KR20160112827A - Identification and quantitative analysis method of detergent deflux composition using mass spectrometry - Google Patents
Identification and quantitative analysis method of detergent deflux composition using mass spectrometry Download PDFInfo
- Publication number
- KR20160112827A KR20160112827A KR1020150039181A KR20150039181A KR20160112827A KR 20160112827 A KR20160112827 A KR 20160112827A KR 1020150039181 A KR1020150039181 A KR 1020150039181A KR 20150039181 A KR20150039181 A KR 20150039181A KR 20160112827 A KR20160112827 A KR 20160112827A
- Authority
- KR
- South Korea
- Prior art keywords
- deflux
- detergent
- components
- mass spectrometer
- composition
- Prior art date
Links
Images
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/62—Detectors specially adapted therefor
- G01N30/72—Mass spectrometers
- G01N30/7206—Mass spectrometers interfaced to gas chromatograph
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/62—Detectors specially adapted therefor
- G01N30/72—Mass spectrometers
Landscapes
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
Abstract
Description
The present invention relates to a method of identifying and quantifying a deflux detergent using a mass spectrometer, and more particularly, to a method of determining the composition of a deflux detergent used for removing a flux in a semiconductor process using a mass spectrometer, And a method for quantitatively analyzing the content.
Among the semiconductor processes, FCBGA (Flip-Chip Ball Grid Array) process is a process of applying a solder paste, which is a form in which a metal powder and a flux are kneaded, to form a bump, a heat process Forming a spherical bump through the through hole, and removing the flux included in the application process. Here, flux is a substance that removes the oxide film on the metal surface, prevents the re-oxidation of the metal during heating during the soldering operation, and lowers the surface tension, thereby improving solder spreadability and wettability. And so on. However, since the flux or residue remaining on the surface after the semiconductor processing directly affects the reliability or yield of the semiconductor, it is very important to remove the remaining flux, fine particles, and metal contamination using the deflux. to be.
The deflux detergent means a detergent used to remove such fluxes and the like. The components of the deflux detergent are largely composed of amine containing compounds that neutralize the flux material, abietic acid, to neutralize it, and glycol ether compounds that increase the residence time on the substrate during the cleaning process. However, because the differences in the composition and content of these compounds will vary greatly in the performance and efficiency of the deflux detergent product, the composition and content analysis of the deflux detergent will not only identify the cause of the difference in performance and efficiency, And can be used for the study of the preparation of a deflux detergent.
Previously, groups containing glycol ether groups and amines, the major constituents of the deflux detergents, have been analyzed via a chromatographic-mass spectrometer. However, these two groups have limitations in that they can not be analyzed at the same time because of their different structures. Also, there is a desperate need for an analytical method that can more easily and easily perform an analysis of unknown components and contents by using a chromatography-mass spectrometer.
As a method of analyzing an existing unknown component, Korean Patent No. 10-0782712 discloses a method of predicting the ratio of components of an unknown mixture by using an independent component analysis (ICA) from an X-ray diffraction (XRD) spectrum measured for an unknown mixture We have proposed a method for predicting the composition ratio of the unknown mixture by separating the independent components and predicting the mixing ratio of the components constituting the unknown mixture. However, this analytical method has a limitation in that it can not be applied to the analysis of the organic compound, which is a constituent of the difflux proposed in the present invention, as a method for predicting the component ratio of the inorganic compound present in the unknown sample.
Korean Patent Laid-Open Publication No. 2012-6884 discloses a qualitative and quantitative analysis method of a plating solution, which comprises adding an organic solvent to a plating solution, mixing the plating solution with an organic solvent to dissolve the polymer substance contained in the plating solution in an organic solvent, Separating the organic solvent in which the polymer material is dissolved, and obtaining a polymer material by vaporizing the organic solvent; extracting the polymer material from the plating solution; subjecting the extracted polymer material to qualitative analysis by mass spectrometry And then quantitatively analyzed by liquid chromatography.
However, these analytical methods are not able to simultaneously analyze two heterogeneous components due to the completely different properties of the group containing glycol ether groups and amines, I hold it.
In addition, Jhon M, Halket, Org. Biomol. Chem., 2011, Vol. 9, pp3854-3862 analyzes retention time, mass spectra and molecular weight through GC / MS and LC / MS. GC / TOF / MS can be used for fractionation of unknown samples. And identifying the component using a standard MS / MS spemtrum.
However, since the above-described analysis method is a method of identifying compounds having similar structures and characteristics by using the generally used GC or LC separation conditions as they are, it is difficult to identify components having mutually different polarities, It is very inadequate for application to the analysis of a deflocculant detergent composition as it is inconvenient to apply the same to the quantitative analysis.
The present invention solves the above conventional problems by simultaneously analyzing the components of the group containing the glycol ether group and the amine which are the main constituents of the deflux detergent and analyzing the contents of the unknown components and the respective components by the chromatography- And to provide an analysis method that can be more easily and effectively performed using an analyzer.
Accordingly, it is an object of the present invention to provide a method for simultaneously analyzing components of a glycol ether group and a group containing an amine, which are major constituents of a deflux detergent, to confirm the composition and quantitatively analyze the composition.
Another object of the present invention is to provide a method for accurately and easily analyzing the composition and content of each component of the deflashing detergent, which is an unknown sample, using a mass spectrometer.
It is still another object of the present invention to provide a method for identifying the cause of product performance and efficiency difference for various deflux detergents by quantitatively analyzing the content of the deflux composition materials.
In order to solve the above-mentioned problems, the present invention provides a method of detecting detlux purifying agent, comprising: obtaining a retention time and a mass spectra of a deflux component by using a gas chromatography-mass spectrometer on a deflux detergent as an unknown sample; Predicting the molecular weight through the preccus ion value of each of the difflux components using a liquid chromatography-mass spectrometer; Comparing components predicted through the two steps with an experimental value and a theoretical value using a gas chromatography-high resolution mass spectrometer; Identifying the diffuse angle components using a standard material of the predicted components; And concurrently quantifying the contents of the respective components of the deflux using a gas chromatography-mass spectrometer or a liquid-chromatograph-mass spectrometer. The composition of the deflux detergent is analyzed and quantitatively analyzed using a mass spectrometer ≪ / RTI >
According to the present invention, a new analytical method through an efficient analysis step simultaneously analyzes the components of the glycol ether group and the amine-containing group, which are major constituents of the unknown sample degassing detergent, while analyzing the contents of unknown components and components Can be more effectively and easily performed.
Particularly, when the method of confirming the deterioration of the deflux composition of the present invention and the quantitative analysis method of the present invention are used, it is possible to determine the composition of the main component constituting the deflux detergent as well as the unknown deflux component and the content by using a gas or liquid chromatography- It is possible to identify the cause of the difference in performance and efficiency depending on the kind of the diffusing material, and it can be used in the study of the more effective production of the diffusing material.
1 is a schematic view of a procedure for confirming the composition and quantitative analysis of an unknown sample de-flux detergent using the mass spectrometer according to the present invention.
FIGS. 2A to 2C show ion chromatograms (2a) analyzed by gas chromatography-mass spectrometry of Company A and the results of mass spectra [9.5 minutes (2b) and 10.9 minutes (2c)], respectively.
3A to 3E show the ion chromatogram (3a) analyzed by gas chromatography-mass spectrometry and the mass spectra [3.6 minutes (3b), 8.8 minutes (3c), and 9.5 minutes 3d), 12.9 minutes (3e)].
4A to 4C are the results of ion chromatogram (4a) and the mass spectra [1.80 minutes (4b) and 3.43 minutes (4c)] of the Company A, respectively, which were analyzed using a liquid chromatography-mass spectrometer.
5a to 5e show the ion chromatogram (5a) analyzed by liquid chromatography-mass spectrometry and the mass spectra [0.87 minutes (5b), 0.89 minutes (5c) and 3.43 minutes 5d), 3.51 min (5e)].
Hereinafter, the present invention will be described in more detail as an embodiment.
The present invention relates to a method for identifying the composition of deflux cleaners used for removal of flux in a semiconductor process using a mass spectrometer and quantitatively analyzing the content of each constituent, And a method for analyzing the components of a deflux detergent that can identify the cause of the difference in efficiency.
The analytical method according to the present invention uses a mass analyzer to predict the molecular weight through the retention time, the mass spectra, and the pre-cus ion value of each component of the de-flux, and then the predicted components are analyzed by gas chromatography- And comparing the experimental value with the theoretical value using an analyzer, and performing the composition confirmation and the quantitative analysis using the standard material.
FIG. 1 is a schematic diagram of a procedure for confirming the composition and quantitative analysis of an unknown sample de-flux detergent using the mass spectrometer according to the present invention.
As the composition of the deflux detergent, which is an unknown sample to be applied to the present invention, a mixture of at least one of the components selected from the group containing the glycol ether group and the amine can be used. The analytical method of the present invention can simultaneously analyze and quantify these unknown samples through gas or liquid chromatography-mass spectrometry.
According to the present invention, the retention time and the mass spectra of the respective components of the de-flux are obtained by using a gas chromatograph-mass spectrometer on an unknown sample of the deflux detergent to be analyzed.
According to a preferred embodiment of the present invention, in order to simultaneously analyze and separate the groups containing the glycol ether groups and the amine, which are the diffusing components, the gas chromatography column is DB-1HT (30 m x 0.25 mm x 0.1 mu m) capillary column is preferably used. The temperature is preferably maintained at 25 to 35 DEG C for 0.5 to 3 minutes to separate the components of the amine-containing group in the difflux, then raised to 170 to 200 DEG C at 5 to 15 DEG C, It is preferable to raise the temperature to 260 to 300 ° C at a rate of 15 to 30 ° C per minute and maintain the temperature at 260 to 300 ° C for 5 minutes in order to separate the components of the glycol ether group after maintaining the temperature for 3 to 10 minutes. Using the gas chromatographic temperature conditions of the preferred embodiment of the present invention as described above, it is possible in one experiment to simultaneously isolate the polyfunctional components selected from the group containing the glycol ether group and the amine in the diflux.
According to the present invention, a step of predicting the molecular weight based on the preccus ion value of each of the deflux components is performed using a liquid chromatography-mass spectrometer.
In this step, the glycol ether group and the amine-containing group, which are the constituents of the deflux detergents to be applied to the present invention, have a structure in which the structure thereof is likely to protonate them both. Therefore, when analyzed by a liquid chromatography-mass spectrometer, Mode electrospray ionization method is preferably used.
In accordance with a preferred embodiment of the present invention, the developing solvent used as a liquid chromatographic mobile phase for separation of the glycol ether groups and the amine containing groups, the diluent components, is a 10 mM ammonium acetate buffer solution and acetonitrile , And it is most preferable to use this as a gradient elution method for chromatographic separation and mass spectrometer sensitivity.
The components predicted through the two steps are compared with experimental values and theoretical values using gas chromatography-high resolution mass spectrometry.
In this step, by comparing the components, it is possible to identify the basic constituents contained in the unknown sample of the deflux detergent.
Next, the overall composition of various unknown components such as impurities as well as the basic composition contained in the unknown sample can be confirmed through the step of confirming the diffuse angle components using the standard material of the predicted components.
According to the present invention, once the composition is confirmed, quantitative analysis of the contents of each component of the de-flux is simultaneously performed using a gas chromatography-mass spectrometer or a liquid-chromatograph-mass spectrometer in order to confirm the content of each component It goes through. When this process is performed, it is possible to accurately confirm and analyze the composition and content of each component contained in the unknown sample.
According to a preferred embodiment of the present invention, the quantitative analysis step is preferably performed in a selected ion monitoring mode in terms of improving the accuracy and reproducibility of a quantitative amount.
Therefore, when the analytical method according to the present invention as described above is applied, it is possible to find a deflux constituent component and an amount of which the component and content are unknown by using a gas or liquid chromatography-mass spectrometer, Can be used to investigate the cause of the difference in performance and efficiency as well as to study more effective dephasing.
Therefore, the analysis method of the present invention as described above may further include a step of identifying the cause of the difference in performance and efficiency of the deflux product.
Also, according to the present invention, it is possible to apply the method of the present invention as an efficient process of producing a deflux detergent composition effective for removing flux by using the above-described analysis method of the present invention. That is, the analysis method according to the present invention is applied to the analysis, and based on the analysis, the most suitable deflux detergent composition is searched to produce a deflux detergent having desired properties.
Therefore, the present invention includes a method for producing a Diproflex detergent composition comprising the above-described analytical method according to the present invention.
Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited to the Examples.
Example
(1) Preparation of experimental sample
A sample of A and B diffluent products was made into 0.1 g / mL and diluted 1000 times with water.
(2) obtaining the retention time and mass spectra of each component of the diffusing agent
To obtain the retention time and mass spectra of each component of the diffusing agent, the total scanning mode was used for gas chromatography (Agilent 6890N Gas Chromatograph) connected with a mass spectrometer (5973N Mass Selective Detector). The separation of each component was carried out using an Agilent DB-1HT (30 m x 0.25 mm x 0.1 m) capillary column. The temperature of the injection part was 260 ° C, and the temperature condition at the time of analysis was as follows. The oven starting temperature was maintained at 30 ° C for 1 minute, then raised to 180 ° C at 10 ° C, held at 180 ° C for 5 minutes, then raised to 280 ° C at 20 ° C and maintained at 280 ° C for 5 minutes. Electron Impact (EI) method was used for the ionization method, and the electron energy used was 70 eV.
The ion chromatograms of the defluxes of Company A and Company B and the mass spectra of the peaks respectively are shown in Figs. 2A to 2C and Figs. 3A to 3E, respectively.
2A to 2C show ion chromatograms (2a) analyzed by Gas Chromatography-Mass Spectrometry analyzer of Company A and results of mass spectra [9.5 minutes (2b) and 10.9 minutes (2c) will be.
3A to 3E show the ion chromatogram (3a) analyzed by gas chromatography-mass spectrometry and the mass spectra [3.6 minutes (3b), 8.8 minutes (3c), and 9.5 minutes ), 12.9 minutes (3e)].
(3) Prediction of molecular weight of each component
An ACQUITY UPLC H-Class ultra high performance liquid chromatography-
The mass spectrometer was a cation - mode electrospray ionization method. The ion spraying voltage, ionization voltage, convalve, capillary temperature and source temperature were 3 KV, 30 V, 300 ℃ and 120 ℃, respectively.
The ion chromatograms of the diplexes of Company A and Company B and the mass spectra of the peaks respectively obtained as described above are shown in Figs. 4A to 4C and Figs. 5A to 5E, respectively.
4A to 4C are graphs showing ion chromatograms (4a) analyzed by liquid chromatography-mass spectrometry of Company A and the results of mass spectra [1.80 minutes (4b) and 3.43 minutes (4c) will be.
5a to 5e show the ion chromatogram (5a) analyzed by liquid chromatography-mass spectrometry and the mass spectra [0.87 minutes (5b), 0.89 minutes (5c), and 3.43 minutes d), 3.51 min (5e)].
(4) comparing experimental values and theoretical values of predicted components
The predicted diffusive component materials of A and B after the above steps (1) and (2) are shown in Table 1 below. The predicted diffusive component materials were compared with experimental values and theoretical values by gas chromatography - high resolution mass spectrometry.
The comparative values thus compared are shown in Table 2 below.
(5) Identification of each component of the difflux
Each predicted standard material was purchased to confirm predicted diflux components of Company A and Company B, and the gas chromatography-mass spectrometer of the above (2) and the liquid chromatography-mass spectrometer of the above (3) were used To confirm the respective components.
(6) Diffuse Each component quantification step
The quantitation was analyzed using MS's SIM (selected ion monitoring) mode. The diffusive constituents were quantified by choosing m / z, which is the [M + H] + value.
In the results of Table 1 above, components contained in the D-plus composition for A and B can be identified and compared.
Also, in Table 2, it is possible to check the actual content of each component contained in the degassing composition, and compare the actual content with the standard value, so that the quality of the actual composition of the product can be confirmed. It can be confirmed that this analysis can contribute to the manufacture and research of the product of the deflux detergent composition.
The composition confirmation and quantitative analysis method of the deflux detergent using the mass spectrometer according to the present invention confirms the composition of the deflux detergent used for removing the flux in the semiconductor process and quantitatively analyzes each constituent material to determine the content of the constituent substances in the deflux And it is possible to control the quality of the deflux detergent.
Also, quantitative analysis of the unknown component and content of the deflux composition materials can identify the cause of the difference in performance and efficiency of various deflux products, and can be very conveniently used for the production and research of the deflux detergent.
Claims (8)
Predicting the molecular weight through the preccus ion value of each of the difflux components using a liquid chromatography-mass spectrometer;
Comparing components predicted through the two steps with an experimental value and a theoretical value using a gas chromatography-high resolution mass spectrometer;
Identifying the diffuse angle components using a standard material of the predicted components; And
Simultaneous quantitative analysis of the content of each component of the difflux using a gas chromatography-mass spectrometer or a liquid chromatograph-mass spectrometer
And a method of quantifying and analyzing the composition of the deflux detergent using the mass spectrometer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020150039181A KR101719756B1 (en) | 2015-03-20 | 2015-03-20 | Identification and quantitative analysis method of detergent deflux composition using mass spectrometry |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020150039181A KR101719756B1 (en) | 2015-03-20 | 2015-03-20 | Identification and quantitative analysis method of detergent deflux composition using mass spectrometry |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| KR20160112827A true KR20160112827A (en) | 2016-09-28 |
| KR101719756B1 KR101719756B1 (en) | 2017-03-24 |
Family
ID=57101878
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1020150039181A KR101719756B1 (en) | 2015-03-20 | 2015-03-20 | Identification and quantitative analysis method of detergent deflux composition using mass spectrometry |
Country Status (1)
| Country | Link |
|---|---|
| KR (1) | KR101719756B1 (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005083952A (en) * | 2003-09-10 | 2005-03-31 | Shimadzu Corp | Liquid chromatograph mass spectroscope |
| KR100782712B1 (en) | 2006-12-19 | 2007-12-05 | 주식회사 포스코 | Method for predicting component ratio of unknown mixture |
| US20120006884A1 (en) | 2006-04-27 | 2012-01-12 | Neomax Materials Co., Ltd. | Clad material for wiring connection and wiring connection member processed from the clad material |
| KR101145758B1 (en) * | 2010-04-12 | 2012-05-16 | 재단법인 하동녹차연구소 | Method for screening residual pesticide in food |
-
2015
- 2015-03-20 KR KR1020150039181A patent/KR101719756B1/en active IP Right Grant
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005083952A (en) * | 2003-09-10 | 2005-03-31 | Shimadzu Corp | Liquid chromatograph mass spectroscope |
| US20120006884A1 (en) | 2006-04-27 | 2012-01-12 | Neomax Materials Co., Ltd. | Clad material for wiring connection and wiring connection member processed from the clad material |
| KR100782712B1 (en) | 2006-12-19 | 2007-12-05 | 주식회사 포스코 | Method for predicting component ratio of unknown mixture |
| KR101145758B1 (en) * | 2010-04-12 | 2012-05-16 | 재단법인 하동녹차연구소 | Method for screening residual pesticide in food |
Non-Patent Citations (1)
| Title |
|---|
| 1. Jhon M, Halket, Org. Biomol. Chem.,2011, Vol.9, pp3854-3862. |
Also Published As
| Publication number | Publication date |
|---|---|
| KR101719756B1 (en) | 2017-03-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Cui et al. | Development of a hydrophilic interaction liquid chromatography (HILIC) method for the chemical characterization of water-soluble isoprene epoxydiol (IEPOX)-derived secondary organic aerosol | |
| Coscollà et al. | Combined target and post-run target strategy for a comprehensive analysis of pesticides in ambient air using liquid chromatography-Orbitrap high resolution mass spectrometry | |
| Parshintsev et al. | Methods for characterization of organic compounds in atmospheric aerosol particles | |
| JP5696787B2 (en) | Analytical method of halogen oxyacid | |
| CN108398479B (en) | Method and apparatus for isotope ratio mass spectrometry | |
| Zhang et al. | Bioanalytical strategies for developing highly sensitive liquid chromatography/tandem mass spectrometry based methods for the peptide GLP‐1 agonists in support of discovery PK/PD studies | |
| KR101719756B1 (en) | Identification and quantitative analysis method of detergent deflux composition using mass spectrometry | |
| JP7295942B2 (en) | mass correction | |
| WO2017077389A1 (en) | Quantification of drugs in biological samples | |
| KR101921978B1 (en) | Organic analytical method for the raw materials | |
| EP3669185B1 (en) | Quantitative method for determining the organic acid content of crude oil | |
| EP3047506B1 (en) | Automated adjustment of capillary voltage based on the elution conditions to retain optimal ionization conditions | |
| Hasan et al. | Development of an HPLC method for formic acid analysis through peak exclusion approach | |
| AU2020364006A2 (en) | Liquid chromatography-mass spectrometry (LC-MS) methods for analyzing ampholyte lot variation | |
| KR102033005B1 (en) | The mass spectrometry of hydrogen/deuterium exchange | |
| JP2009069053A (en) | Sample for analyzing generated gas, generated gas analyzing method and gas generation behavior analysis method | |
| JP2021518567A (en) | Mass Spectrometry Determination of Testosterone in Multiplexed Patient Samples | |
| Ai et al. | Simple and rapid determination of N6‐(Δ2‐isopentenyl) adenine, zeatin, and dihydrozeatin in plants using on‐line cleanup liquid chromatography coupled with hybrid quadrupole‐Orbitrap high‐resolution mass spectrometry | |
| Alelyunas et al. | Quantitation by high resolution mass spectrometry: using target enhancement and Tof-MRM to achieve femtogram-level on-column sensitivity for quantitation of drugs in human plasma | |
| Aceña et al. | Liquid chromatography–mass spectrometry: quantification and confirmation aspects | |
| Schultz et al. | Fundamentals of LC-MS/MS for regulated bioanalysis | |
| Marino Ed D et al. | Rapid screening and quantification of synthetic cannabinoids in DART-MS and NMR spectroscopy | |
| Tisler et al. | Separation Science: The State of the Art: Nontargeted Screening in Environmental Analysis: An Example Showing Migration of Chemicals from Reusable Sports Plastic Bottles into Drinking Water | |
| DE112015002519T5 (en) | Monitoring a liquid chromatography elution to determine when to run a reference mass calibration | |
| DE10393486T5 (en) | Improved separation of a dissolved analyte on hydrophobic surface by desolvation of organic solvents |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A201 | Request for examination | ||
| E902 | Notification of reason for refusal | ||
| E701 | Decision to grant or registration of patent right | ||
| GRNT | Written decision to grant |