A method for determining the content of diazonaphthoquinone sensitizer in photoresist

Abstract

The present application relates to the technical field of analytical chemistry and specifically discloses a method for determining the content of diazonaphthoquinone sensitizers in photoresists. The determination method disclosed in the present application specifically comprises the following steps: diluting a sample to be tested and a standard sample of diazonaphthoquinone sensitizer using an organic solvent, filtering, and obtaining a sample solution to be tested and a standard solution; testing the sample solution to be tested and the standard solution using a high-performance liquid chromatograph, and calculating the content of the diazonaphthoquinone sensitizer in the sample to be tested. The determination method provided in the present application is simple to operate and has high detection efficiency. The determination method also has the advantages of good linearity, good experimental repeatability, high precision of the determination results, and high accuracy.

Description

Technical Field

[0001] The present application relates to the technical field of analytical chemistry, and in particular to a method for determining the content of diazonaphthoquinone sensitizer in photoresist. Background Art

[0002] Photoresist, also known as photoresist, is a light-sensitive liquid mixture composed of three main components: a photosensitive resin, a photosensitizer (PAC), and a solvent. Among them, photoresists containing diazonaphthoquinone-based sensitizers and alkali-soluble resins can be used as positive photoresists. This is because when exposed to ultraviolet light, the diazonaphthoquinone groups decompose to form carboxyl groups, making the originally alkali-insoluble composition alkali-soluble and accelerating the alkali dissolution rate of the photoresist composition. In unexposed areas, the diazonaphthoquinone groups will form a certain degree of bond with the resin, thereby reducing the alkali dissolution rate of the photoresist composition. This difference in dissolution rate between exposed and unexposed areas can be exploited to achieve pattern transfer.

[0003] In panel photoresists, commonly used PACs are diazonaphthoquinone compounds, which are generally prepared by the esterification reaction of diazonaphthoquinone (benzo)quinone sulfonyl chloride with phenolic compounds. There are hundreds of industrially synthesized diazonaphthoquinone PACs, a typical one being shown in formula (III): In the structural formula, D represents diazonaphthoquinone (DNQ):

[0004]

[0005] In panel photoresists, naphthoquinone azido-2,3,4-trihydroxybenzophenone PAC-3 (3-THBP) and naphthoquinone azido-2,3,4,4'-tetrahydroxybenzophenone PAC-4 (4-THBP) are the most widely used. Because naphthoquinone azido-based photosensitive products contain monoester, diester, triester, and tetraester structures, and each ester has several isomers, their quantification is difficult using conventional methods.

[0006] Currently, there is still a blank in the technical field of determining the content of diazonaphthoquinone sensitizers in photoresists. Summary of the Invention

[0007] In order to accurately quantify the content of diazonaphthoquinone sensitizer in photoresist, the present application provides a method for determining the content of diazonaphthoquinone sensitizer in photoresist.

[0008] The present application provides a method for determining the content of diazonaphthoquinone sensitizer in a photoresist, which adopts the following technical solution:

[0009] A method for determining the content of naphthoquinone diazide sensitizer in a photoresist comprises the following steps:

[0010] Diluting the sample to be tested and the standard solution of naphthoquinone diazide sensitizer with an organic solvent, filtering, and obtaining a sample solution to be tested and a standard solution;

[0011] The sample solution and the standard solution are tested by high performance liquid chromatography, and the content of the diazonaphthoquinone sensitizer in the sample is calculated;

[0012] The test conditions of the high performance liquid chromatography are as follows: the chromatographic column filler is an alkyl bonded phase; the column temperature is 20-45°C; the mobile phase is a 1-2 v / v% acid aqueous solution-methanol-tetrahydrofuran mixed solution with a volume ratio of (46-58): (7-13): (34-42); the elution mode is isocratic elution; the flow rate is 0.5-2 mL / min; and the injection volume is 5-50 μL.

[0013] This application uses an organic solvent to pre-treat the sample to be tested, and then uses high-performance liquid chromatography to separate and test the sample to be tested, and reasonably adjusts the test conditions such as column temperature, mobile phase, flow rate and injection volume, providing a method for determining the content of diazonaphthoquinone sensitizers in photoresists. This determination method has the advantage of high detection accuracy.

[0014] The mobile phase of high-performance liquid chromatography can be composed of a single solvent or two or more solvents, and different solvents have different elution abilities for the target. This application utilizes a mixed solution of 1-2 v / v% acid aqueous solution, methanol, and tetrahydrofuran as the mobile phase, and controls the volume ratio of the components in the mobile phase to perform isocratic elution on the sample to be tested. This can significantly improve the separation of diazonaphthoquinone sensitizers and other impurities in the sample to be tested, thereby greatly improving the detection efficiency. Furthermore, this assay method has the advantages of good linearity, good experimental repeatability, and high precision and accuracy of the results.

[0015] In addition, the present application uses isocratic elution to separate and test the samples to be tested. Since the ratio of the mobile phase does not change when the method is running, it does not have high requirements on the instrument. Only one unit pump is needed to run the method, and the type of chromatographic column and detector of the high performance liquid chromatography can be flexibly selected.

[0016] Preferably, in the method for determining the content of naphthoquinone diazide photosensitizer in the photoresist, the sample to be tested and the naphthoquinone diazide photosensitizer standard are diluted and detected under a yellow light room environment.

[0017] In order to prevent the photosensitivity of the photosensitive materials, the entire operation is carried out in a yellow light room as much as possible during the testing process to further ensure the accuracy of the test results.

[0018] Preferably, the organic solvent is selected from one or more of alkanes, ketones and furans.

[0019] Furthermore, the organic solvent is selected from one or more of chloroform, N-methylpyrrolidone, and tetrahydrofuran.

[0020] The present application selects the above-mentioned organic solvent to pre-treat the sample to be tested, which can be fully mixed with the photoresist sample to be tested, ensuring that the diazonaphthoquinone sensitizer in the sample to be tested is fully dissolved, thereby ensuring the accuracy of the test result; at the same time, this operation process is simple and easy, and the reagents are easy to purchase, further reducing the cost of testing. In the process of selecting solvents, the applicant of the present application found that compared with alkanes, ketones, and furan solvents, alcohol solvents (such as methanol, ethanol), ether solvents (such as ether, petroleum ether) and benzene solvents (such as toluene) have poor compatibility with the sample to be tested, and therefore are not used as the preferred solution for the organic solvent of the present application.

[0021] Preferably, the chromatographic column filler is selected from one of C4, C8, C12, and C18 alkyl bonded phases; the specifications are: length 10-25 cm, inner diameter 3.2-4.6 mm, and particle size 3-5 μm.

[0022] Furthermore, the chromatographic column is Shim-pack C18, with a specification of 250 mm×4.6 mm and a particle size of 3 μm.

[0023] Preferably, the mobile phase is a 1-2 v / v% acid aqueous solution-methanol-tetrahydrofuran mixed solution with a volume ratio of (50-54): (9-11): (36-40).

[0024] In a specific embodiment, the mobile phase can be: a mixed solution of acid aqueous solution-methanol-tetrahydrofuran with a volume ratio of 52:10:38, 46:10:44, 50:10:40, 54:10:36, 58:7:35, 52:9:39, or 52:11:37.

[0025] In some specific embodiments, the mobile phase can be: a mixed solution of acid aqueous solution-methanol-tetrahydrofuran with a volume ratio of (50-54):10:38, 46:(9-11):44, 50:10:(36-40).

[0026] Preferably, the acid aqueous solution is one or both of a formic acid aqueous solution and an acetic acid aqueous solution.

[0027] Furthermore, the concentration of the acid aqueous solution is 1.3-1.7 v / v%.

[0028] In a specific embodiment, the concentration of the acid aqueous solution can be 1 v / v%, 1.3 v / v%, 1.5 v / v%, 1.7 v / v%, or 2 v / v%.

[0029] In some specific embodiments, the concentration of the acid aqueous solution can also be 1-1.3 v / v%, 1-1.5 v / v%, 1-1.7 v / v%, 1.3-1.5 v / v%, 1.3-2 v / v%, 1.5-1.7 v / v%, 1.5-2 v / v%, 1.7-2 v / v%.

[0030] Preferably, the column temperature is 30-45°C.

[0031] In a specific embodiment, the column temperature can be 20°C, 30°C, 35°C, or 45°C.

[0032] In some specific embodiments, the column temperature can also be 20-30°C, 20-35°C, 30-35°C, or 35-40°C.

[0033] Preferably, the flow rate is 1-2 mL / min.

[0034] In a specific embodiment, the flow rate can be 0.5 mL / min, 1 mL / min, or 2 mL / min.

[0035] In some specific embodiments, the flow rate may also be 0.5-1 mL / min.

[0036] Preferably, the detector used in the high performance liquid chromatography is one of an ultraviolet detector, a diode array detector, and a differential detector.

[0037] Furthermore, when the detector used in the high performance liquid chromatography is an ultraviolet detector or a diode array detector, the detection wavelength is 280-380 nm.

[0038] In some specific embodiments, when the detector used in the high performance liquid chromatography is an ultraviolet detector, the detection wavelength is 365 nm.

[0039] Optionally, the naphthoquinone diazide photosensitizer includes any one or more of the following structures:

[0040]

[0041] In summary, the technical solution of this application has the following effects:

[0042] The present application utilizes an organic solvent to pre-treat a sample to be tested, and then utilizes high performance liquid chromatography to separate and test the sample to be tested, providing a method for determining the content of diazonaphthoquinone sensitizer in a photoresist.

[0043] This application greatly improves the detection efficiency by screening organic solvents and rationally adjusting the test conditions such as column temperature, mobile phase, flow rate and injection volume in the high performance liquid chromatography test conditions. At the same time, the determination method has the advantages of good linearity, good experimental repeatability, and high precision and accuracy of the determination results.

[0044] The present application uses isocratic elution to separate and test the sample to be tested, and can flexibly select the type of chromatographic column and detector of the high performance liquid chromatography. BRIEF DESCRIPTION OF THE DRAWINGS

[0045] Figure 1 This is the liquid phase spectrum of the 3-THBP standard in Example 1.

[0046] Figure 2 This is the standard curve of the 3-THBP standard in Example 1.

[0047] Figure 3 This is the liquid phase spectrum of photoresist sample 1 in Example 1.

[0048] Figure 4 This is the liquid phase spectrum of the 4-THBP standard in Example 2.

[0049] Figure 5 This is the standard curve of the 4-THBP standard in Example 2.

[0050] Figure 6 This is the liquid phase spectrum of photoresist sample 2 in Example 2.

[0051] Figure 7 This is the liquid chromatography spectrum of the mixed standard of 3-THBP and 4-THBP in Example 3.

[0052] Figure 8 This is the standard curve of the mixed standard of 3-THBP and 4-THBP in Example 3.

[0053] Figure 9 This is the liquid phase spectrum of photoresist sample 3 in Example 3. DETAILED DESCRIPTION

[0054] In a first aspect, the present application provides a method for determining the content of a diazonaphthoquinone sensitizer in a photoresist, which specifically comprises the following steps:

[0055] Diluting the sample to be tested and the standard solution of naphthoquinone diazide sensitizer with an organic solvent, filtering, and obtaining a sample solution to be tested and a standard solution;

[0056] The sample solution and the standard solution are tested by high performance liquid chromatography, and the content of the diazonaphthoquinone sensitizer in the sample is calculated;

[0057] Among them, the test conditions of high performance liquid chromatography are as follows: the chromatographic column packing is an alkyl bonded phase; the column temperature is 20-45°C; the mobile phase is a 1-2 v / v% acid aqueous solution-methanol-tetrahydrofuran mixed solution with a volume ratio of (46-58): (7-13): (34-42); the elution mode is isocratic elution; the flow rate is 0.5-2 mL / min; and the injection volume is 5-50 μL.

[0058] The organic solvent is selected from one or more of alkanes, ketones and furans.

[0059] Specifically, the organic solvent is selected from one or more of chloroform, N-methylpyrrolidone, and tetrahydrofuran.

[0060] The chromatographic column filler is selected from one of C4, C8, C12, and C18 alkyl bonded phases; the specifications are: length 10-25 cm, inner diameter 3.2-4.6 mm, and particle size 3-5 μm.

[0061] Furthermore, the chromatographic column is Shim-pack C18, with a specification of 250 mm × 4.6 mm and a particle size of 3 μm.

[0062] Meanwhile, the acid aqueous solution is one or both of a formic acid aqueous solution and an acetic acid aqueous solution.

[0063] Furthermore, the concentration of the acid aqueous solution is 1.3-1.7 v / v%.

[0064] In addition, the detector used in high performance liquid chromatography is one of an ultraviolet detector, a diode array detector, and a differential detector.

[0065] When the detector used in the high performance liquid chromatography is an ultraviolet detector or a diode array detector, the detection wavelength is 280-380 nm.

[0066] Furthermore, when the detector used in the high performance liquid chromatography is an ultraviolet detector, the detection wavelength is 365 nm.

[0067] Furthermore, the naphthoquinone diazide sensitizer includes any one or more of the following structures:

[0068]

[0069] The present application is further described in detail below in conjunction with examples, comparative examples and performance testing experiments. These examples should not be construed as limiting the scope of protection claimed in this application.

[0070] Example

[0071] Example 1

[0072] Example 1 provides a method for determining the content of diazonaphthoquinone sensitizer (3-THBP) in photoresist.

[0073] (1) Pretreatment of the sample to be tested

[0074] The sample to be tested is photoresist sample 1 (purchased from Merck, containing 5.35 wt % of diazonaphthoquinone photosensitizer 3-THBP).

[0075] In a yellow light room, weigh 99.3 mg, 105.5 mg, and 103.6 mg of sample 1, respectively, accurate to 0.1 mg, place them in a 10 mL volumetric flask, dissolve them in tetrahydrofuran, and dilute to the scale.

[0076] The prepared sample solution was allowed to stand for 0.5 h, and part of the solution was removed with a 2 mL syringe. After filtering with a 0.45 μm filter membrane, the sample solution to be tested was obtained and tested by high performance liquid chromatography.

[0077] (2) Preparation of standard solution

[0078] 95.6 mg of 3-THBP standard sample (purchased from Migen Trading Co., Ltd.) was weighed to the nearest 0.1 mg, placed in a 50 mL volumetric flask, dissolved in tetrahydrofuran, and diluted to the mark.

[0079] Use a 5mL pipette to measure 0.5mL, 1mL, 2.0mL, and 5mL of the above solution into a 10mL volumetric flask, and dilute to the scale to obtain 4 standard solutions of different concentrations. Add the mother solution to obtain a total of 5 standard solutions.

[0080] The solution was transferred with a 2 mL syringe, filtered with a 0.45 μm filter membrane, and then tested on a high performance liquid chromatograph. A standard curve was drawn based on the test results.

[0081] (3) Test conditions

[0082] Shimadzu LC-20AD high performance liquid chromatograph, chromatographic column (Shim-pack C18, 250 mm × 4.6 mm); UV detector; detection wavelength, 365 nm; mobile phase, a mixture of formic acid aqueous solution (the volume concentration of formic acid aqueous solution is 1.5 v / v%)-methanol-tetrahydrofuran in a volume ratio of 52:10:38; isocratic elution; flow rate, 1 mL / min; column temperature, 35 °C; injection volume, 10 μL.

[0083] (4) Drawing of 3-THBP standard curve and calculation of 3-THBP in the photoresist sample to be tested

[0084] The peak areas of 3-THBP standard solutions with different concentrations (see Figure 1 and Table 1) as the horizontal axis and the concentration as the vertical axis, and draw the standard curve (see Figure 2 ) to obtain the standard curve equation (see Table 1).

[0085] The 3-THBP (see Figure 3 ) into the standard curve equation to calculate the concentration of 3-THBP in the sample solution to be tested, and then substitute it into formula (1) to obtain the content of 3-THBP in photoresist sample 1; and calculate the concentration recovery rate and relative standard deviation RSD based on 3 parallel samples to be tested to examine the accuracy and precision of the detection method. Among them, formula (1) is

[0086]

[0087] In formula (1):

[0088] Wt, %—the content of 3-THBP in the photoresist sample to be tested;

[0089] V—the constant volume of the photoresist sample to be tested, in mL;

[0090] m—mass of the photoresist sample to be tested, in mg.

[0091] Test results: Figure 1 This is the liquid phase spectrum of the 3-THBP standard in this example; Figure 2 is the standard curve of the 3-THBP standard in this example; Table 1 is the test results of the 3-THBP standard solutions of different concentrations in this example; Figure 3 is the liquid phase spectrum of the photoresist sample 1 in this embodiment; Table 2 is the detection result of 3-THBP in the photoresist sample 1 in this embodiment.

[0092] Table 1 Detection results of 3-THBP standard solution and standard curve in Example 1

[0093]

[0094] Table 2 Detection results of 3-THBP in the photoresist sample 1 to be tested in Example 1

[0095]

[0096] Through Table 1 and Figure 2 The test results show that the standard curve of the 3-THBP standard has a good linear relationship using the detection method provided by this application, and can be used to detect the content of 3-THBP in the test samples. Combined with the test results in Table 2, the detection recovery rate of 3-THBP in the test photoresist samples using the detection method provided by this application ranges from 99.25% to 101.31%, with an RSD of 1.06%. This result demonstrates that the detection method of this application has high accuracy, repeatability, and precision.

[0097] Example 2

[0098] Example 2 provides a method for determining the content of diazonaphthoquinone sensitizer (4-THBP) in photoresist.

[0099] (1) Pretreatment of the sample to be tested

[0100] The sample to be tested is photoresist sample 2 (purchased from Merck, containing 2.42 wt % of diazonaphthoquinone photosensitizer 4-THBP).

[0101] In a yellow light room, weigh 101.9 mg, 103.5 mg, and 98.6 mg of sample 2, respectively, accurate to 0.1 mg, place them in a 10 mL volumetric flask, dissolve them in N-methylpyrrolidone, and dilute to the scale.

[0102] The prepared sample solution was allowed to stand for 0.5 h, and part of the solution was removed with a 2 mL syringe. After filtering with a 0.45 μm filter membrane, the solution was tested by high performance liquid chromatography.

[0103] (2) Preparation of standard solution

[0104] Weigh 99.2 mg of 4-THBP standard (purchased from Migen Trading Co., Ltd.) to the nearest 0.1 mg, place it in a 50 mL volumetric flask, and dissolve and dilute to the mark with N-methylpyrrolidone.

[0105] Use a 5mL pipette to measure 0.5mL, 1mL, 2.0mL, and 5mL of the above solution into a 10mL volumetric flask. Dilute to the mark with N-methylpyrrolidone to obtain four 4-THBP standard solutions of varying concentrations. Add the mother solution to obtain a total of five 4-THBP standard solutions. Use a 2mL syringe to remove a portion of the solution, filter through a 0.45μm filter membrane, and analyze each solution on a high-performance liquid chromatograph to generate a standard curve.

[0106] (3) Test conditions

[0107] The test conditions are the same as those provided in Example 1.

[0108] (4) Drawing of 4-THBP standard curve and calculation of 4-THBP in the photoresist sample to be tested

[0109] The calculation method is the same as that provided in Example 1.

[0110] Test results: Figure 4 This is the liquid phase spectrum of the 4-THBP standard in this example; Figure 5 Table 3 is the standard curve of the 4-THBP standard in this example; Table 4 is the test results of the 4-THBP standard solutions of different concentrations in this example; Figure 6 is the liquid phase spectrum of the photoresist sample 2 in this embodiment; Table 4 is the detection result of 4-THBP in the photoresist sample 2 in this embodiment.

[0111] Table 3 Detection results of 4-THBP standard solution and standard curve in Example 2

[0112]

[0113] Table 4 Detection results of 4-THBP in the photoresist sample 2 to be tested in Example 2

[0114]

[0115] Through Table 3 and Figure 5 The test results show that the standard curve of the 4-THBP standard has a good linear relationship using the detection method provided by this application, and can be used to detect the content of 4-THBP in the test samples. Combined with the test results in Table 4, the detection recovery rate of 4-THBP in the test photoresist samples using the detection method provided by this application ranges from 97.52% to 102.89%, with an RSD of 2.96%. This result demonstrates that the detection method of this application has high accuracy, repeatability, and precision.

[0116] Example 3

[0117] Example 3 provides a method for determining the content of diazonaphthoquinone sensitizers (3-THBP and 4-THBP) in a photoresist.

[0118] (1) Pretreatment of the sample to be tested

[0119] The sample to be tested is photoresist sample 3 (purchased from Merck, containing 1.75wt% of diazonaphthoquinone sensitizer 3-THBP and 0.89wt% of 4-THBP)

[0120] In a yellow light room, weigh 102.9 mg, 100.8 mg, and 99.6 mg of sample 3, respectively, accurate to 0.1 mg, place them in a 10 mL volumetric flask, dissolve them in chloroform, and dilute to the scale.

[0121] The prepared sample solution was allowed to stand for 0.5 h, and part of the solution was removed with a 2 mL syringe. After filtering with a 0.45 μm filter membrane, the solution was tested by high performance liquid chromatography.

[0122] (2) Preparation of standard solution

[0123] Weigh 95.5 mg of 3-THBP and 99.3 mg of 4-THBP to the nearest 0.1 mg, place them in a 50 mL volumetric flask, and dissolve and dilute to the mark with chloroform to prepare a mixed standard solution.

[0124] Use a 5mL pipette to measure 0.5mL, 1mL, 2.0mL, and 5mL of the above solution into a 10mL volumetric flask and dilute to the mark to obtain four PAC mixed standard solutions of varying concentrations. Add the mother solution for a total of five PAC mixed standard solutions. Use a 2mL syringe to remove a portion of the solution, filter through a 0.45μm filter membrane, and analyze each solution on a high-performance liquid chromatograph to generate a standard curve.

[0125] (3) Test conditions

[0126] The test conditions are the same as those provided in Example 1.

[0127] (4) Drawing of the standard curves of 3-THBP and 4-THBP in the mixed standard and calculation of 3-THBP and 4-THBP in the photoresist sample to be tested

[0128] The calculation method is the same as that provided in Example 1.

[0129] Test results: Figure 7 This is the liquid phase spectrum of the mixed standard of 3-THBP and 4-THBP in this example; Figure 8 Table 5 is the standard curve of 3-THBP standard and 4-THBP standard in the mixed standard in this example; Table 6 is the test results of 3-THBP and 4-THBP standard solutions of different concentrations in this example; Figure 9 is the liquid phase spectrum of the photoresist sample 3 in this embodiment; Table 6 is the detection results of 3-THBP and 4-THBP in the photoresist sample 3 in this embodiment.

[0130] Table 5 Detection results of 3-THBP and 4-THBP standard solutions and standard curves in Example 3

[0131]

[0132] Table 6 Detection results of 3-THBP and 4-THBP in the photoresist sample 3 to be tested in Example 3

[0133]

[0134] Through Table 5 and Figure 8The test results show that, using the detection method provided by this application, the standard curves of the 3-THBP standard and the 4-THBP standard in the mixed standard have a good linear relationship and can be used to detect the content of 3-THBP and 4-THBP in the test sample. Combined with the test results in Table 6, using the detection method provided by this application, the detection recovery rate of 3-THBP in the test photoresist sample ranged from 97.71-101.71%, with an RSD of 2.18%; the detection recovery rate of 4-THBP ranged from 97.75-103.37%, with an RSD of 2.97%. These results indicate that the detection method of this application has high accuracy, repeatability, and precision.

[0135] Example 4

[0136] Example 4 provides a method for determining the content of diazonaphthoquinone sensitizers (3-THBP and 4-THBP) in a photoresist.

[0137] The difference between this embodiment and embodiment 3 is that the mobile phase is a mixed solution of formic acid aqueous solution (the volume concentration of formic acid aqueous solution is 1.5 v / v%)-methanol-tetrahydrofuran in a volume ratio of 46:13:41.

[0138] Test results: as shown in Table 7.

[0139] Example 5

[0140] Example 5 provides a method for determining the content of diazonaphthoquinone sensitizers (3-THBP and 4-THBP) in photoresist.

[0141] The difference between this embodiment and embodiment 3 is that the mobile phase is a mixed solution of formic acid aqueous solution (the volume concentration of formic acid aqueous solution is 1.5 v / v%)-methanol-tetrahydrofuran in a volume ratio of 58:7:35.

[0142] Test results: as shown in Table 7.

[0143] Table 7 Detection results of 3-THBP and 4-THBP in the photoresist sample 3 to be tested in Example 4-5

[0144]

[0145] Combining the test results of Example 3 in Table 6 with the test results of Examples 4-5 in Table 7, when the present application selects a 1-2 v / v% acid aqueous solution-methanol-tetrahydrofuran mixed solution with a volume ratio of (48-54): (9-11): (36-40) as the mobile phase, the recovery rate is closer to 100% and the RSD is smaller, indicating that the accuracy, repeatability and precision of the test results can be further improved.

[0146] Comparative Example

[0147] Comparative Example 1

[0148] This comparative example provides a method for determining the content of naphthoquinone diazide photosensitizers (3-THBP and 4-THBP) in a photoresist.

[0149] The difference between this comparative example and Example 3 is that the mobile phase is a mixed solution of formic acid aqueous solution (the volume concentration of formic acid aqueous solution is 1.5 v / v%) and methanol in a volume ratio of 52:10.

[0150] Test results: The separation of diazonaphthoquinone sensitizers 3-THBP and 4-THBP in photoresist is poor, the peak areas of 3-THBP and 4-THBP overlap, and the peak areas cannot be integrated.

[0151] Comparative Example 2

[0152] This comparative example provides a method for determining the content of naphthoquinone diazide photosensitizers (3-THBP and 4-THBP) in a photoresist.

[0153] The difference between this comparative example and Example 3 is that the mobile phase is a mixed solution of formic acid aqueous solution (the volume concentration of formic acid aqueous solution is 1.5 v / v%) and tetrahydrofuran in a volume ratio of 52:38.

[0154] Test results: The separation of diazonaphthoquinone sensitizers 3-THBP and 4-THBP in photoresist is poor, the peak areas of 3-THBP and 4-THBP overlap, and the peak areas cannot be integrated.

[0155] Comparative Example 3

[0156] This comparative example provides a method for determining the content of naphthoquinone diazide photosensitizers (3-THBP and 4-THBP) in a photoresist.

[0157] The difference between this comparative example and Example 3 is that the mobile phase is a methanol-tetrahydrofuran mixed solution with a volume ratio of 10:38.

[0158] Test results: The separation of diazonaphthoquinone sensitizers 3-THBP and 4-THBP in photoresist is poor, the peak areas of 3-THBP and 4-THBP overlap, and the peak areas cannot be integrated.

[0159] Comparative Example 4

[0160] This comparative example provides a method for determining the content of naphthoquinone diazide photosensitizers (3-THBP and 4-THBP) in a photoresist.

[0161] The difference between this comparative example and Example 3 is that the mobile phase is a mixed solution of formic acid aqueous solution (the volume concentration of formic acid aqueous solution is 1.5 v / v%)-methanol-tetrahydrofuran in a volume ratio of 60:7:33.

[0162] Test results: The peak areas of 3-THBP and 4-THBP have little overlap, as shown in Table 8.

[0163] Table 8 Detection results of 3-THBP and 4-THBP in the photoresist sample 3 to be tested in comparative example 4

[0164]

[0165]

[0166] Combined with the test results of Comparative Example 4 in Table 8, when the volume ratio of each component in the mobile phase of the present application does not conform to the selection range of the present application, the test results recovery rate of 3-THBP and 4-THBP in the photoresist sample 3 to be tested is far from 100%, and the accuracy of the test results is low.

[0167] Although the present invention has been described in detail above using general descriptions and specific embodiments, it will be apparent to those skilled in the art that modifications and improvements may be made based on the present invention. Therefore, such modifications and improvements, which do not depart from the spirit of the present invention, are intended to be within the scope of protection claimed herein.

Claims

1. A method for determining the content of naphthoquinone diazide sensitizer in a photoresist, characterized in that: The specific steps include: Diluting the sample to be tested and the standard solution of naphthoquinone diazide sensitizer with tetrahydrofuran, and filtering to obtain a sample solution to be tested and a standard solution; The sample solution and the standard solution are tested by high performance liquid chromatography, and the content of the diazonaphthoquinone sensitizer in the sample is calculated; The test conditions of the high performance liquid chromatography are as follows: the chromatographic column packing is a C18 alkyl bonded phase with the following specifications: length 10-25 cm, inner diameter 3.2-4.6 mm, particle size 3 μm; column temperature 20-45° C.; the mobile phase is a 1-2 v / v% acid aqueous solution-methanol-tetrahydrofuran mixed solution with a volume ratio of (48-54):(9-11):(36-40); the elution mode is isocratic elution; the flow rate is 0.5-1 mL / min; the injection volume is 5-50 μL; the acid aqueous solution is one or both of formic acid aqueous solution and acetic acid aqueous solution; the detector is an ultraviolet detector with a detection wavelength of 365-380 nm; The naphthoquinone diazide photosensitizer includes the naphthoquinone diazide photosensitizer corresponding to the following formula (I) and formula (II):

2. The method for determining the content of naphthoquinone diazide sensitizer in photoresist according to claim 1, wherein: The column temperature is 30-45°C.

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