近日，來(lái)自山東師范大學(xué)光學(xué)與光子器件技術(shù)重點(diǎn)實(shí)驗(yàn)室的聯(lián)合研究團(tuán)隊(duì)發(fā)表了一篇題為 Open-path sensor based on QCL for atmospheric N₂O measurement 的研究論文。

Recently, a collaborative research team from the Shandong Provincial Engineering and Technical Center of Light Manipulations & Shandong Provincial Key Laboratory of Optics and Photonic Device, School of Physics and Electronics, Shandong Normal University published a research paper titled Open-path sensor based on QCL for atmospheric N₂O measurement.

簡(jiǎn)介

作為重要的溫室氣體之一，氧化亞氮（N₂O）可能導(dǎo)致空氣污染和全球變暖。N₂O在大氣中的壽命很長(zhǎng)，更糟糕的是，其全球變暖潛力比二氧化碳高300倍。因此，開(kāi)發(fā)一種快速、實(shí)時(shí)和高精度的氣體傳感器系統(tǒng)，用于檢測(cè)大氣中的N₂O濃度水平，對(duì)于更好地理解全球變暖和氣候變化至關(guān)重要。

調(diào)諧二極管激光吸收光譜學(xué)（TDLAS）在高靈敏度、選擇性和快速響應(yīng)領(lǐng)域廣泛報(bào)道，并已被證明是實(shí)時(shí)檢測(cè)N₂O的可靠工具?；诓ㄩL(zhǎng)調(diào)制光譜學(xué)（WMS）的TDLAS已被證明是提高檢測(cè)靈敏度和降低電子噪聲的良好方法。大多數(shù)傳感器是封閉路徑系統(tǒng)。這嚴(yán)重限制了在遠(yuǎn)程或露天研究中進(jìn)行連續(xù)監(jiān)測(cè)的實(shí)際適用性，并限制了測(cè)量的空間覆蓋范圍。為解決這一問(wèn)題，本文開(kāi)發(fā)了一種緊湊的開(kāi)放光學(xué)路徑氣體傳感器系統(tǒng)。

Introduction

As one of the important greenhouse gases, nitrous oxide (N₂O), can give rise to air pollution and global warming. N₂O has a long atmospheric lifetime, and worse its global warming potential is 300 times higher than carbon dioxide. Therefore, the development of a fast, real-time, and high-precision gas sensor system for detecting the atmospheric N₂O concentration level is essential for the better understanding of global warming and climate changes.

Tunable diode laser absorption spectroscopy (TDLAS), as a versatile technique, has be widely reported for real-time analysis of gas compositions in the field of high sensitivity, selectivity, and fast response and it has been demonstrated as a dependable tool for real-time detection of N₂O. Wavelength modulation spectroscopy (WMS) based TDLAS has been proved to be a good method for improving the detection sensitivity and reducing the electronic noise. Most of sensors are closed-path systems. This severely restricts the practical applicability of continuous monitoring in remote or open-field researches, and limits the spatial coverage of the measurements. To address this problem, in this paper, we develop a compact openoptical-path gas sensor system.

實(shí)驗(yàn)細(xì)節(jié)

基于QCL的開(kāi)路N₂O氣體傳感器的系統(tǒng)框架如圖1所示。它主要由三部分組成：激光系統(tǒng)、光學(xué)元件和數(shù)據(jù)處理部分。激光系統(tǒng)由QCL、激光驅(qū)動(dòng)器和信號(hào)發(fā)生器組成。光學(xué)部件具有檢測(cè)光路和參考光路。數(shù)據(jù)處理部分包括數(shù)據(jù)采集、信號(hào)處理和顯示模塊。

The system framework of the open-path N₂O gas sensor based on QCL is depicted in Fig. 1. It mainly consists of three parts: the lasersystem, the optical elements, and the data processing section. The laser-system consists of a QCL, a laser drive and a signal generator. The optical component has the detecting and reference optical paths. The data processing section includes the data acquisition, signal processing and display modules.

Fig. 1. The N₂O sensor system schematic diagram.

寧波海爾欣光電科技有限公司為此項(xiàng)目提供了HPQCL-Q™ 標(biāo)準(zhǔn)量子級(jí)聯(lián)激光發(fā)射頭，QC750-Touch™ 量子級(jí)聯(lián)激光屏顯驅(qū)動(dòng)器，HPPD-M-B 前置放大制冷一體型碲鎘汞（MCT）光電探測(cè)器。

HealthyPhoton Technology Co., Ltd. , provided a QCL(HPQCL-Q™ ), a driver(QC750-Touch™), a HgCdTe photodetector (HPPD-M-B) for this project.

HPQCL-Q™            QC750-Touch™             HPPD-M-B

在這項(xiàng)工作中，需要考慮N₂O或其他物質(zhì)（主要是水蒸氣）的光譜吸收干擾，以減少它們對(duì)系統(tǒng)特異性和準(zhǔn)確性的副作用。如圖2(c)所示，根據(jù)HITRAN 2016數(shù)據(jù)庫(kù)，已經(jīng)模擬了N₂O、CO和CO₂的吸收線強(qiáng)度，范圍從2020 ~ 2220 cm^-1。幸運(yùn)的是，N₂O的基本振動(dòng)帶在波數(shù)為2200cm^-1左右，遠(yuǎn)離水蒸氣的吸收帶。因此，室溫下的QCL可以達(dá)到N₂O的基本振動(dòng)帶，檢測(cè)靈敏度為ppb級(jí)?？紤]到靈敏度和成本，選擇了中心波數(shù)為2203.73  cm^-1的QCL來(lái)檢測(cè)N₂O。QCL的中心電流和溫度分別設(shè)置為330 mA和36.0 °C。

Details

In this work, we need to take the spectral absorption interference of N₂O or other substances (mostly water vapor) into consideration in order to reduce their side effects on the specificity and accuracy of the system. As depicted in Fig. 2(c), the absorption line intensity of N₂O, CO and CO₂ have been simulated from 2020 ~ 2220cm^-1, according to the HITRAN 2016 database. Fortunately, the unique fundamental vibration band of N₂O is around wavenumber of 2200cm^-1, which is stay away from the absorption band of water vapor. Therefore, the N₂O fundamental vibration band can be reached by room-temperature QCL, and the detection sensitivity is ppb level. Taking sensitivity and cost into consideration, a QCL emitting at center wavenumber of 2203.73 cm^-1 was selected for detection of N₂O. Of the QCL, the central  current and temperature were set at 330 mA and 36.0 ?C, respectively.

Fig. 2. (a): The relationship between the QCL emission wavenumber and drive current. (b): The dependence the QCL emission wavenumber and temperature. (c): The intensity distribution of absorption lines of N₂O, CO and CO₂ in the range of 2020 ~ 2220 cm^-1.

結(jié)論

我們實(shí)現(xiàn)了用一種緊湊的開(kāi)路氣體傳感器檢測(cè)大氣中的N₂O。在這種傳感器中，采用了波長(zhǎng)調(diào)制光譜學(xué)與1f-歸一化WMS檢測(cè)策略，以提高檢測(cè)靈敏度并消除光強(qiáng)度波動(dòng)的影響。對(duì)20 ppm N₂O標(biāo)準(zhǔn)氣體進(jìn)行了校準(zhǔn)，標(biāo)準(zhǔn)偏差為0.011 ppm，表明具有高精度。對(duì)實(shí)驗(yàn)室N₂O空氣進(jìn)行了連續(xù)7小時(shí)的測(cè)量，濃度的標(biāo)準(zhǔn)偏差低于1.5 ppb。我們使用Allan偏差分析得出，在1秒的積分時(shí)間下，N₂O的檢測(cè)限為1.1 ppb，而在最佳積分時(shí)間為95秒時(shí)，靈敏度可以提高到0.14 ppb。通過(guò)在自然環(huán)境中進(jìn)行的為期兩天的實(shí)時(shí)測(cè)量驗(yàn)證了所開(kāi)發(fā)傳感器系統(tǒng)的長(zhǎng)期穩(wěn)定性。得出的結(jié)果充分證明我們的開(kāi)放光學(xué)路徑氣體傳感器系統(tǒng)具有快速響應(yīng)、良好穩(wěn)定性、高靈敏度和高精度。

在實(shí)際應(yīng)用方面，該系統(tǒng)可用于檢測(cè)農(nóng)田和汽車尾氣中的N₂O排放。此外，我們認(rèn)為通過(guò)更新具有不同發(fā)射波長(zhǎng)的QCL，傳感器系統(tǒng)還可以檢測(cè)不同類型的微量氣體。

參考來(lái)源：

Open-path sensor based on QCL for atmospheric N₂O measurement,

Results in Physics 31 (2021) 104909