CN113504289A - Method for identifying phenolic skeleton in quinone diazide compound-containing sample - Google Patents

Method for identifying phenolic skeleton in quinone diazide compound-containing sample Download PDF

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CN113504289A
CN113504289A CN202110732386.5A CN202110732386A CN113504289A CN 113504289 A CN113504289 A CN 113504289A CN 202110732386 A CN202110732386 A CN 202110732386A CN 113504289 A CN113504289 A CN 113504289A
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solvent
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solution
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CN113504289B (en
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高剑琴
李冰
鲁代仁
董栋
张宁
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Beijing Red Avenue Innova Co ltd
KEMPUR MICROELECTRONICS Inc
Tongcheng Chemical China Co ltd
Shanghai Tongcheng Electronic Materials Co Ltd
Red Avenue New Materials Group Co Ltd
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Beijing Red Avenue Innova Co ltd
KEMPUR MICROELECTRONICS Inc
Tongcheng Chemical China Co ltd
Shanghai Tongcheng Electronic Materials Co Ltd
Red Avenue New Materials Group Co Ltd
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    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
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    • G01N1/00—Sampling; Preparing specimens for investigation
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N1/00—Sampling; Preparing specimens for investigation
    • G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N1/00—Sampling; Preparing specimens for investigation
    • G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N1/00—Sampling; Preparing specimens for investigation
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    • G01N1/40—Concentrating samples
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    • G01N2001/4027—Concentrating samples by thermal techniques; Phase changes evaporation leaving a concentrated sample
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    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
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    • G01N1/40—Concentrating samples
    • G01N1/4055—Concentrating samples by solubility techniques
    • G01N2001/4061—Solvent extraction
    • G—PHYSICS
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    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
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    • G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
    • G01N1/40—Concentrating samples
    • G01N1/4077—Concentrating samples by other techniques involving separation of suspended solids
    • G01N2001/4094—Concentrating samples by other techniques involving separation of suspended solids using ultrasound

Abstract

The application relates to a method for identifying a phenolic skeleton in a quinone diazide compound-containing sample, which relates to the field of compound analysis and comprises the following steps: in the presence of alcohol, a sample to be detected and a strong base reagent are subjected to hydrolysis reaction to obtain a mixed solution containing a target product; carrying out water removal treatment on the mixed solution, then adding an organic solvent and filtering to obtain a supernatant containing a target product; taking the supernatant containing the target product to perform field desorption mass spectrometry system test to obtain a mass spectrogram; the sample to be tested contains one or more of a quinone diazide compound and an exposed product of the quinone diazide compound. The application has the effect of being able to detect and identify the photosensitizer.

Description

Method for identifying phenolic skeleton in quinone diazide compound-containing sample
Technical Field
The application relates to the field of compound analysis, in particular to a method for identifying a phenolic skeleton in a quinone diazide compound sample.
Background
Photoresist, also called photoresist, is a mixed liquid sensitive to light, is a key material for processing fine patterns in microelectronic technology, and is composed of Photosensitizer (PAC), resin, solvent, etc.
A photoresist containing a compound having a quinonediazide group (e.g., naphthoquinonediazide group, benzoquinonediazide group, etc., and a composition thereof) and an alkali-soluble resin can be used as a positive photoresist. Because the quinonediazido group is decomposed to form carboxyl when exposed to ultraviolet rays, the composition which is not dissolved in alkali originally becomes alkali-soluble, and the alkali-soluble rate of the photoresist composition is accelerated; the non-exposed area of the quinonediazide layer is combined with the resin to a certain degree, so that the alkali dissolution rate of the photoresist composition is reduced, and the difference of the dissolution rates of the exposed area and the non-exposed area is utilized to realize the pattern transfer.
Figure BDA0003139583060000011
Compounds having a quinonediazido group are generally prepared by esterification of diazonaphthoquinonesulfonyl chloride with phenolic compounds, which are useful as photosensitizers in positive resists. The photosensitizer product with quinonediazido group contains monoester, diester, triester and tetraester structures, and the preparation process of the compounds is described by taking the esterification reaction of diazonaphthoquinone sulfonyl chloride (DNQ) and trihydroxybenzophenone as an example (see the following formula).
Figure 1
Wherein D represents DNQ, and
Figure BDA0003139583060000022
the structure is as follows:
Figure BDA0003139583060000023
the PACs synthesized industrially are of hundreds, and typically:
Figure BDA0003139583060000024
meanwhile, the methods for determining the structure of a compound include mass spectrometry and spectroscopy. For the wave spectrum, the requirement on the purity of a sample is high, the sample needs to be further enriched and purified, the enrichment is not convenient enough, meanwhile, the PAC product has a structure which is too similar, the main functional group is on the quinonediazide group, and the wave spectrum is not easy to distinguish a specific phenol skeleton structure; for mass spectrometry, the molecular weight of the quinonediazide compound is too large and the boiling point is too high to be vaporized into mass spectrometry.
In conclusion, PAC products have similar functional groups and structures and belong to macromolecular, high-boiling-point and unstable substances, and the PAC products are difficult to detect and identify through conventional spectral chromatography direct analysis.
Disclosure of Invention
In order to detect and identify a photosensitizer, the application provides a method for identifying a phenolic skeleton in a sample containing a quinonediazide compound.
The identification method for the phenolic skeleton in the quinone diazide compound-containing sample provided by the application adopts the following technical scheme:
a method for identifying a phenolic skeleton in a sample containing a quinonediazide compound, comprising the steps of:
in the presence of alcohol, a sample to be detected and a strong base reagent are subjected to hydrolysis reaction to obtain a mixed solution containing a target product;
carrying out water removal treatment on the mixed solution, then adding an organic solvent and filtering to obtain a supernatant containing a target product;
taking the supernatant containing the target product to perform field desorption mass spectrometry system test to obtain a mass spectrogram;
the sample to be tested contains one or more of a quinone diazide compound and an exposed product of the quinone diazide compound.
By adopting the technical scheme, under the action of strong alkali, the exposed products of the quinonediazide-containing compound and the quinonediazide-containing compound in a sample to be detected are hydrolyzed to obtain the phenolic skeleton, the diazonaphthoquinone sodium sulfonate or the exposed diazonaphthoquinone sodium sulfonate and water, then the water is further removed, the phenolic skeleton is the target product contained in the supernatant, then the phenolic skeleton is extracted by an organic solvent, the field desorption mass spectrometry is carried out on the phenolic skeleton, and the structure of the phenolic skeleton can be judged according to the obtained mass spectrogram, so that the structure of the quinonediazide-containing compound is further obtained.
Preferably, the quinonediazide-containing compound is formed by esterification of a quinonediazide sulfonyl halide and a phenol compound.
Wherein the quinonediazido group includes, but is not limited to, Diazonaphthoquinone (DNQ), diazobenzoquinone; the compound is one or more of monoester, diester, triester and tetraester structures.
The sample size of the compound may be as low as 10mg, for example, the sample size may be 10mg, 30mg, 50mg, 100 mg.
The amount of NaOH is enough to hydrolyze the sample to be tested.
In one embodiment, the amount of NaOH is in excess, so that the amount of target product formed after hydrolysis of the test sample is sufficient for field desorption mass spectrometry system testing.
In one embodiment, the weight ratio of the sample to be tested to NaOH is not less than 1:0.2, for example, the weight ratio of the sample to be tested to NaOH may be 1:50, 1: 6.
In the present application, the sample to be tested is a mixture, the specific structure of the compounds contained therein is unknown, so it is difficult to determine the specific amount of NaOH. In order to ensure that the target product is produced in an amount sufficient for subsequent detection after hydrolysis of the sample to be tested, it is preferred to use an excess of NaOH. After many trials, it was found that NaOH in the above range ensures that the amount of target product produced is sufficient for subsequent detection.
In one embodiment, the alkali-alcohol solution may be obtained first, and then the sample to be tested is added to the alkali-alcohol solution to perform the hydrolysis reaction.
The alcoholic base solution can be, for example, a NaOH-alcoholic solution, a KOH-alcoholic solution.
The alcoholic base solution can be obtained by conventional methods. For example, NaOH solids can be dissolved in methanol.
Preferably, the hydrolysis comprises the steps of: the hydrolysis conditions were: heating and refluxing at 80-100 deg.C for 5-100min until the color of the solution becomes dark to obtain mixed solution.
By adopting the technical scheme, along with the hydrolysis of the quinone diazide compound and the exposure product of the quinone diazide compound, the generated phenol skeleton and the diazo naphthoquinone sodium sulfonate become more, the color of the alcoholic solution of the diazo naphthoquinone sodium sulfonate is darker, so the color of the solution becomes darker gradually, namely the hydrolysis is carried out gradually; when the concentration of the product of the quinonediazide-containing compound or the quinonediazide-containing compound after exposure is low, the product can finally turn into red, and when the concentration of the product of the quinonediazide-containing compound or the quinonediazide-containing compound after exposure is high, the product can finally turn into purple red;
in addition, the quinonediazide group-containing compound is a non-polar substance which cannot be directly dissolved in an alcohol solution, but the hydrolysis under the action of NaOH can obtain a phenolic skeleton, diazonaphthoquinone sodium sulfonate and water, wherein the phenolic skeleton belongs to polyphenols and can be well dissolved in the alcohol solution, and the diazonaphthoquinone sodium sulfonate is also dissolved in the water, so that when a sample of the quinonediazide group-containing compound is completely dissolved, the quinonediazide group-containing compound is considered to be completely hydrolyzed.
Preferably, in the NaOH-alcohol solution, the alcohol is one or more of methanol, ethanol and isopropanol. The alcohol is preferably methanol.
In the present application, an alcohol is chosen as solvent, on the one hand as solvent for the hydrolysis reaction and on the other hand for dissolving the products of the hydrolysis reaction, in order to precipitate the sulfonate by-product. In addition, in the subsequent organic solvent extraction process, the alcohol can be mutually soluble with the organic solvent, so that the sulfonate byproduct can be washed out more conveniently, and the separation of the target product and the byproduct is realized.
By adopting the technical scheme, the full and rapid hydrolysis of the quinonediazido group-containing compound is facilitated under the condition.
Preferably, the mass concentration of NaOH in the NaOH-alcohol solution is 0.5-10%.
By adopting the technical scheme, the quinonediazide-containing compound can be hydrolyzed fully and rapidly under the concentration and the addition of the NaOH-alcohol solution.
Preferably, after the hydrolysis, the pH is adjusted to 5 to 7.
By adopting the technical scheme, under the PH condition, the finally extracted phenol skeleton has fewer impurities, and the accuracy of the result is favorably improved.
Preferably, the hydrolysis solution is cooled to normal temperature during the pH adjustment, and then an aqueous hydrochloric acid solution is added to the hydrolysis solution.
Preferably, when the water in the mixed solution is removed, anhydrous sodium sulfate is added to the mixed solution until the water in the mixed solution is removed.
Preferably, the organic solvent is THF, the THF is mixed uniformly and then is kept stand for layering, and then the supernatant is taken to enter a field desorption mass spectrometry system for testing.
By adopting the technical scheme, THF and an alcohol solution are mutually soluble, a mixed solution of THF and the alcohol solution is used for further extracting the phenolic skeleton, and sodium salt substances (diazonaphthoquinone sodium sulfonate, sodium chloride and the like) in the mixed solution are separated out through oscillation, so that layering is realized, and the purity of the extracted phenolic skeleton is improved.
Preferably, the THF is added in an amount of 1-5 times the volume of the NaOH-alcohol solution. Specifically, the amount of THF added may be 1 time, 2 times, 3 times, 4 times, or 5 times the volume of the NaOH-alcohol solution.
In the present application, the target product is one or more compounds containing a phenolic backbone structure.
In one embodiment, the desired product comprises any one of the structures of formula I and formula II:
Figure BDA0003139583060000051
in the formula I, n is 0 or 1;
-the number of OH is at least 1;
R1and R4Are identical or different, each being
Figure BDA0003139583060000052
R6、R7And R8Identical or different and are each a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an alkoxy group, an aryl group or
Figure BDA0003139583060000053
R2、R3、R5And R9The same or different, each is a hydrogen atom, an alkyl group, an aryl group, a halogen atom or a hydroxyl group;
Figure BDA0003139583060000054
in the formula II, R1，R2Or R5Is C1-C4 alkyl;
R3、R4is a hydrogen atom or C1-C4 alkyl group.
Preferably, the compound comprises a structure of formula iii or formula iv:
Figure BDA0003139583060000061
in the formula III, Y1-Y4Identical or different, each being a hydrogen atom, an alkyl group, a halogen atom or a hydroxyl group, Y1，Y2，Y3And Y4At least one of which is a hydroxyl group;
Z1-Z6the same or different, each is a hydrogen atom, an alkyl group, an aryl group, a halogen atom or a hydroxyl group;
Z1-Z4at least one of which is a hydroxyl group;
Z5and Z6Is a hydroxyl group;
x is of structure
Figure BDA0003139583060000062
Wherein R is1And R2The same or different, each is a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an alkoxy group or an aryl group;
Figure BDA0003139583060000063
in the formula IV, R1，R2Or R3Is C1-C4 alkyl;
R1、R2or R3An integer in number from 0 to 4;
R4is hydrogen atom, alkyl, aryl, halogen atom or hydroxyl.
Preferably, the sample to be tested is subjected to the following pretreatment steps before hydrolysis:
s1: adding a sample to be detected into a solvent A for ultrasonic extraction, and performing centrifugal separation to obtain a solid precipitate;
s2: adding a solvent B into the solid precipitate, performing ultrasonic extraction, and performing centrifugal separation to obtain a supernatant;
s3: exposing the supernatant under ultraviolet light, adding a solvent C, performing ultrasonic extraction, and performing centrifugal separation to obtain a solid precipitate;
s4: adding a solvent A into the solid precipitate, performing ultrasonic extraction, performing centrifugal separation, and reserving supernatant;
wherein the solvent A is a polar solvent, and the solvent B, C is a non-polar solvent.
Preferably, the solvent C is more non-polar than the solvent B.
By adopting the technical scheme, the quinonediazide group-containing compound is a non-polar substance and cannot be dissolved in the solvent A, but a polar substance in the sample to be detected is dissolved, and meanwhile, the polar phenolic resin and other phenolic small-molecule interferents are also dissolved in the solvent A, so that the polar phenolic interferents are removed in the step S1;
in step S2, the nonpolar solvent B dissolves the quinonediazide-containing compound or the conjugate of the quinonediazide-containing compound and the resin, and the nonpolar polymer resin, glue, or the like is also the solvent B;
in step S3, after exposure to ultraviolet light, the structure of the quinonediazide-containing compound is changed so that the exposed quinonediazide-containing compound becomes a polar substance, and after the solvent C is added, both the solvent B and the solvent C are nonpolar and dissolve in each other, so that the exposed quinonediazide-containing compound is different from the solvent B and the solvent C, and thus the supernatant is removed, i.e., the solvent B, the solvent C, and the nonpolar substances dissolved in the solvent B and the solvent C are removed;
in step S4, a polar solvent a is further added to dissolve the exposed quinonediazide compound in the solid substance, and the exposed quinonediazide compound is further separated;
if the sample to be detected is a mixture of the quinonediazide group-containing compound and other polymers, the target substance is separated through the steps, and the structural identification of the quinonediazide group compound in the product is realized.
Preferably, in step S4, the supernatant is concentrated to obtain a sample to be tested containing the exposed quinonediazide compound. The concentration is carried out by blowing nitrogen.
Preferably, in the step S3, the exposure energy is 5-100 mW/S.
Preferably, in step S3, the exposure time is 3-30 min.
By adopting the above technical scheme, the quinonediazide group of the quinonediazide-containing compound can be sufficiently decomposed to form a carboxyl group under the limitation of the exposure conditions.
Preferably, the solvent A is selected from one or more of alcohol and alkylbenzene.
Further preferably, the solvent A is selected from one or more of methanol, ethanol and toluene.
Preferably, the solvent B is selected from one or more of ketone, ether and ester.
Preferably, the addition amount of the solvent A is 2-10 times of the volume of the sample to be detected.
Further preferably, the solvent B is one or more selected from acetone, anisole, propylene glycol monomethyl ether, ethyl lactate and propylene glycol monomethyl ether acetic acid.
Further preferably, the solvent B is selected from one or more of acetone, ethyl lactate and propylene glycol monomethyl ether acetate.
Preferably, the addition amount of the solvent B is 2-10 times of the volume of the sample to be detected.
Preferably, the solvent C is selected from one or more of alkane and cycloalkane.
Further preferably, the solvent C is selected from one or more of n-heptane, n-hexane and cyclohexane.
Preferably, the amount of the solvent C added is 2 to 10 times the volume of the solution after exposure.
By adopting the technical scheme, the selection of the solvent A, the solvent B and the solvent C enables the separated exposed quinonediazide compound to be more pure.
In summary, the present application includes at least one of the following beneficial technical effects:
1. the method comprises the steps of obtaining a phenolic skeleton in the PAC by a hydrolysis method, and identifying the PAC structure by the skeleton identification of a field desorption mass spectrum, so that the identification of the PAC structure is realized, and the purchased raw materials, the analysis of raw material abnormity and the analysis of product abnormity are facilitated;
2. the method can be used for identification under a lower sampling amount, so that the identification of trace materials is realized, and the requirement that the actual test sample amount is limited is met;
3. the pretreatment method and the used equipment are relatively simple, so that the identification of the PAC structure is more accurate and convenient.
Drawings
FIG. 1 is a field resolved mass spectrum of the supernatant of example 1.
FIG. 2 is a field resolved mass spectrum of the supernatant of example 2.
FIG. 3 is a field resolved mass spectrum of the supernatant of example 3.
FIG. 4 is a field resolved mass spectrum of the supernatant of example 4.
FIG. 5 is a field resolved mass spectrum of the supernatant of example 5.
FIG. 6 is a field resolved mass spectrum of the supernatant of example 6.
Detailed Description
The present application is described in further detail in conjunction with the following.
Aqueous HCl solution prepared from concentrated hydrochloric acid and water at a certain volume ratio, i.e. VHCl:VWater (W)V inHClThe volume of concentrated hydrochloric acid, analytically pure, the manufacturer is Huaxi Hengchang chemical company in Buddha mountain.
Example 1
Known sample analysis: identification and analysis of commercial product D006(TOYO GOSET CO. LTD):
d006 is a common photosensitizer in positive resists, and the structure of the photosensitizer is as follows:
Figure BDA0003139583060000081
wherein R represents a quinonediazido group. The structure of the material is analyzed, and the test steps are as follows:
1.1A 100mg sample of D006 was placed in a glass flask, 10mL of 5 wt% NaOH-methanol solution was added, and the mixture was heated under reflux at 90 ℃ for 15min until the sample was completely dissolved, at which time the methanol solution changed from yellow to dark purple.
1.2 dropping 3-4 drops of V into the cooled dark purple solutionHCl:VWater (W)Dropwise adding HCl aqueous solution at a ratio of 1:2 while stirring to uniformly mix; then continuously dropwise adding V inwardsHCl:VWater (W)The solution was stirred with 1:15 aqueous HCl and the PH was monitored while observing the solution color, and the addition of HCl was stopped at about PH 6 at the instant the solution color changed from dark purple to bright red.
1.3 Add 500mg anhydrous sodium sulfate to the flask and shake gently to remove a small amount of water from the solution.
1.4 adding 10mL THF into the flask, precipitating NaCl in the solution system, standing for layering, taking the supernatant, and sending to a field analysis mass spectrometry, wherein the test result is shown in figure 1.
And (3) analysis: the molecular weight of the phenol compound skeleton of D006 is 376, and the above-mentioned treatment steps are intended to hydrolyze the ester group to obtain the skeleton structure of the intact phenol compound (see the following formula), and the identification and analysis of the quinonediazide-containing compound are accomplished by the identification of the skeleton structure. The strong M-376.27 signal was detected in fig. 1, which illustrates that the pretreatment approach resulted in a complete phenolic backbone, which can be used for the identification and analysis of quinonediazide-containing compounds.
Hydrolysis process of D006 sample:
Figure BDA0003139583060000091
example 2
Known sample analysis: identification and analysis of commercial product D006:
the difference from example 1 is that: the pH in step 1.2 was adjusted to 3. The test results are shown in FIG. 2.
And (3) analysis: as can be seen from fig. 2, when PH is 3, M is 376.27, which is weak, indicating that the amount of the pretreatment by-product is large, but the phenolic skeleton is still detectable.
Example 3
Identification and analysis of a commercially available sensitizer TPPA-250 (Meiyuan commercial Co., Ltd.):
3.1 about 50mg of TPPA-250 sample was placed in a glass flask, 10mL of 3 wt% NaOH-ethanol solution was added, and heated under reflux at 70 ℃ for 30min until the sample was completely dissolved, at which time the solution changed from yellow to dark purple.
3.2 dropping 3-4 drops of V into the cooled dark purple solutionHCl:VWater (W)Dropwise adding HCl aqueous solution at a ratio of 1:2 while stirring to uniformly mix; then continuously dropwise adding V inwardsHCl:VWater (W)The solution PH was measured while stirring under dropwise addition of 1:15 aqueous HCl. When the color of the solution is changed from dark purple to orange red, the pH value is between 5 and 6, and the HCl solution is stopped dripping.
3.3 Add 300mg of anhydrous sodium sulfate to the flask and shake gently to remove a small amount of water from the solution.
3.4, continuously adding 10mL of THF into the flask, shaking uniformly, separating out NaCl in the solution system, standing for layering, taking supernatant, and sending the supernatant to a field resolution mass spectrometry, wherein the test result is shown in figure 3.
And (3) analysis: from the field-resolved mass spectrum shown in fig. 3, the strongest signal peak is M ═ 424.26, which is judged as tetraphenyl ring skeleton structure, and the structure of the identical polyphenol is shown as formula (3-1), so that the photosensitizer is judged as TPPA PAC, and the structure is shown as formula (3-2).
Figure BDA0003139583060000101
Figure BDA0003139583060000102
Wherein R represents a quinonediazido group.
Example 4
Identification and analysis of PAC in the laboratory self-made photoresist products (formula: Novolac resin 15 wt%, TPPA 25015 wt%, Dye 2 wt%, Polyacrylate 3 wt%, MAK 65 wt%):
4.1 taking about 3mL of photoresist product (500mg) into a 10mL centrifuge tube, adding 6mL of methanol, performing ultrasonic extraction for 3min to obtain a large amount of precipitate in the solution, performing centrifugal separation (3000r/min, 4min), removing the upper red clear liquid, and keeping the lower precipitate;
4.2 adding 6mL of PGMEA into the centrifuge tube, performing ultrasonic extraction for 5min, dissolving the precipitate at the lower layer, continuously placing the centrifuge tube into a centrifuge for centrifugal separation (3000r/min, 4min), and keeping the solution at the upper layer;
4.3 the supernatant solution was spread on the bottom of a petri dish and exposed to full wavelength light for 5min on an ABM Mask Aligners & Exposure Systems UV Exposure machine with Exposure energy of 14 mW/s. The exposed solution was transferred to a 50mL centrifuge tube, the petri dish was washed with 3mL of PGMEA, and the wash solution was transferred to the centrifuge tube. Adding n-hexane with volume three times that of the existing PGMEA solution into a centrifugal tube, precipitating a large amount of precipitate, placing the centrifugal tube into an ultrasonic cleaning instrument for ultrasonic treatment for 5min, performing centrifugal separation, and removing supernatant.
4.4, continuously adding 10mL of methanol into the centrifuge tube, performing ultrasonic extraction and centrifugal separation, placing the separated supernatant into a flask, and performing nitrogen blowing concentration to 1mL to obtain a sample to be detected containing the exposed quinonediazide group compound.
4.5 to the concentrated sample was added 10mL of a 10 wt% NaOH-ethanol solution, and the mixture was heated under reflux at 70 ℃ for 15min, at which time the solution changed from red to dark purple.
4.6 dropping 4-5 drops of V into the cooled dark purple solutionHCl:VWater (W)Dropwise adding HCl aqueous solution at a ratio of 1:1 while stirring to uniformly mix; then continuously dropwise adding V inwardsHCl:VWater (W)The solution PH was measured while stirring under dropwise addition of 1:15 aqueous HCl. When the color of the solution is changed from dark purple to red, the pH value is 6-7, and the dropwise addition of the HCl solution is stopped.
4.3A small amount of anhydrous sodium sulfate was added to the flask and gently shaken to remove a small amount of water from the solution.
4.4 continue to add 10mL THF, precipitate the solution system of NaCl, after standing and layering, the supernatant is sent to the field analysis mass spectrometry test, the test results are shown in figure 4.
And (3) analysis: from fig. 4, the strongest signal peak in the field resolved mass spectrum is M424.56, and the molecular weight of most of the hetero peaks in the mass spectrum is the same as that of example 3, so the commercial photoresist product PAC is judged to be TPPA.
Example 5
The difference from example 4 is that: the film is placed on an ABM Mask Aligners and Exposure Systems ultraviolet Exposure machine for Exposure for 5min at full wavelength and 5mW/s of Exposure energy.
After ultrasonic extraction with methanol and centrifugal separation in the corresponding 4.4 steps, the separated supernatant is light yellow, which indicates that the extracted sample amount is very small. To the concentrated sample was added 10mL of a 10 wt% NaOH-methanol solution, and the mixture was heated under reflux at 70 ℃ for 15min, at which time the solution remained pale yellow.
The subsequent steps are the same as in example 4, and the mass spectrum obtained is shown in FIG. 5.
And (3) analysis: from fig. 5, no signal peak of M ═ 424.56 was found in the field-resolved mass spectrum, indicating that 5mW/s exposure energy was too low to achieve the test purpose.
Example 6
The difference from example 4 is that: exposing for 2min at full wavelength and 20mW/s of Exposure energy on ABM Mask Aligners and Exposure Systems ultraviolet Exposure machine
Ultrasonic extracting with methanol at the corresponding step 4.4, and centrifuging to separate supernatant as orange red. 10mL of 10 wt% NaOH-methanol solution was added to the concentrated sample, and the mixture was heated under reflux at 70 ℃ for 15min, at which time the solution remained orange-red.
The subsequent steps are the same as in example 4, and the mass spectrum obtained is shown in FIG. 6.
And (3) analysis: as can be seen from fig. 6, the peak of the signal with M being 424.56 in the field resolved mass spectrum is weak, which indicates that the 2min exposure time is too short, and the detected signal is weak and is not enough to support accurate qualitative determination.
Comparative example 1
The difference from example 1 is that:
to the sample was added 10mL of a sulfuric acid-water-methanol solution of V sulfuric acid, V water, V methanol, 1:1: 10. Wherein the sulfuric acid is concentrated sulfuric acid, and the sulfuric acid is analytically pure, and the manufacturer is Huaxi chemical company, Buddha city.
And (3) analysis: PAC is not dissolved in the alcohol water phase, but the hydrolyzed phenol and sulfonic acid are dissolved in the alcohol water phase, and after the experiment is heated and refluxed for 1 hour, a large amount of samples are still insoluble, which indicates that the acid hydrolysis method is not suitable.
Comparative example 2
The difference from example 1 is that:
adding 5 wt% NaOH-water solution into a sample to be detected for hydrolysis, and then carrying out EI mass spectrum detection.
And (3) analysis: the hydrolysis process takes longer, the sample can be completely dissolved in about 40min, but under the strong alkali aqueous solution, the conventional organic extraction solvent (such as alkane, cyclane, halogenated hydrocarbon, aromatic hydrocarbon and the like) is mutually dissolved with water, the reaction product can not be extracted, a large amount of water can not be easily removed, and the sample contains water, so the equipment is not beneficial, and the selection is not made.
Performance detection
Detection conditions of field-resolved mass spectrometry:
a field desorption mass spectrometer (FD-MS) instrument adopts a German Thermo Fisher DFS high-resolution double-focusing magnetic mass spectrometer and is matched with a German Linden CMS field desorption source, the heating rate of an emission wire is 10-30mA/min, the ionization voltage is 5-8kV, the acceleration voltage is 5kV, and the sample concentration is 10-15 mg/mL.
The above embodiments are preferred embodiments of the present application, and the protection scope of the present application is not limited by the above embodiments, so: all equivalent changes made according to the structure, shape and principle of the present application shall be covered by the protection scope of the present application.

Claims (10)

1. A method for identifying a phenolic skeleton structure in a quinone diazide compound-containing sample, which is characterized by comprising the following steps: the method comprises the following steps:
in the presence of alcohol, a sample to be detected and a strong base reagent are subjected to hydrolysis reaction to obtain a mixed solution containing a target product;
carrying out water removal treatment on the mixed solution, then adding an organic solvent and filtering to obtain a supernatant containing a target product;
taking the supernatant containing the target product to perform field desorption mass spectrometry system test to obtain a mass spectrogram;
the sample to be detected is one or more of a quinone diazide compound and an exposed product of the quinone diazide compound.
2. The identification method according to claim 1, characterized in that: and mixing the alcohol and the strong base reagent to obtain an alcohol-base solution, and carrying out hydrolysis reaction on the sample to be detected in the alcohol-base solution.
3. The identification method according to claim 1, characterized in that: the strong alkaline reagent is selected from NaOH and KOH.
4. The identification method according to any one of claims 1 to 3, characterized in that: the hydrolysis conditions are as follows: heating and refluxing at 80-100 deg.C until the color of the solution becomes dark to obtain mixed solution.
5. The identification method according to any one of claims 1 to 3, characterized in that: after the hydrolysis, the pH is adjusted to 5-7.
6. The identification method according to any one of claims 1 to 3, characterized in that: the organic solvent is THF.
7. The identification method according to any one of claims 1 to 3, characterized in that: the target product contains any one of the following structures of formula I and formula II:
Figure 510612DEST_PATH_IMAGE001
formula I
In the formula I, n is 0 or 1;
-the number of OH is at least 1;
R1and R4Are identical or different, each being
Figure 474020DEST_PATH_IMAGE002
、
Figure 6632DEST_PATH_IMAGE003
Or
Figure 471112DEST_PATH_IMAGE004
；
R6、R7And R8Identical or different and are each a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an alkoxy group, an aryl group or
Figure 795783DEST_PATH_IMAGE005
；
R2、R3、R5And R9The same or different, each is a hydrogen atom, an alkyl group, an aryl group, a halogen atom or a hydroxyl group;
Figure 726830DEST_PATH_IMAGE006
formula II
In the formula II, R1，R2Or R5Is C1-C4 alkyl;
R3、R4is a hydrogen atom or a C1-C4 alkyl group.
8. The identification method according to claim 7, characterized in that: the compound contains any one of the structures of formula III and formula IV:
Figure 746738DEST_PATH_IMAGE007
formula III
In the formula III, Y1-Y4Identical or different, each being a hydrogen atom, an alkyl group, a halogen atom or a hydroxyl group, Y1，Y2，Y3And Y4At least one of which is a hydroxyl group;
Z1-Z6the same or different, each is a hydrogen atom, an alkyl group, an aryl group, a halogen atom or a hydroxyl group;
Z1-Z4at least one of which is a hydroxyl group;
Z5and Z6Is a hydroxyl group;
x is of structure
Figure 749329DEST_PATH_IMAGE008
Wherein R is1And R2The same or different, each is a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an alkoxy group or an aryl group;
Figure 538294DEST_PATH_IMAGE009
formula IV
In the formula IV, R1，R2Or R3Is C1-C4 alkyl;
R1、R2or R3An integer in number from 0 to 4;
R4is hydrogen atom, alkyl, aryl, halogen atom or hydroxyl.
9. The identification method according to any one of claims 1 to 3, characterized in that: the method comprises the following pretreatment steps before hydrolysis of a sample to be detected:
s1: adding a sample to be detected into a solvent A for ultrasonic extraction, and performing centrifugal separation to obtain a solid precipitate;
s2: adding a solvent B into the solid precipitate, performing ultrasonic extraction, and performing centrifugal separation to obtain a supernatant;
s3: exposing the supernatant under ultraviolet light, adding a solvent C, performing ultrasonic extraction, and performing centrifugal separation to obtain a solid precipitate;
s4: adding a solvent A into the solid precipitate, performing ultrasonic extraction, performing centrifugal separation, and reserving supernatant;
wherein the solvent A is a polar solvent, and the solvent B, C is a non-polar solvent.
10. The identification method according to claim 8, characterized in that: in the step S3, the exposure energy is 5-100mW/S, and the exposure time is 3-30 min.
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