly reducing the yield of the wafer. With the continuous reduction of device geometry, integrated circuit manufacturers have increasingly lower tolerance for metal corrosion. Therefore, it is urgent to develop a new type of photoresist cleaning liquid to solve the problem of metal corrosion. SUMMARY
[0004] The purpose of the present application is to solve the problem that the traditional photoresist cleaning liquid is easy to cause corrosion of the chip. A chip photoresist cleaning liquid is provided, which can achieve efficient cleaning only through pure immersion process without relying on ultrasonic assistance, and has almost no corrosion to the chip. The chip photoresist cleaning liquid of the present application has very good application prospect and large-scale industrialization potential in the field of photoresist cleaning.
[0005] It should be noted that in the present application, unless otherwise specified, the specific meaning of "including" involved in the composition limitation and description includes both the open "including", "containing" and the like, and the closed "consisting of", "consisting of" and the like.
[0006] To achieve the above purpose, the technical scheme adopted by the present application is: a chip photoresist cleaning liquid, comprising the following components in a weight ratio:
[0007]
[0008] The corrosion inhibitor is a mixture of phenyl phosphate ester derivatives and fluorinated dendritic polymers.
[0009] Further, the quaternary ammonium hydroxide is one or more of tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide and choline hydroxide.
[0010] Further, the quaternary ammonium hydroxide is preferably tetramethylammonium hydroxide.
[0011] Further, the quaternary ammonium hydroxide is 2-3 parts.
[0012] Further, the alkanolamine is one or more of monoethanolamine, diethanolamine, triethanolamine, methyldiethanolamine, diglycolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine, and hydroxyethylethylenediamine.
[0013] Further, the alkanolamine is preferably diglycolamine.
[0014] Further, the alkanolamine is 3-10 parts.
[0015] Further, the sulfoxide is one or more of dimethyl sulfoxide, diethyl sulfoxide, dibutyl sulfoxide, and tetramethylene sulfoxide.
[0016] Further, the sulfoxide is preferably tetramethylene sulfoxide.
[0017] Further, the sulfoxide is 60-80 parts.
[0018] Further, the phenyl phosphate derivative and fluorinated dendrimer weight ratio is 1-3:1.
[0019] Further, the phenyl phosphate derivative and fluorinated dendrimer weight ratio is preferably 1.7:1.
[0020] Further, the phenyl phosphate derivative is one or more of tetraphenyl bisphenol A diphosphate, resorcinol tetraphenyl diphosphate, di(2,6-dimethylphenyl) phosphate, triisopropylphenyl phosphate, O,O-diethyl S-phenyl phosphate, bis(4-aminophenyl) phosphate, monomethyl phenyl phosphate, di(2-ethylhexyl) phenyl phosphate, bis(4-nitrophenyl) phosphate hydrate, t-butyl phenyl phenyl phosphate, and 4-biphenyloxy diphenyl phosphate.
[0021] Further, the phenyl phosphate derivative is preferably tetraphenyl bisphenol A diphosphate and / or resorcinol tetraphenyl diphosphate.
[0022] Further, the fluorinated dendrimer is one or more of Nafion perfluorinated resin, polychlorotrifluoroethylene-co-vinylidene fluoride copolymer, and fluorinated benzothiadiazole core dendrimer.
[0023] Further, the fluorinated dendrimer is preferably fluorinated benzothiadiazole core dendrimer.
[0024] The present application adopts a complex inhibitor: phenyl phosphate derivative and fluorinated dendritic polymer are compounded to form a micelle-membrane bilayer structure. In alkaline conditions, the phenyl phosphate derivative will have a binding force with the metal surface, adsorbed on the metal surface to form a monolayer, and the fluorinated dendritic polymer is easy to form micelles or lamellar structure in the solution, the hydrophobic core can wrap the trace amount of water molecules absorbed by the cleaning solution in contact with air, reduce the water activity, and the fluorinated dendritic polymer wraps water molecules in the solution by hydrophobic interaction, double isolation of water and metal contact, thereby reducing the corrosion rate of the metal.
[0025] Further, the inhibitor is 0.5-3 parts.
[0026] Another object of the present application also discloses a preparation method of a chip photoresist cleaning solution, comprising the following steps:
[0027] The quaternary ammonium hydroxide, alkanolamine, sulfoxide and inhibitor are weighed respectively, mixed and stirred uniformly to obtain the chip photoresist cleaning solution.
[0028] Further, the mixing and stirring time is 0.5-1h.
[0029] Another object of the present application also discloses the application of the chip photoresist cleaning solution in the field of semiconductor chip cleaning.
[0030] Further, the steps of cleaning the semiconductor chip using the chip photoresist cleaning solution are as follows:
[0031] Step 1: soaking the semiconductor chip in the chip photoresist cleaning solution for cleaning;
[0032] Step 2: after the semiconductor chip cleaned in step 1 is immersed in isopropyl alcohol, it is washed with ultrapure water and dried with normal temperature nitrogen, the semiconductor chip cleaning is completed.
[0033] Further, the cleaning method in step 1 is not limited, and can be one or a combination of immersion stripping cleaning, swing stripping cleaning, single wafer stripping cleaning, spinner rotating stripping cleaning and ultrasonic stripping cleaning.
[0034] Further, the cleaning temperature in step 1 is 35-60℃, and the cleaning time is 10-50min.
[0035] Further, the immersion time in step 2 is 5-10min.
[0036] The chip photoresist cleaning solution, the preparation method and the application thereof have the following advantages compared with the prior art:
[0037] 1) The photoresist cleaning solution of the present application adopts a combination of phenyl phosphate ester derivatives and fluorinated dendritic polymers to obtain a compounded corrosion inhibitor. The phenyl phosphate ester derivatives can form a protective film on the metal surface that needs protection, and the fluorinated dendritic polymers have a three-dimensional dendritic structure to provide a high specific surface area, tightly cover the metal surface through van der Waals force, and fill the pores not covered by the phosphate ester. This protective film can isolate the metal from the corrosive medium and prevent the release of metal ions, thereby protecting the metal from corrosion. The fluorinated chain (-CF2 or -CF3) in the fluorinated dendritic polymer forms a superhydrophobic effect, wrapping water molecules in the solution, while the fluorinated dendritic polymer in the solution easily forms micelles or lamellar structures, with the hydrophobic core wrapping water molecules, reducing water activity, and double isolating water from the metal, thereby reducing the corrosion rate of the metal.
[0038] 2) The alkanolamine in the chip photoresist stripping agent of the present application is preferably diglycolamine, and the quaternary ammonium hydroxide is preferably tetramethylammonium hydroxide. Both have the effect of reducing metal corrosion in a specific ratio, and can better protect the electrode and reduce the attack on the electrode.
[0039] In summary, the chip photoresist cleaning solution of the present application has good application prospects and large-scale promotion potential in the field of semiconductor chip cleaning. BRIEF DESCRIPTION OF DRAWINGS
[0040] Figure 1 The surface microscope picture of the semiconductor wafer before cleaning is magnified 50 times.
[0041] Figure 2 The microscope picture of the semiconductor wafer after cleaning with the chip photoresist cleaning solution of Example 1 is magnified 50 times.
[0042] Figure 3 The microscope picture of the semiconductor wafer soaked for 2h with the chip photoresist cleaning solution of Example 1 is magnified 50 times.
[0043] Figure 4 The microscope picture of the semiconductor wafer soaked for 2h with the cleaning solution of Comparative Example 1 is magnified 50 times. DETAILED DESCRIPTION
[0044] Hereinafter, the present application will be further described in conjunction with examples. The description of the technical features described below is based on representative embodiments, specific examples of the present application, but the present application is not limited to these embodiments, specific examples. It should be noted that:
[0045] Unless otherwise stated, the units used in this specification are international standard units, and the numerical values and numerical ranges appearing in this application should be understood to include the systematic errors that are unavoidable in industrial production.
[0046] In the present specification, a numerical range indicated using "numerical value A to numerical value B" means a range including the end point numerical values A and B.
[0047] In the present specification, a numerical range indicated using "above" or "below" means a range including the present numerical value.
[0048] In the present specification, the meaning indicated using "may" includes both the meaning of performing a certain process and the meaning of not performing a certain process.
[0049] In the present specification, "optionally" or "optional" means that a certain substance, component, execution of a step, application of a condition, and the like is used or not used.
[0050] In the present specification, when "ordinary temperature" or "room temperature" is used, the temperature can be 15-25°C.
[0051] In the present specification, when a manufacturer of a reagent or an instrument is not indicated, it is a general product that can be obtained by purchase in the market.
[0052] Examples 1-8
[0053] Examples 1-8 disclose various chip photoresist cleaning solutions, which contain components and weight ratios as shown in Table 1, and the preparation method is as follows: each component is weighed, and quaternary ammonium hydroxide, alkanolamine, sulfoxide, and corrosion inhibitor are added to a container, respectively, stirred for 1 h, and mixed and stirred uniformly to obtain the chip photoresist cleaning solution.
[0054] The steps of cleaning the semiconductor chip using the chip photoresist cleaning solution are as follows:
[0055] Step 1: immerse the semiconductor chip in the chip photoresist cleaning solution at 40°C for cleaning for 30 min;
[0056] Step 2: after cleaning the semiconductor chip in step 1, immerse it in isopropanol for 10 min, then wash it with ultrapure water, and then blow dry it with normal temperature nitrogen, thereby completing the cleaning of the semiconductor chip.
[0057] Table 1 Components and weight ratios of chip photoresist cleaning solutions in Examples 1-8
[0058]
[0059]
[0060] Comparative Examples 1-4
[0061] Comparative Examples 1-4 disclose various cleaning solutions, which contain components and weight ratios as shown in Table 2, and the preparation method is the same as that of Example 1.
[0062] Table 2: Components and weight ratio of cleaning solution of Comparative Examples 1-4
[0063]
[0064]
[0065] The chip photoresist cleaning solution of Examples 1-8 and the cleaning solution of Comparative Examples 1-4 were tested respectively, and the test method and test results are as follows.
[0066] Table 3: Test results
[0067]
[0068] As can be seen from Table 3, the corrosion rate of the chip photoresist cleaning solution prepared by Examples 1-8 on the metal copper is less than It is proved that the chip photoresist cleaning solution has good corrosion resistance to the metal copper layer; and the corrosion rate of the cleaning solution prepared by Comparative Examples 1-4 is larger after cleaning, which shows that the absence of corrosion inhibitor or the replacement of corrosion inhibitor will lead to the increase of the corrosion of the metal copper layer.
[0069] Comparative Example 1 and Example 1, due to the absence of phenyl phosphate ester derivatives, the copper corrosion is increased from to From the two data, it can be proved that the cleaning solution prepared by Comparative Example 1 has poor corrosion resistance to the metal copper layer; Comparative Example 2 and Example 1, due to the absence of fluorinated dendritic polymer, the copper corrosion is increased from to Comparative Examples 3-4 and Example 1, due to the replacement of corrosion inhibitor to benzothiazole and catechol, the cleaning solution prepared by Comparative Examples 3-4 has poor corrosion resistance to the metal copper layer.
[0070] Figure 1 It is a 50 times magnified surface microscope picture of the semiconductor wafer before cleaning; it can be seen that the photoresist is reserved on the semiconductor wafer. Figure 2 It is a 50 times magnified microscope picture of the semiconductor wafer after cleaning using the chip photoresist cleaning solution of Example 1. It can be seen that the photoresist on the semiconductor wafer has been removed; Figure 3 It is a 50 times magnified microscope picture of the semiconductor wafer soaked for 2h using the chip photoresist cleaning solution of Example 1. It can be seen that the Cu surface is not corroded, which shows that the corrosion inhibitor compounded by phenyl phosphate ester derivatives and fluorinated dendritic polymer has good protection performance on Cu. Figure 4 It is a 50 times magnified microscope picture of the semiconductor wafer soaked for 2h using the cleaning solution of Comparative Example 1. It can be seen that the Cu surface is corroded to a certain extent, which shows that when the composition of the corrosion inhibitor is changed from two components to one component, the corrosion rate is obviously increased.
[0071] The test method of performance 1 metal corrosion is that four-probe tester is used to test the corrosion performance of different cleaning solutions on metal Cu. The specific test method is that the Cu sheet with a size of 2*2 cm is tested by four-probe tester before wafer thickness, immersed in the cleaning solution at 40℃, the immersion time is 2 hours, then the wafer thickness after test is tested by four-probe tester, and the corrosion rate of each is calculated by the difference 2 Thus the corrosion rate of different examples and comparative examples on metal Cu is obtained.
[0072] Finally, it should be pointed out that: the above examples are only used to illustrate the technical solutions of the present application, but not to limit it; although the present application has been described in detail with reference to the foregoing examples, those skilled in the art should understand that: it can still modify the technical solutions recorded in the foregoing examples, or make equivalent replacement for part or all of the technical features; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the scope of the technical solutions of the embodiments of the present application.
Claims
1. A chip photoresist cleaning solution, characterized by, The components include the following components in the following proportions by weight: The corrosion inhibitor is a mixture of a phenyl phosphate derivative and a fluorinated dendrimer.
2. The chip photoresist cleaning solution according to claim 1, wherein The quaternary ammonium hydroxide is one or more of tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide, and choline hydroxide.
3. The chip photoresist cleaning solution of claim 1, wherein The alkanolamine is one or more of monoethanolamine, diethanolamine, triethanolamine, methyldiethanolamine, diglycolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine, and hydroxyethylethylenediamine.
4. The chip photoresist cleaning solution of claim 1, wherein The sulfoxide is one or more of dimethyl sulfoxide, diethyl sulfoxide, dibutyl sulfoxide, and tetramethylene sulfoxide.
5. The chip photoresist cleaning solution of claim 1, wherein The weight ratio of the phenyl phosphate derivative to the fluorinated dendrimer is 1-3:
1.
6. The chip photoresist cleaning solution of claim 1, wherein The phenyl phosphate derivative is one or more of tetraphenyl bisphenol A diphosphate, resorcinol tetraphenyl diphosphate, di(2,6-dimethylphenyl)phosphate, triisopropylphenyl phosphate, O,O-diethyl S-phenylphosphate, bis(4-aminophenyl)phosphate, monomethyl phenylphosphate, di(2-ethylhexyl)phenyl phosphate, bis(4-nitrophenyl)phosphate hydrate, t-butyl phenyl phenylphosphate, and 4-biphenyloxy diphenyl phosphate.
7. The chip photoresist cleaning solution of claim 1, wherein The fluorinated dendrimer is one or more of Nafion perfluorinated resin, polychlorotrifluoroethylene-vinylidene fluoride copolymer, and fluorinated benzothiadiazole core dendrimer.
8. A method for preparing the chip photoresist cleaning solution according to any one of claims 1 to 7, characterized by, The steps include: The quaternary ammonium hydroxide, the alkanolamine, the sulfoxide, and the corrosion inhibitor are weighed and mixed to obtain the chip photoresist cleaning solution.
9. Use of the chip photoresist cleaning solution of any one of claims 1-7 in the field of semiconductor chip cleaning.
10. Use according to claim 9, characterized in that, The steps of cleaning the semiconductor chip using the chip photoresist cleaning solution are as follows: Step 1: Soaking the semiconductor chip in the chip photoresist cleaning solution for cleaning; Step 2: After cleaning the semiconductor chip in step 1, immersing the semiconductor chip in isopropanol, rinsing with ultrapure water, and blowing dry with nitrogen, the cleaning of the semiconductor chip is completed.