Gas chromatographic analysis method of high-purity triethyl borate

Abstract

The invention discloses a gas chromatographic analysis method of high-purity triethyl borate, which comprises the following steps: a preparation step: preparing a sample, cleaning a sample injection needle and a chromatographic column, the purity of the sample is at least 4N, and the sample injection needle is repeatedly cleaned by isopropanol and then repeatedly cleaned by the sample; and an analysis step: loading a sample, carrying out gas chromatographic analysis, and carrying out TEB purity calculation by adopting a peak area normalization method. According to the method, a high-purity sample is taken as an analysis object, under the condition that impurities are not introduced, impurity components in a product are identified as much as possible, and the accuracy of a detection result is ensured.

Description

Technical Field

[0001] This invention belongs to the field of gas chromatography technology, specifically relating to a gas chromatography analysis method for high-purity triethyl borate. Background Technology

[0002] In the semiconductor industry, TEB (Thin Film Embedded Batch) is mainly used in thin film deposition and photolithography processes. Insufficient purity can lead to deposition failure due to excessive metal ions, resulting in abnormal deposition rates and uneven film thickness. Excessive organic impurities can cause photolithography defects, increasing the linewidth roughness of EUV photoresist and affecting product performance. In the photovoltaic industry, it is primarily used in the production of PERC / TOPCon cells. Excessive carbon impurities can cause uneven boron atom diffusion, affecting product lifespan and increasing cleaning process costs, leading to unnecessary losses. Therefore, the semiconductor and photovoltaic industries currently typically use 4N or higher purity TEB, strictly controlling carbon and other organic impurities.

[0003] Currently, the industry typically uses organic solvent dilution for pretreatment before analysis. This not only introduces additional impurities but also fails to identify and quantify trace impurities. Therefore, this type of method is only suitable for the analysis of TEB with a purity of 3N or lower.

[0004] Therefore, to address the aforementioned technical problems, it is necessary to provide a gas chromatographic analysis method for high-purity triethyl borate. Summary of the Invention

[0005] The purpose of this invention is to provide a gas chromatographic analysis method for high-purity triethyl borate.

[0006] To achieve the above objectives, a specific embodiment of the present invention provides the following technical solution:

[0007] Gas chromatographic analysis method for high-purity triethyl borate, including

[0008] Preparation steps include preparing the sample, cleaning the injection needle and chromatographic column. The purity of the sample is at least 4N. The injection needle is cleaned repeatedly with isopropanol and then repeatedly with the sample.

[0009] Analytical steps: Sample loading and gas chromatography analysis were performed, and the TEB purity was calculated using the peak area normalization method.

[0010] In one or more embodiments of the present invention, the conditions for gas chromatography analysis are as follows:

[0011] Detector: FID detector;

[0012] Chromatographic column: Non-polar chromatographic column;

[0013] Carrier gas: High-purity carrier gas with a purity of not less than 4N, with a flow rate of 1.2-1.5 mL / min.

[0014] In one or more embodiments of the present invention, the nonpolar chromatographic column is selected from HP-5, DB-5, DB-5ms, HP-5Q, DB-5Q, μLtra-2, Rtx-5, Rtx-5ms, BPX-5, BP-5, CP-Sil 8 CB, CP-8940, TR-5, TR-5ms, Rxi-5ms, Rxi-5Sil MS, PTE-5, AT-5, AT-5ms, ZB-5, ZB-5ms, ZB-5ms Plus, SLB-5ms, Equity-5, GC8890.

[0015] In one or more embodiments of the present invention, the high-purity carrier gas is selected from helium, argon, and nitrogen.

[0016] In one or more embodiments of the present invention, during sample loading, a split injection method is used, with an injection volume of 2 μL and a split ratio of 45-50:1.

[0017] In one or more embodiments of the present invention, during analysis, the column temperature is programmed to rise: the initial column oven temperature is 35-40°C, held for 6-10 min, then increased to 60-65°C at a rate of 8-10°C / min, held for 1-3 min, and then increased to 270-280°C at a rate of 30-35°C, held for 5-8 min.

[0018] In one or more embodiments of the present invention, cleaning the injection needle specifically involves repeatedly rinsing it with isopropanol at least three times and then repeatedly rinsing it with the sample at least three times.

[0019] In one or more embodiments of the present invention, the injection needle is further subjected to a post-rinse after sample loading, wherein the post-rinse is performed by rinsing with isopropanol at least three times.

[0020] Compared with existing technologies, the gas chromatography analysis method for high-purity triethyl borate of the present invention uses high-purity samples as the analysis object, and identifies as many impurity components in the product as possible without introducing impurities, thus ensuring the accuracy of the detection results. Taking TEB with a purity of 4N as an example, since TEB will violently hydrolyze to produce boric acid and ethanol when it comes into contact with water, resulting in a decrease in purity, the sampling and analysis process of this method can be controlled in a nitrogen atmosphere as much as possible to isolate moisture in the air. Attached Figure Description

[0021] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments recorded in the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0022] Figure 1 This is a chromatogram of the 4N product in one embodiment of the present invention;

[0023] Figure 2 This is a table showing the analysis results of a 4N product in one embodiment of the present invention;

[0024] Figure 3 This is a chromatogram of the 5N product in one embodiment of the present invention;

[0025] Figure 4 This is a table showing the analysis results of the 5N product in one embodiment of the present invention. Detailed Implementation

[0026] To enable those skilled in the art to better understand the technical solutions in this disclosure, the technical solutions of this invention will be clearly and completely described below in conjunction with the embodiments disclosed herein. Obviously, the described embodiments are only some embodiments of this disclosure, and not all embodiments. Based on the embodiments in this disclosure, all other embodiments obtained by those skilled in the art without creative effort should fall within the scope of protection of this disclosure.

[0027] Example 1

[0028] Purchase 3N TEB, purify it to obtain 4N product, and dispense it into two vials in a glove box (via vial A: needle washing solution, used to rinse the injection needle, vial B: used for sample injection analysis).

[0029] Chromatographic configuration and key parameters:

[0030] Instrument: Agilent GC8890;

[0031] Detector: FID detector, temperature 250℃;

[0032] Chromatographic column: non-polar HP-5 column (30m×0.25mm×0.25μm) or other equivalent column; carrier gas: high-purity He carrier gas, flow rate 1.2ml / min;

[0033] Injection method: split injection, injection volume 2 μL, split ratio 50:1;

[0034] Programmed temperature rise: Initial column oven temperature 40℃, hold for 6 min, increase to 60℃ at a rate of 10℃, hold for 1 min, then increase to 280℃ at a rate of 30℃, hold for 5 min;

[0035] First, rinse the injection needle three times with needle washing solution (isopropanol) (to remove any residual TEB from the previous injection). Then, rinse vial A (the sample to be tested) three times (to remove isopropanol and reduce interference from impurities). Next, take a sample from vial B for analysis. After injecting the sample, rinse the injection needle 5-10 times with isopropanol and allow it to air dry. Analytical results are shown below. Figure 1 , Figure 2 As shown.

[0036] Example 2

[0037] Purchase 3N TEB, purify it to obtain a 5N purity product, and dispense it into two vials in a glove box (via vial A: needle washing solution, used to rinse the injection needle, vial B: used for sample injection analysis).

[0038] Chromatographic configuration and key parameters:

[0039] Instrument: Agilent GC8890;

[0040] Detector: FID detector, temperature 250℃;

[0041] Chromatographic column: non-polar HP-5 column (30m×0.25mm×0.25μm) or other equivalent column; carrier gas: high-purity He carrier gas, flow rate 1.2ml / min;

[0042] Injection method: split injection, injection volume 2 μL, split ratio 50:1;

[0043] Programmed temperature rise: Initial column oven temperature 40℃, hold for 6 min, increase to 60℃ at a rate of 10℃, hold for 1 min, then increase to 280℃ at a rate of 30℃, hold for 5 min;

[0044] First, rinse the injection needle three times with needle washing solution (isopropanol) (to remove any residual TEB from the previous injection). Then, rinse vial A (the sample to be tested) three times (to remove isopropanol and reduce interference from impurities). Next, take a sample from vial B for analysis. After injecting the sample, rinse the injection needle 5-10 times with isopropanol and allow it to air dry. Analytical results are shown below. Figure 3 , Figure 4 As shown.

[0045] Example 3

[0046] The only difference between this embodiment and Embodiment 1 is that: 3N TEB is purchased, purified to obtain 4N product, and then dispensed into two vials in a glove box (via vial A: needle washing solution, used to rinse the injection needle, and vial B: used for sample analysis).

[0047] Chromatographic configuration and key parameters:

[0048] Instrument: Agilent GC8890;

[0049] Detector: FID detector, temperature 250℃;

[0050] Chromatographic column: non-polar HP-5 column (30m×0.25mm×0.25μm) or other equivalent column; carrier gas: high-purity He carrier gas, flow rate 1.2ml / min;

[0051] Injection method: split injection, injection volume 2 μL, split ratio 45:1;

[0052] Temperature program: Initial column oven temperature 35℃, hold for 10 min, increase to 65℃ at a rate of 8℃ / min, hold for 3 min, then increase to 270℃ at a rate of 35℃, hold for 8 min.

[0053] The retention time and peak value of each component in the detection method of this embodiment are stable, with good repeatability. High-concentration samples are completely separated, with a resolution of over 1.5 and a content of over 99.9913%.

[0054] Example 4

[0055] The only difference between this embodiment and embodiment 2 is that: 3N TEB is purchased, purified to obtain a product with a purity of 5N, and then dispensed into two vials in a glove box (via vial A: needle washing solution, used to rinse the injection needle, and vial B: used for sample analysis).

[0056] Chromatographic configuration and key parameters:

[0057] Instrument: Agilent GC8890;

[0058] Detector: FID detector, temperature 250℃;

[0059] Chromatographic column: non-polar HP-5 column (30m×0.25mm×0.25μm) or other equivalent column; carrier gas: high-purity He carrier gas, flow rate 1.2ml / min;

[0060] Injection method: split injection, injection volume 2 μL, split ratio 45:1;

[0061] Temperature program: Initial column oven temperature 35℃, hold for 10 min, increase to 65℃ at a rate of 8℃ / min, hold for 3 min, then increase to 270℃ at a rate of 35℃, hold for 8 min.

[0062] The retention time and peak value of each component in the detection method of this embodiment are stable, with good repeatability. High-concentration samples are completely separated, with a resolution of over 1.5 and a content of over 99.99972%.

[0063] Example 5

[0064] The only difference between this embodiment and Embodiment 1 is that: 3N TEB is purchased, purified to obtain 4N product, and then dispensed into two vials in a glove box (via vial A: needle washing solution, used to rinse the injection needle, and vial B: used for sample analysis).

[0065] Chromatographic configuration and key parameters:

[0066] Instrument: Agilent GC8890;

[0067] Detector: FID detector, temperature 250℃;

[0068] Chromatographic column: non-polar HP-5 column (30m×0.25mm×0.25μm) or other equivalent column; carrier gas: high-purity He carrier gas, flow rate 1.2ml / min;

[0069] Injection method: split injection, injection volume 2 μL, split ratio 47:1;

[0070] Temperature program: Initial column oven temperature 37℃, hold for 8 min, increase to 63℃ at a rate of 9℃ / min, hold for 2 min, then increase to 275℃ at a rate of 33℃, hold for 7 min.

[0071] The retention time and peak value of each component in the detection method of this embodiment are stable, with good repeatability. High-concentration samples are completely separated, with a resolution of over 1.5 and a content of over 99.9958%.

[0072] Example 6

[0073] The only difference between this embodiment and embodiment 2 is that: 3N TEB is purchased, purified to obtain a product with a purity of 5N, and then dispensed into two vials in a glove box (via vial A: needle washing solution, used to rinse the injection needle, and vial B: used for sample analysis).

[0074] Chromatographic configuration and key parameters:

[0075] Instrument: Agilent GC8890;

[0076] Detector: FID detector, temperature 250℃;

[0077] Chromatographic column: non-polar HP-5 column (30m×0.25mm×0.25μm) or other equivalent column; carrier gas: high-purity He carrier gas, flow rate 1.2ml / min;

[0078] Injection method: split injection, injection volume 2 μL, split ratio 47:1;

[0079] Temperature program: Initial column oven temperature 37℃, hold for 8 min, increase to 63℃ at a rate of 9℃ / min, hold for 2 min, then increase to 275℃ at a rate of 33℃, hold for 7 min.

[0080] The retention time and peak value of each component in the detection method of this embodiment are stable, with good repeatability. High-concentration samples are completely separated, with a resolution of over 1.5 and a content of over 99.99936%.

[0081] It will be apparent to those skilled in the art that this disclosure is not limited to the details of the exemplary embodiments described above, and that this disclosure can be implemented in other specific forms without departing from its spirit or essential characteristics. Therefore, the embodiments should be considered in all respects as exemplary and non-limiting, and the scope of this disclosure is defined by the appended claims rather than the foregoing description. Thus, all variations falling within the meaning and scope of equivalents of the claims are intended to be included within this disclosure. No reference numerals in the claims should be construed as limiting the scope of the claims.

[0082] Furthermore, it should be understood that although this specification describes embodiments, not every embodiment contains only one independent technical solution. This narrative style is merely for clarity. Those skilled in the art should consider the specification as a whole, and the technical solutions in each embodiment can also be appropriately combined to form other embodiments that can be understood by those skilled in the art.

Claims

1. A method for gas chromatography analysis of high-purity triethyl borate, comprising a preparation step, including preparing a sample, cleaning a sample injection needle and a chromatographic column, wherein the purity of the sample is at least 4N, and the sample injection needle is repeatedly cleaned with isopropyl alcohol and then repeatedly cleaned with the sample; an analysis step, including sample injection and gas chromatography analysis, and calculating the purity of TEB by peak area normalization method.

2. The method of gas chromatographic analysis of high-purity triethyl borate according to claim 1, characterized in that, The conditions for the gas chromatography analysis are as follows: a detector: FID detector; a chromatographic column: a non-polar chromatographic column; carrier gas: high-purity carrier gas with a purity of not less than 4N, and a flow rate of 1.2-1.5 mL / min.

3. The method of gas chromatographic analysis of high-purity triethyl borate according to claim 2, characterized in that, The non-polar chromatographic column is selected from HP-5, DB-5, DB-5ms, HP-5Q, DB-5Q, μLtra-2, Rtx-5, Rtx-5ms, BPX-5, BP-5, CP-Sil 8 CB, CP-8940, TR-5, TR-5ms, Rxi-5ms, Rxi-5Sil MS, PTE-5, AT-5, AT-5ms, ZB-5, ZB-5ms, ZB-5ms Plus, SLB-5ms, Equity-5, GC8890.

4. The method of gas chromatographic analysis of high-purity triethyl borate according to claim 2, characterized in that, The high-purity carrier gas is selected from helium, argon and nitrogen.

5. The method of gas chromatographic analysis of high-purity triethyl borate according to claim 1, characterized in that, During sample injection, split injection is used, the injection amount is 2 μL, and the split ratio is 45-50:

1.

6. The method of gas chromatographic analysis of high purity triethyl borate according to claim 1, characterized in that, During analysis, the column temperature is programmed as follows: the initial column oven temperature is 35-40℃, maintained for 6-10 min, then increased to 60-65℃ at a rate of 8-10℃ / min, maintained for 1-3 min, then increased to 270-280℃ at a rate of 30-35℃, and maintained for 5-8 min.

7. The method of gas chromatographic analysis of high purity triethyl borate according to claim 1, characterized in that, The cleaning of the sample injection needle is specifically repeated at least 3 times with isopropyl alcohol and then repeated at least 3 times with the sample.

8. The method of gas chromatographic analysis of high-purity triethyl borate according to any one of claims 1 to 7, characterized in that, The method further comprises post-rinsing the sample injection needle after sample injection, wherein the post-rinsing is repeated at least 3 times with isopropyl alcohol.

Images