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High-purity gases are widely used in semiconductor device manufacturing and fuel cell industries. However, the impurities have a significant influence on the processing accuracy directly. Thus, it is particularly necessary to carry out the concentration diagnosis of key trace impurity gases. In this work, an integrated system for the simultaneous detection of trace NO/NOx is designed based on the chemiluminescence spectrum theory and the catalytic conversion mechanism of nitrogen oxides. The test experiments reveal that the measurement system has the advantages of high linearity (R2 = 0.99967), high sensitivity, low detection limit (~25 ppt), and easy operation. Subsequently, the measurement method for NOx with different high-purity gases are established considering the quenching effects of different background gases on fluorescence and phosphorescent. The detection system is then used to measure the ppb-level NOx impurities in four commonly used high-purity gases (Ar, O2, CO2, N2) in the laboratory. The results show that the NO impurity in CO2 gas is the highest, approximately 9 ppb,but relatively low, 0–4 ppb, in the other high-purity gases. The NO2 impurities in all four high-purity gases are very low (< 6 ppb). Finally, the NOx impurity content values in high-purity gases are evaluated and analyzed based on the gas preparation and purification approach. The aim of the work is to provide a reliable diagnostic approach and data basis of the impurity composition for the fuel cell, semiconductor and other cutting-edge technological fields.
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Keywords:
- chemiluminescence /
- high-purity gas /
- trace gas /
- quenching
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Shan J, Wang Y, Wang J, Jin P J, Ji X X 2020 Low Temper. Speci. Gas. 38 32
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Pan Y, Deng F F, Wang W K, Yang J W, Zhang T, Lin J J, Long Z, Yao W M, Fang
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[6] 牛丽红, 李胜, 于世林 2017 广东化工 44 117
Google Scholar
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Google Scholar
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Google Scholar
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Google Scholar
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Google Scholar
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[21] Putluru S S R, Schill L, Jensen A D, Fehrmann R S N 2015 Appl Catal. B 165 628
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Google Scholar
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图 1 NO与O3化学发光反应能级跃迁原理示意图
Figure 1. Schematic diagram of chemiluminescence reaction level transition of NO and O3.
图 2 化学发光测量系统装置示意图. V为可调节脉冲型高压电源; MFC为流量控制计; CL为化学发光; PMT为光电倍增管; T0为NO测量模式通道; T1为NO2测量模式通道
Figure 2. Schematic diagram of chemiluminescence measurement system. V is adjustable pulse high voltage power supply; MFC is flow control meter; CL is chemiluminescence; PMT is photomultiplier tube, T0 is NO measurement mode channel; T1 is NO2 measurement mode channel.
图 3 化学发光探测系统对63.3 ppb NO2和39 ppb NO混合标气的动态测量结果
Figure 3. Dynamic measurement results of 63.3 ppb NO2 and 39 ppb NO mixed standard gas by chemiluminescence detection system.
图 4 不同NO2标气浓度测量结果 (a)不同NO2浓度下对应5个周期的原始测量信号; (b)不同NO2标气浓度的电压信号及其线性拟合曲线
Figure 4. Different NO2 standard gas concentration measurement: (a) Original measurement signals corresponding to 5 cycles at different NO2 concentrations; (b) voltage signals of different NO2 gas concentrations and their linear fitting curves.
图 5 “零气”和空气源时测量系统电压信号的Allan标准差
Figure 5. Allan standard deviation of the voltage signal of zero gas and air for the measurement system.
图 7 空气、“零气”及高纯气体中NOx浓度测量
Figure 7. Measurement of NOx concentration in air, zero gas and high purity gas.
表 1 不同组分高纯气体的NOx转换系数及其测量结果修正值
Table 1. NOx conversion coefficient of different high-purity gas components and modification of measurement results.
高纯气体
组分线性
系数(m)$I_{\rm N_2}/I_{\rm M}$ 浓度修正值
(ppb, 高纯气体)NO NO2 O2 0.115 1.115 ~1.4 ~2.9 CO2 1.047 2.047 ~ 8.9 ~2.3 Ar –0.48 0.73 ~0.5 ~5.2 N2 0 1 ~3.9 ~4.4 注: 相对淬灭系数Rm可以用公式Rm = 1+ m*d{M}描述, 式中m为线性拟合系数, {M}为M的物质的量的比. 具体公式推导见文献[31]. 
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[1] Funke H H, Grissom B L, McGrew C E, Raynor M W 2003 Rev. Sci. Instrum. 74 3909
Google Scholar
[2] 单静, 王莹, 王杰, 靳鹏杰, 吉雪霞 2020 低温与特气 38 32
Google Scholar
Shan J, Wang Y, Wang J, Jin P J, Ji X X 2020 Low Temper. Speci. Gas. 38 32
Google Scholar
[3] Z 2021 Nat. Gas Ind. 41 115 (in Chinese) [潘义, 邓凡锋, 王维康, 杨嘉伟, 张婷, 林俊杰, 龙舟, 姚伟民, 方正 2021 天然气工业 41 115]
Pan Y, Deng F F, Wang W K, Yang J W, Zhang T, Lin J J, Long Z, Yao W M, Fang
[4] Sethuraman V A, Weidner J W 2010 Electrochim. Acta 55 5683
Google Scholar
[5] Myrberg T, Jacob A P, Nur O, Friesel M, Willander M, Patel C J, Campidelli Y, Hernandez C, Kermarrec O, Bensahel D 2004 J. Mater Sci. Mater. Electron. 15 411
Google Scholar
[6] 牛丽红, 李胜, 于世林 2017 广东化工 44 117
Google Scholar
Niu L H, Li S, Yu S L 2017 Guangzhou Chem. Indust. 44 117
Google Scholar
[7] Engel G S, Moyer E J 2007 Opt. Lett. 32 704
Google Scholar
[8] Chao X, Jeffries J B, Hanson R K 2011 Appl. Phys. B 106 987
Google Scholar
[9] 孙逊运 1988 色谱 6 334
Sun X Y 1988 Chin. J. Chromatogr. 6 334
[10] Li H, Liu W Q, Kan R F 2019 Rev. Sci. Instrum. 90 046103
Google Scholar
[11] Dickerson R R, Delany A C, Wartburg A F 1984 Rev. Sci. Instrum. 55 1995
Google Scholar
[12] Delany A C, Dickerson R R, Melchior F L, Wartburg A F 1982 Rev. Sci. Instrum. 53 1899
Google Scholar
[13] Johnston H S, Crosby H J 1954 J. Phys. Chem. C 22 689
Google Scholar
[14] Douglas A E, Huber K P 1965 Can. J. Phys. 43 74
Google Scholar
[15] Clough P N, Thrush B A 1967 J. Chem. Soc. , Faraday trans. 63 915
Google Scholar
[16] Steffenson D M, Stedman D H 1974 Anal. Chem. 46 1704
Google Scholar
[17] Ridley B A, Grahek F E 1990 J. Atmos. Ocean. Tech. 7 307
Google Scholar
[18] Kliner D A V, Daube B C, Burley J D, Wofsy S C 1997 J. Geophys. Res. Atmos. 102 10759
[19] Day D A, Dillon M B, Wooldridge P J, Thornton J A, Rosen R S, Wood E C, Cohen R C 2003 J. Geophys. Res. 108 4501
Google Scholar
[20] McClenny W A, Williams E J, Cohen R C, Stutz J 2002 J. Air. Waste Manag. Assoc. 52 542
Google Scholar
[21] Putluru S S R, Schill L, Jensen A D, Fehrmann R S N 2015 Appl Catal. B 165 628
[22] Bollinger M J, Sievers R E, Fahey D W, Fehsenfeld F C 1983 Anal. Chem. 55 1980
Google Scholar
[23] Yagi S, Tanaka M 1979 J. Phys. D. Appl. Phys. 12 1509
Google Scholar
[24] Thrush B A 1973 J. Phys. Chem. C 58 5191
Google Scholar
[25] Smith W H, Liszt H S 1971 J. Quant. Spectrosc. Ra. 11 45
Google Scholar
[26] Fereja T H, Hymete A, Gunasekaran T 2013 ISRN Spectroscopy 2013 1
Google Scholar
[27] Zabielski M F, Seery D J, Dodge L G 1984 Environ. Sci. Technol. 18 88
Google Scholar
[28] Fontijn A, Meyer C B, Schiff H I 1964 J. Chem. Phys. 40 64
Google Scholar
[29] Moonen P C, Cape J N, Storeton-West R L, McColm R 1998 J. Atmos. Chem. 29 299
Google Scholar
[30] Mehrabzadeh A A, O'Brien R J, Hard T M 1983 Anal. Chem. 55 1660
Google Scholar
[31] Tidona R J, Nizami A A, Cernansky N P 1988 JAPCA 38 806
Google Scholar
[32] Nakayama T, Ide T, Taketani F, Kawai M, Takahashi K, Matsumi Y 2008 Atmospheric Environ. 42 1995
Google Scholar
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