CN1206493A - Laser ionization mass spectroscope and mass spectrometric analysis method - Google Patents

Laser ionization mass spectroscope and mass spectrometric analysis method Download PDF

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CN1206493A
CN1206493A CN 97191457 CN97191457A CN1206493A CN 1206493 A CN1206493 A CN 1206493A CN 97191457 CN97191457 CN 97191457 CN 97191457 A CN97191457 A CN 97191457A CN 1206493 A CN1206493 A CN 1206493A
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laser
ionization
mass
pulse
vacuum
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宫泽邦夫
宫本等
今坂藤太郎
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日本钢管株式会社
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Abstract

一种质量分析装置,具有质量分析仪(4),质量分析仪(4)又包括:具有形成分子射流的脉冲阀的试样导入部(1);脉冲激光振荡器(2);以及分析用该激光离子化了的分子的质量的质量分析仪(4)。 A quality-analyzing device having a mass analyzer (4), mass analyzer (4) in turn comprising: a sample introducing portion having a pulse jet valve formed molecules (1); a pulse laser oscillator (2); and analysis the mass of the molecular ion laser mass analyzer (4). 上述脉冲激光振荡器产生最大输出功率为1MW以上的超短脉冲激光。 The pulsed laser oscillator to generate a maximum output power of 1MW or more ultrashort pulse laser. 真空离子化室(3)用涡轮分子泵排气,上述试样导入部的喷嘴(12)由两个以上的针孔喷嘴构成,设有狭缝喷嘴和狭缝分离器(14)。 Vacuum ionization chamber (3) with an exhaust turbo-molecular pump, a nozzle (12) of the sample supply unit composed of two or more pinholes nozzle, a slit and a slit nozzle separator (14). 本发明的装置灵敏度高且精确度高,由于能使结构紧凑,所以能发挥迅速分析燃烧后排放的气体等的能力。 Device of high sensitivity and high precision according to the present invention, since the compact structure can, so the ability to play the combustion exhaust gas quickly analyze the like.

Description

激光离子化质量分析装置及质量分析方法 Laser ionization mass spectrometer and the mass spectrometry method

技术领域 FIELD

本发明涉及利用激光照射而使被测定物的试样分子离子化、通过测定该离子的质谱进行试样的质量分析的激光离子化质量分析技术。 The present invention relates to the object to be measured is irradiated with a laser ionizing a sample molecule, analysis by laser ionization mass of the mass analysis of the sample by measuring the ion mass spectrum.

背景技术 Background technique

在煤、重油等燃烧时排放的气体、城市垃圾或工业废弃物焚烧时排放的气体、塑料热解产生的气体等中含有微量的氮氧化合物、硫氧化合物、芳香族化合物、氯系列有机化合物、氯化芳香族化合物、以及卤素系列化合物等各种化合物,在多数情况下,这些化合物中的两种以上同时存在、即以混合状态存在。 Containing traces of nitrogen oxides in the exhaust gases of the combustion of coal, heavy oil, gas emissions when municipal refuse or industrial waste incineration, pyrolysis gas or the like in plastic, sulfur oxides, aromatic compounds, chlorine series organic compound various compounds, chlorinated aromatic compounds, etc., and halogen series compounds, in most cases, more than two of these compounds exist, i.e. exist in a mixed state. 这些化合物的迅速测定技术之一是检测测定对象化合物的选择性的激光多光子离子化质量分析法。 Rapid assay techniques, one of these compounds are selective detection of the measuring object compound laser multiphoton ionization mass spectrometry.

在《Analytical Chemistry》杂志,第66卷,1062~1069页(1994年)中介绍了通过激光多光子离子化质量分析测定混合气体试样的一个技术例。 In "Analytical Chemistry" magazine, Vol. 66, 1062 - 1069 (1994) describes a technique Determination embodiment the mixed gas sample by laser multiphoton ionization mass. 即,在通常的通过导入试样进行的激光多光子离子化质量分析技术中,由于与各化合物对应的峰值都较宽,所以峰值相重叠,难以进行定量分析。 That is, the laser is typically performed by introducing a sample multi-photon ionization mass spectrometry technique, since the peak corresponding to the respective compounds are broad, overlapped peaks so difficult to perform quantitative analysis. 因此,使气体试样通过孔径小的试样导入真空管而导入到离子化真空室中,对它进行激光照射,使其离子化,用质量分析仪进行测定。 Accordingly, the gas introduced into the vacuum sample through a small aperture and a sample introduced into the ionization chamber, it laser irradiation, and ionizing, measured by a mass analyzer. 这时,由于气体试样绝热膨胀而被冷却到接近于绝对零度,所以各化合物分子的振动、转动都受到抑制。 In this case, since the adiabatic expansion of gas sample is cooled to near absolute zero, the vibration of each compound molecule, the rotation was inhibited. 因此,与各化合物对应的峰值变得尖锐而彼此分开,所以容易进行定量分析。 Thus, with each peak corresponding compound sharpened and separated from each other, it is easy for quantitative analysis. 由于被导入的分子的速度是声速的数十倍,所以该方法被称为超声速分子射束分光分析法或超声速分子射流分光分析法。 Since the speed is introduced into the molecule is the number of times the speed of sound, this method is referred to as the supersonic molecular beam spectroscopy or supersonic jet molecular spectroscopy. 另外,该文献中记载的激光照射标准时间为10ns。 Further, the laser irradiation time of the standard described in the literature is 10ns.

在进行该超声速分子射流试样导入时,一般来说,为了维持离子化室的高真空度,在连续地或脉冲式地导入气体试样时,存在着单位时间内的导入量必须少的限制。 When the sample is introduced into the supersonic jet carrying molecule, in general, in order to maintain a high degree of vacuum of the ionization chamber, in a continuous or pulsed gas sample is introduced, there is introduced an amount per unit time must be less restricted . 因此,由于测定对象试样的量极少,所以,存在总体灵敏度低的问题。 Accordingly, since the amount of sample to be measured very small, so there is low overall sensitivity problem. 作为其对策,可以考虑增加激光照射的能量。 As a countermeasure, consider increasing the energy of the laser irradiation. 可是,如果增加激光能量,则会引起测定对象分子的分解、即碎裂,产生不能准确定量的问题。 However, if the increase in the laser energy, would cause decomposition of the measurement target molecule, i.e. fragmentation, a problem can not be accurately quantified.

另外,作为因上述测定对象物的量微小而造成的灵敏度低的对策,如《Review Science Instrumentation》第67卷第410~416页(1996年)中所述,使用狭缝状的喷嘴,这是一种只在激光通过得多的地方将试样导入得多的方法。 Further, as the amount of low sensitivity due to the above-described countermeasure minute measurement object caused, as described in "Review Science Instrumentation" vol. 67, pages 410 416 (1996), using a slit-like nozzle, which is only one kind of laser light through the sample where a much method of introducing much. 该方法是将激光从横向照射在呈平面状喷出的分子射流的同一平面上,增大分子和激光相互作用的空间,增加离子的生成量。 This method is to form a laser irradiated from a transverse plane on the same molecule planar discharged jet, laser and space increase molecular interaction, increases the amount of generated ions.

可是,该方法的有效性在于:从原理上说,在狭缝的开口部分的大小和照射激光的口径(大小)成正比的空间中生成离子。 However, this method is effective in that: in principle that the aperture size and space the laser beam irradiated portion of the slit opening (size) proportional to generate ions. 即,增大狭缝开口部分和送给质量分析仪时的分子离子的空间分布相关联,与离子生成量成正比的部分同信噪比(S/N比)的增大无关。 I.e., the space is increased when the molecular ion of the slit opening portion and to the mass distribution analyzer associated with the amount of ions generated is proportional to the portion of the same signal to noise ratio (S / N ratio) is increased independent. 另外,如果考虑狭缝喷嘴加给排气系统的负担,则在极端情况下不能增大狭缝的开口部分。 Further, in consideration of the burden applied to the slit nozzle exhaust system, in the extreme case of the slit opening portion can not be increased. 即,对信号有用的部分是沿狭缝开口部分的长轴的中心部分,在其外围存在对信号无用的分子,这是造成真空度下降的原因。 That is, the signal of the useful part of the major axis is the central portion of the opening portion along the slit, which is present in the periphery of unwanted molecular signals which cause the degree of vacuum is lowered. 再者,相反地,由于分子射流的冷却不好,所以灵敏度即S/N比有可能下降。 Also, in contrast, is not good due to cooling jet, so that is the sensitivity S / N ratio is likely decrease. 这些都会成为不仅是狭缝喷嘴、而且即使是针孔喷嘴在以导入大量试样为目的而增大开口部分时的问题。 These will not only be a slit nozzle, and even the problem of pinholes when the nozzle to introduce a large number of samples for the purpose of increasing the opening portion.

因此,不增加试样的流量就不能提高灵敏度,这会降低下一级的质量分析仪的真空度,对装置起保护作用的安全装置开始工作,引起质量分析仪的工作停止。 Thus, without increasing the flow rate can not increase the sensitivity of the sample, which reduces a degree of vacuum of the mass analyzer, to work safety means for protection, causing a stop mass analyzer. 特别是如果脉冲式地导入试样,则由于压力变化大,所以以提高灵敏度为目的而在排气系统能力极限附近测定时,问题更加显著。 In particular, if a pulsed sample introduced, the pressure change due to the large, so in order to improve measurement sensitivity near the capacity limit for the purposes of the exhaust system, the problem is more significant.

另外,为了形成这样的超声速分子射流,必须使离子化室或相关联的部位等成为高真空状态,如日本化学会编第4版《实验化学讲座》第8卷第119页(1993年)所述,排气时一般最好采用扩散泵、即油扩散泵等。 In order to form such a supersonic molecular jet must ionization chamber and other parts of or associated with a high vacuum state, such as the Chemical Society of Japan, 4th edition "Jikken Kagaku Koza" vol. 8, page 119 (1993) described later, the exhaust is generally preferred to use a diffusion pump, i.e., an oil diffusion pump or the like. 另外,也有的使用油旋转泵等,还有的两者并用。 Both addition, some oil using a rotary pump, and used in combination. 可是,油扩散泵或油旋转泵通常为排气速度快的、即能维持高真空状态的泵,其使用的油会存在于离子化室中,即使其数量极少。 However, an oil diffusion pump or a rotary pump is generally an oil discharge speed, i.e., the pump can maintain a high vacuum state, the oil may be used which is present in the ionization chamber, even very small amount thereof. 在脉冲激光的照射下,它会被直接离子化,或经过分解反应等再被离子化,其问题是这成为本底增加的原因。 Pulse laser irradiation, it will be directly ionized, or the like after the decomposition reaction is then ionized, it becomes a problem that the reason for the increase of the background.

本发明的目的在于在利用超声速分子射流进行试样导入的激光多光子离子化质量分析技术中,提供一种能以高灵敏度进行检测且能稳定地进行测定的装置及方法。 The object of the present invention is the use of a laser molecular supersonic jets sample introduction multiphoton ionization mass analysis, an apparatus and method which can be detected with high sensitivity and can be stably measured.

本发明的另一目的在于在利用超声速分子射流进行试样导入的激光多光子离子化质量分析技术中,提供一种能谋求试样的导入量大、但不降低S/N比、从而能以高灵敏度进行检测的装置。 Another object of the present invention is to utilize supersonic jets sample molecules introduced laser multiphoton ionization mass spectrometry techniques, seek to provide a large amount of sample is introduced, but without reducing the S / N ratio, and thus capable of means for detecting a high sensitivity.

本发明的再一个目的在于在利用超声速分子射流进行试样导入的激光多光子离子化质量分析技术中,提供一种通过降低本底而增大信号强度的测定装置。 A further object of the present invention is the use of a laser molecular supersonic jets sample introduction multiphoton ionization mass spectrometry techniques, to provide a background is increased by reducing the signal strength measuring means.

发明的公开本发明者们进行仔细研究的结果发现,分子的碎裂与所照射的激光的能量有关,但分子的离子化与激光的最大输出有关。 The results disclosed in the present inventors have conducted careful studies invention found that the energy of the laser irradiated fragmentation and related molecules, but the maximum output of the laser ionization and related molecules. 已判明:如果照射最大输出功率大的超短脉冲激光,则若超过引起分子碎裂的极限能量,即使不增大激光能量,也能提高离子化效率。 It has revealed that: if the irradiation large maximum output power ultrashort pulse laser, if it exceeds the limit due to molecular fragmentation energy, without increasing the laser energy, the ionization efficiency can be improved. 即,如果采用最大输出功率大的激光,则既能抑制分子的碎裂,又能增加分子离子化的生成量。 That is, if a large maximum output power of the laser, the molecule can inhibit fragmentation, but also increase the production amount of the molecular ion.

因此,利用下述的激光离子化质量分析装置就能解决上述课题,该激光离子化质量分析装置备有:具有形成分子射流的脉冲阀的试样导入部;脉冲激光振荡器;具有使从该振荡器发出的激光通过的窗口的真空离子化室或与其相当的部位;以及分析被该激光离子化了的分子质量的质量分析仪,其特征在于:上述脉冲激光振荡器能发生最大输出功率为1MW以上的超短脉冲激光。 Thus, using the following laser ionization mass spectrometer can solve the above problems, laser ionization mass spectrometry means includes: a sample introducing portion forming molecules pulse jet valve; pulsed laser oscillator; from having to make the vacuum ionization chamber through a window of the laser oscillator sent or equivalent parts; and analyzing the laser light is ionized molecular mass of the mass analyzer, wherein: the pulsed laser oscillator capable of undergoing a maximum output power more than 1MW ultrashort pulse laser.

另外,利用下述的质量分析方法能解决上述课题,该质量分析方法的特征在于:由形成分子射流的脉冲阀将试样气体喷射到真空离子化室或与其相当的部位,形成脉冲状分子射流,用最大输出功率为1MW以上的超短脉冲激光照射该分子射流,使其离子化,分析被该激光离子化了的分子的质量。 Further, mass analysis using the following methods can solve the above problems, the mass analysis method comprising: a pulse jet valve formed molecules injected into the sample gas ionization vacuum chamber or equivalent parts, a pulsed jet molecules , with a maximum output power of the irradiated molecules jet 1MW or more ultrashort pulse laser, and ionizing, the laser beam is analyzed by mass of ionized molecules.

另外,利用下述的激光离子化质量分析装置能解决上述课题,该激光离子化质量分析装置备有:具有形成分子射流的脉冲阀的试样导入部;脉冲激光振荡器;具有使从该振荡器发出的激光通过的窗口的真空离子化室或与其相当的部位;以及分析被该激光离子化了的分子质量的质量分析仪;上述试样导入部的喷嘴由两个以上的针孔喷嘴构成。 Further, using the following laser ionization mass spectrometer can solve the above problems, the laser ionization mass spectrometer apparatus provided with: a sample introducing portion forming molecules pulse jet valve; pulsed laser oscillator; from the oscillator has a ionization vacuum chamber through a window laser light emitted by portions or equivalent; and analyzing the laser light is ionized molecular mass of the mass analyzer; the sample introduction nozzle portion consists of two or more pinholes nozzle .

本发明者们还发现分子射流的中心部分有方向性,由于分子流方向一致,所以,如果离子化,就对信号有利(提高灵敏度),而外围分子不大具有方向性,对于信号没有用处。 The present inventors have also found that the jet directional central portion of the molecule, since the same molecular flow direction, so that, if the ionization signal would advantageously (increased sensitivity), while the periphery of the molecule is not directional, the signal useless. 因此,如果用分离器将外围的分子除去而不送给质量分析仪,那么即使将试样导入得很多,也能减轻加在质量分析仪的排气系统上的负载。 Thus, if the periphery of the separator will not remove a molecule to the mass analyzer, even if the sample is introduced too many, it can also be applied to reduce the exhaust gas mass analyzer system load.

因此,利用下述的激光离子化质量分析装置能解决上述课题,该激光离子化质量分析装置备有:具有形成分子射流的脉冲阀的试样导入部;脉冲激光振荡器;具有使从该振荡器发出的激光通过的窗口的真空离子化室或与其相当的部位;以及分析被该激光离子化了的分子质量的质量分析仪;将上述狭缝喷嘴和真空离子化室之间隔开,设置能阻止该分子射流周围部分的分子流进入真空离子化室的狭缝分离器。 Thus, using the following laser ionization mass spectrometer can solve the above problems, the laser ionization mass spectrometer apparatus provided with: a sample introducing portion forming molecules pulse jet valve; pulsed laser oscillator; from the oscillator has a ionization vacuum chamber through a window laser light emitted or equivalent parts; and analyzing the laser light is ionized molecular mass of the mass analyzer; separating the vacuum between the slit nozzle and the ionization chamber, can be provided the molecular jet molecular flow preventing peripheral portion of the separator into the slot of the vacuum chamber of the ion.

可是,一般来说,由于无油涡轮分子泵的排气速度低,如果只使用该泵连续地进行测定后,试样会被多少残留在离子化室中,所以,存在试样或试样的分解物等被离子化后测定本底变高的问题。 However, in general, since the low oil-pumping speed of the turbo molecular pump, if the pump is used only continuously measured, the sample will be much remains in the ionization chamber, so that the presence of a sample or a sample the background becomes high decomposition measuring the like are ionized. 在本发明中,除了使用涡轮分子泵以外,还同时使用工作时间短的脉冲泵作为试样导入装置,使试样导入量适合于涡轮分子泵的能力,成功地降低了本底。 In the present invention, except that a turbomolecular pump, it also use a short working time of the pump pulse as a sample introduction device, amount of introduced sample is adapted to the capacity of the turbomolecular pump, we succeeded in reducing the background.

因此,利用下述的激光离子化质量分析装置能解决上述课题,该激光离子化质量分析装置备有:具有形成分子射流的脉冲阀的试样导入部;脉冲激光振荡器;具有使从该振荡器发出的激光通过的窗口的真空离子化室或与其相当的部位;以及分析被该激光离子化了的分子质量的质量分析仪;使上述真空离子化室排气的泵采用涡轮分子泵。 Thus, using the following laser ionization mass spectrometer can solve the above problems, the laser ionization mass spectrometer apparatus provided with: a sample introducing portion forming molecules pulse jet valve; pulsed laser oscillator; from the oscillator has a ionization vacuum chamber window of laser light emitted by portions or equivalent; and analyzing the laser light is ionized molecular mass of the mass analyzer; ionization chamber so that the vacuum exhaust pump is a turbomolecular pump.

附图的简单说明图1是表示本发明的一实施例的装置的结构图。 BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a configuration diagram showing an embodiment of the present invention.

图2是表示由实施例1获得的氯苯分子的离子峰值强度的变化曲线图。 FIG 2 is a graph showing the change in molecular chlorobenzene obtained in Example 1 ion peak intensity.

图3是表示由实施例2获得的氯苯分子的离子峰值强度的变化曲线图。 3 is a graph showing the change of a molecule chlorobenzene obtained in Example 2 ion peak intensity.

图4是表示由实施例2获得的溴化苯分子的离子峰值强度变化的曲线图。 FIG 4 is a graph showing changes in peak intensity by bromination of benzene obtained in Example 2 ions.

图5是表示由实施例2获得的碘化氯苯分子的离子峰值强度变化的曲线图。 FIG 5 is a graph showing the iodinated molecules chlorobenzene obtained in Example 2 ion peak intensity changes.

图6是表示本发明的另一实施例的装置的结构图。 FIG 6 is a block diagram of an apparatus according to another embodiment of the present invention.

图7是表示使用图6所示的装置测定的O-氯代苯酚的离子强度随时间变化和激光停止时检测系统的信号(短时间试样导入·涡轮分子泵排气)的曲线图。 FIG 7 is a graph showing the signal strength O- ionic chlorophenols measuring apparatus shown in FIG. 6 using the change over time and the laser beam stop detection system (short sample introduction · turbomolecular pump exhaust) of.

图8是表示O-氯代苯酚的离子强度随时间变化和激光停止时检测系统的信号(短时间试样导入·油扩散泵排气)的曲线图。 FIG 8 is a graph showing the signal O- chlorophenols ionic strength changes with time and the laser beam stop detection system (short-oil diffusion pump sample introduction exhaust gas) is.

图9是表示O-氯代苯酚的离子强度随时间变化和激光停止时检测系统的信号(通常试样导入·涡轮分子泵排气)的曲线图。 FIG 9 is a graph showing the signal O- chlorophenols ionic strength changes with time and the laser beam stop detection system (typically a turbo molecular pump sample introduction · exhaust) of.

图10是表示本发明的另一实施例的装置的结构图。 FIG 10 is a configuration diagram of an apparatus according to another embodiment of the present invention.

图11是该装置的试样导入部、脉冲激光振荡器及真空离子化室部分的剖面图。 FIG 11 is a sample introduction portion of the apparatus, a pulsed laser oscillator and a cross-sectional view of the vacuum of the ionization chamber portion.

图12是表示使用图10所示的装置获得的氯苯的质谱的曲线图。 FIG 12 is a graph showing the apparatus 10 shown in FIG chlorobenzene mass spectrum obtained.

图13是表示本发明的另一实施例的装置的结构图。 FIG 13 is a configuration diagram showing apparatus according to another embodiment of the present invention.

图14是该装置的试样导入部、狭缝分离器、脉冲激光振荡器及真空离子化室部分的剖面图。 FIG 14 is a sample introduction portion of the apparatus, the separator slit, a pulsed laser oscillator and a sectional view of the vacuum of the ionization chamber portion.

图15是上述装置中使用的两种狭缝分离器的狭缝部分的剖面图。 FIG 15 is a sectional view of the slit portion of the slit of the separator used in the above-described two means.

图16是表示使用图13所示的装置获得的氯苯的质谱曲线图。 FIG 16 is a graph showing a mass spectrum using the apparatus shown in FIG. 13 the obtained chlorobenzene.

用于实施发明的最佳形态试样导入部使用备有形成超声速分子射流的喷嘴或节流孔的脉冲阀。 BEST MODE FOR CARRYING OUT THE INVENTION for sample introduction portion is formed with the use of a nozzle or orifice pulse valve supersonic molecular jet. 脉冲阀在发动机的燃料喷射等等条件下使用,如日本化学会编第4版《实验化学讲座》第8卷、127~129页(1993年)所述,通常将用弹簧压在密封面上的柱塞通过向后方的螺线管(电磁线圈)进行瞬间通电而被电磁性地向后方吸引,只在此期间开口。 Pulse valve used in the engine fuel injection condition and the like, such as Chemical Society of Japan, 4th edition, "Experimental Chemistry", Vol. 8, 127 to 129 (1993), the spring is generally on the sealing surface pressure plunger backward by a solenoid (electromagnetic coil) is electromagnetically energized momentarily attracted backward, only during the opening. 另外,Gentry-Giese式脉冲阀还开发出来了用压电元件进行开闭的脉冲阀,也可以使用这些阀。 Further, Gentry-Giese pulse valve further developed a pulse valve for opening and closing the piezoelectric element, the valves may also be used.

在本发明中,为了进行离子化,激光和测定对象化合物分子相互作用的时间与脉冲激光的振荡时间有关,所以最好使用与所使用的脉冲激光的振荡时间(照射时间)大致相同的、在极短时间内工作的脉冲阀。 In the present invention, in order to carry out pulse laser oscillation time with the time of ionization, and laser target measuring molecular interactions related compound, it is preferable to use a pulsed laser oscillation time of use (irradiation time) is substantially the same, in very short pulse valve work. 具体的工作时间的下限应在0.1μs以上,以1μs以上为好,最好在10μs以上,尤其在50μs以上就更好,上限应在5ms以下,以2ms以下为好,最好在500μs以下,尤其在200μs以下就更好。 The lower limit of the specific working hours should be more than 0.1μs to 1μs or more, more preferably more than 10μs, 50μs especially in the more the better, the upper limit should be less 5ms to 2ms or less, and preferably in 500μs or less especially in 200μs or less the better. 因此,在市售的脉冲阀的工作时间长的情况下,如果增加弹簧的长度,同时提高强度,另外减小线圈的电阻,使之能流过大电流,同时增大工作电压,则能成为在更短的时间内工作的阀。 Thus, in the commercially available long working time pulse valve, if increasing the length of the spring, while improving the strength, further reducing the resistance of the coil, so that it can flow a large current, while increasing the operating voltage, it can be valve operating in a shorter time. 喷嘴的开口部分除了通常的圆孔外,也可以呈狭缝状。 In addition to the opening portion of the nozzle is usually circular holes, may be a slit shape. 开口部分的大小以能形成超声速分子射流而定,这与真空离子化室的排气能力等有关,但开口面积通常为0.01~1mm2左右,特别是0.2~0.5mm2左右为宜。 Size of the opening portion to form a supersonic molecular jet can be, that the exhaust capacity of the vacuum of the ionization chamber so on, but the opening area is usually about 0.01 ~ 1mm2, particularly preferably about 0.2 ~ 0.5mm2 .

试样导入部的喷嘴在使用两个以上的针孔喷嘴或狭缝喷嘴的情况下,只要将市售的质量分析装置中使用的试样导入部换成喷嘴部就能直接使用。 Introducing a sample portion of the nozzle in the case where two or more nozzles pinholes or slit nozzle, as long as the sample introduction section used in the apparatus commercially available mass spectrometer can be used directly into the nozzle portion. 试样导入形式可以是连续的导入、脉冲的地导入什么形式都可以,但如果考虑到加在泵等排气系统上的负担,则脉冲式的导入方式为好。 Introduced in the form of introducing a sample may be continuous, pulsed what form can be introduced, but if considering the increase in the burden on the exhaust system such as a pump, is introduced into the pulse mode as well. 脉冲阀以上述的阀为好。 Pulse valve to said valve as well.

各针孔喷嘴可以安装在同一个阀等上,也可以分别安装在单独的阀等上。 Each pinhole nozzle may be mounted on the same valve or the like, may be mounted on a separate valve, respectively. 即,试样导入部的阀等可以是一个,也可以是多个。 That is, the valve and the like may be introduced into a portion of the sample may be a plurality. 各喷嘴的开口部的大小以能形成超声速分子射流而定,这与真空离子化室的排气能力等有关,但直径为0.05~3mm左右,特别是通常以0.1~1mm为宜。 Size of the opening portion of each nozzle to form a supersonic molecular jet can be, that the exhaust capacity of the vacuum of the ionization chamber so on, but a diameter of about 0.05 ~ 3mm, especially preferably generally 0.1 ~ 1mm . 各喷嘴的间隔为5~200mm左右,通常以20~50mm为好。 Interval each nozzle is about 5 ~ 200mm, generally 20 ~ 50mm as well. 喷嘴数在3个以上的情况下,可以配置成直线状,也可以呈任意的形状。 The number of nozzles in the case where three or more, can be arranged in a straight line, may be in any shape. 喷嘴的方向要能使从各喷嘴喷射出来的分子射流在从反射电极前到加速电极之间,最好在反射电极附近交叉。 The molecular direction of the nozzle jet can be ejected from each nozzle between the reflective electrode from the front to the acceleration electrode, preferably intersect in the vicinity of the reflective electrode. 即,这里重要的是被离子化了的分子不在空间扩散,为此,在质量分析仪的入口部、即在反射电极处必须尽可能地限制在较小的空间。 That is important here is not ionized molecules spatial diffusion, therefore, the inlet portion of the mass analyzer, i.e., must be limited as much as possible in a smaller space at the reflective electrode. 作为其具体的方法,可以使从两个以上的喷嘴喷射出来的分子射流在反射电极附近交叉。 As a concrete method, the molecules can be injected from the jet nozzles of two or more intersecting in the vicinity of the reflective electrode.

在使用两个以上的针孔喷嘴的情况下,也可以不使用分离器,但使用时能在一定程度上减少另一分子射流的干扰,还能减小加在质量分析仪的排气系统上的负担,所以最好是使用。 In the case where two or more pinholes nozzles, separators may not be used, but it can reduce the interference jet another molecule using a certain extent, but also applied to the exhaust system to reduce the mass analyzer burden, so it is best to use. 分离器设置得将喷嘴和真空离子化室隔开,以便阻止分子射流周围部分的分子流进入真空离子化室,只使分子射流的中央部分通过,因此,原则上将喷嘴的开口部和分离器的开口部的中心设置得大致一致。 Separator set nozzle and spaced from the vacuum ionization chamber, so as to prevent the jet molecular flow molecule peripheral portion of the ionization chamber into the vacuum, only the central portion of the molecule through the jet, and therefore, in principle opening of the nozzle portion and the separator the central opening is set to be substantially the same. 形成分子射流的喷嘴的喷出口和分离器的狭缝之间的间隔为2~300mm左右,特别是以7~100mm左右为宜。 The spacing between the molecules forming the jet nozzle and the discharge outlet of the separator slit is about 2 ~ 300mm, especially preferably is about 7 ~ 100mm. 分离器的开口直径为0.1~1mm左右,特别是以0.2~0.8mm左右为宜。 An opening diameter of the separation is about 0.1 ~ 1mm, particularly preferably is about 0.2 ~ 0.8mm. 不使通过狭缝的分子射流扩散这一点最好在试样导入侧突出地形成。 Without diffusion molecules through that slit jet sample introduction side is preferably formed to protrude. 分离器将开口部以外和真空离子化室之间隔开,使气流不能通过。 The opening between the separator and separated from the vacuum chamber outside the ionization section, the airflow can not pass. 分离器的材料可以使用SUS、铝等金属、玻璃、耐热性塑料等。 Separator material of the SUS may be used, a metal such as aluminum, glass, heat resistant plastics and the like. 设有使被分离器隔断的分子射流部分不能进入真空离子化室的排气装置。 Portion of the molecule is provided with a jet separator partition can not enter the vacuum exhaust apparatus ionization chamber.

狭缝喷嘴的狭缝大小以能形成超声速分子射流而定,这与排气能力等有关,但通常宽度为0.01~1.0mm左右,最好为0.1~0.8mm左右,长度为5~200mm左右,最好为10~30mm左右,宽:长比为1∶5~1∶1000左右,最好为1∶10~1∶300左右。 Size of the slits can form the slit nozzle to jet may be supersonic molecule, which is related to exhaust gas ability, but generally a width of about 0.01 ~ 1.0mm, preferably about 0.1 ~ 0.8mm, a length about 5 ~ 200mm, preferably about 10 ~ 30mm, width: length ratio of about 1/5 to 1000, preferably about 1:10 to 1:300. 作为喷嘴的安装方法例如有上述《Review Science Instrumentation》第67卷第410~416页(1996年)中所述的方法,用3个市售的脉冲阀的驱动机构使狭缝喷嘴及阀、即狭缝和带密封它的塞绳(コ-ド)的压板工作。 As a method of mounting a nozzle for example, the above-described method "Review Science Instrumentation" vol. 67, pages 410 416 (1996) was used, the slit nozzle and the valve driving mechanism 3 of a commercially available impulse valve, i.e., and a seal slot with its cord (U - then) of the work platen. 另外,如果狭缝喷嘴的长度不太长,即30mm以下,则可以使用1个驱动机构。 Further, if the length of the slit nozzle is too long, i.e. 30mm or less, may be used a drive mechanism.

在采用狭缝喷嘴的情况下,设置狭缝分离器,将狭缝喷嘴和真空离子化室之间隔开,阻止该分子射流的周围部分的分子流进入真空离子化室。 In the case of the slit nozzle, slit separator spaced between the slit nozzle and the vacuum ionization chamber to prevent molecules surrounding the jet stream of the molecule into the vacuum chamber of the ion. 该分离器的狭缝设置得只使从试样导入部的喷嘴喷出的分子射流的中央部分通过,因此,原则上将喷嘴的狭缝和分离器的狭缝的中心设置得大致一致。 The separator is set to be only the slits discharged from the nozzle portion of the sample molecules introduced into the jet through the central portion, and therefore, in principle central slit nozzle and the separator slit set substantially the same. 形成分子射流的狭缝喷嘴的喷出口和狭缝分离器的狭缝的间隔为3~30mm左右,最好为7~25mm左右。 Slits spaced slits forming molecules jet nozzle discharge outlet slit and the separator is approximately 3 ~ 30mm, preferably about 7 ~ 25mm. 分离器的狭缝的宽和长最好分别大于狭缝喷嘴的宽和长,且以即便最大也在2倍以内为好。 Slit width and length of the separator are preferably larger than the width and length of the slit nozzle, and even less to the maximum are twice as good. 另外最好为1.2~1.5倍。 Further preferably 1.2 to 1.5 times. 分离器的狭缝宽度为0.01~1.2mm左右,最好为0.1~1.0mm左右,长度为5~200mm左右,最好为10~30mm左右,宽:长比为1∶4~1∶1000左右,最好为1∶10~1∶150左右。 Separator slit width is about 0.01 ~ 1.2mm, preferably about 0.1 ~ 1.0mm, a length of about 5 ~ 200mm, preferably about 10 ~ 30mm, width: length ratio of 1 about 4 to about 1000, preferably about 1:10 to 1:150. 本发明的分离器的狭缝是在平板状的分离器上形成狭缝,或者使狭缝在真空离子化室一侧突出,同样有效,但从不使通过狭缝的分子射流扩散、或不会由于聚束·碰撞而干扰气流这一点看,最好在试样导入侧突出形成。 Separator of the present invention is a slit formed in the plate-shaped separator slit, the slit in a vacuum or ionization chamber side protrudes, equally effective, but not to jet slit by molecular diffusion, or due to collision of the interference bunching-stream this point of view, the sample is preferably introduced into the side protrusion is formed. 突出形状最好使狭缝两侧面从底端部向狭缝的前端呈直的平面状或接近凹面状的形状。 Projecting both sides of the slit shape is preferably a straight planar forward end portion of the slit from the bottom or close to a concave shape. 狭缝前端中心和狭缝两面底端之间的角度为20~70度左右,最好为40~50度左右。 The angle between the slits and the slits bottom center of the front end sides about 20 to 70 degrees, preferably about 40 to 50 degrees. 分离器这样隔开,以便使狭缝以外和真空离子化室之间不连通。 Thus the separator spaced apart, so that the vacuum between the outside slits and the ionization chamber is not in communication. 分离器的材料可以使用SUS、铝等金属、玻璃、耐热性塑料等。 Separator material of the SUS may be used, a metal such as aluminum, glass, heat resistant plastics and the like. 设置有排气装置,使被分离器隔断的分子射流部分不能进入真空离子化室。 An exhaust means is provided, the jet portion of the molecule was not cut off the separator into the vacuum chamber of the ion.

脉冲激光振荡器不限定于能发出高输出功率的脉冲激光的振荡器,但例如如果发出毫微秒数量级的脉冲激光,则可以使用如下的激光。 It is not limited to the pulse laser oscillator capable of emitting high output pulse laser oscillator, but for example, if sent nanoseconds laser pulses, a laser may be used as follows. 就是说,最为普遍地使用色素激光。 That is, the most commonly used pigment laser. 它将受激准分子激光器、或钇铁石榴石激光器作为抽运光源用,通过更换激光色素,能使波长在330~1000nm的范围内连续地变化。 It excimer laser, or yttrium iron garnet laser as a pumping light source by replacing the dye laser, the wavelength can be continuously changed in the range of 330 ~ 1000nm. 最近上市一种光参数振荡激光器,可以用它代替色素激光器进行振荡。 An optical parametric oscillation recently launched laser, dye laser can use it instead oscillates. 另外,如果使用色素的倍波发生、混频等,则能扩大到220nm的发生区。 Further, if using dye harmonic wave, mixing, etc., can be expanded to the generating region of 220nm. 毫微微秒数量级的激光大致能由XeCl受激准分子激光器激励的毫微微秒脉冲色素激光器及放大用的受激准分子激光器构成的系统发生。 Pulsed dye laser system femtosecond order of femtoseconds can be substantially affected by the laser XeCl excimer laser excitation and amplification of an excimer laser configuration occurs. 它将毫微秒色素激光器猝熄后,再激励短腔激光器,通过过饱和吸收体,发生9ps的脉冲。 It nanoseconds after quenching dye lasers, short-cavity laser excitation and then, by the supersaturated absorber, 9ps pulse occurs. 该光脉冲被色素放大器放大,用作分布反馈型色素激光器的抽运光。 The light pulse is amplified by the amplifier dye, as the distribution of pumping light feedback dye laser. 最后,能获得紫外线区域的波长、毫微微秒数量级、最大输出功率为20mJ左右的脉冲激光器。 Finally, an ultraviolet wavelength region can be obtained, the order of femtoseconds, the maximum output power of about 20mJ pulsed laser. 另外,如果将毫微微秒激光器部分振荡断开,则能使毫微秒数量级的激光振荡。 Further, when the femtosecond laser oscillation section is turned off, can nanoseconds laser oscillation.

在本发明中,最好采用由脉冲激光振荡器发生的最大输出功率为1MW以上的超短脉冲激光。 In the present invention, it is preferable to use the maximum output power generated by the pulsed laser oscillator 1MW or more ultrashort pulse laser. 最大输出功率最好为10MW~100GW,特别好的是100MW~10GW。 Preferably the maximum output power of 10MW ~ 100GW, particularly preferably 100MW ~ 10GW. 这里所谓的最大输出功率是表示激光的强度,即激光能量(J)/振荡时间(s)。 Here, the term is a maximum output power intensity of the laser, i.e., laser energy (J) / oscillation time (s).

作为提高该最大输出功率的方法,有使一个脉冲的激光振荡时间更短的方法和提高激光输出功率的方法。 As a method of increasing the maximum output power, so there is a pulse of laser oscillation time is shorter and a method to improve the laser output power. 关于照射时间,由于用不使分子碎裂的激光能量尽量产生最大输出功率大的方法来增大离子化效率,所以照射时间越短越好。 The irradiation time, since the laser energy without fragmentation of the molecule generating large maximum possible output power to increase the ionization efficiency of the method, the irradiation time as short as possible. 另一方面,从理论上考虑,所谓激光多光子离子化是这样一种过程,即测定对象化合物的分子利用具有与测定对象化合物的分子从稳态到受激状态的能量差相当的能量的光子,跃迁到受激状态,再利用光子的能量进行离子化。 On the other hand, consider the theory, the so-called laser multiphoton ionization is a process, i.e., measurement target molecule using molecular compound with a compound having the measurement target photon energy corresponding to a difference from the steady state to the excited state energy , transition to the excited state energy of the photon recycling ionized. 因此,如果以滞留在激励状态的时间即激励寿命为目标,照射极大限度地不致使分子分解的程度的功率大的脉冲激光,则能提高离子化效率,显著地增加离子的生成量。 Thus, if the residence time in the excited state lifetime of the target excitation i.e., high power pulse laser irradiation greatly limits the extent of not causing decomposition of the molecule, the ionization efficiency can be improved significantly increases the amount of generated ions. 希望照射时间是在激励寿命的3倍以下,而在2倍以下就更好,最好是使两者时间相同。 The irradiated excitation time is 3 times or less the life, and better at 2 times or less, preferably so that the two same time. 另一方面,好的照射时间的下限是1/10000以上,而在1/4000以上就更好,最好是在1/2000以上。 On the other hand, the lower limit of the irradiation time is good than 1/10000, while better than 1/4000, more preferably 1/2000. 一般来说,希望照射时间为100~500fs左右,最好为200~300fs。 Generally, it is desirable irradiation time is about 100 ~ 500fs, preferably 200 ~ 300fs.

关于激光能量的问题,从理论上说,能量大者能使最大输出功率大,分子不分解的范围越大越好,可是激光束的中心和它的外侧往往有若干差别,所以照射在分子射流上时产生的碎裂也往往按空间分布,所以即使激光能量稍小些,也能获得效果。 Regard to laser energy, in theory, allows the maximum energy of the larger output power, the molecule does not decompose range as large as possible, but the center of the laser beam and the outside of it often has several differences, so that the irradiated molecules jet when fragmentation often generated by the spatial distribution, so that even if the laser energy is slightly less, the effect can be obtained. 希望激光能量为5mJ以下,最好为4mJ以下,而3mJ以下就特别好。 We hope laser energy 5mJ, preferably not less 4mJ, and 3mJ the following is particularly good. 另一方面,希望下限为1mJ以上,最好为2mJ以上。 On the other hand, the lower limit is 1mJ want more, more preferably 2mJ.

从原理上说,照射的激光波长与各个测定对象分子固有的稳定状态和受激状态的能量差相对应,即最好为共振波长,但即使是非共振波长,由于离子化,也能获得充分的效果。 In principle, the irradiation energy of each laser wavelength measurement target molecule with an inherently stable state and the excited state corresponding to the difference, i.e., the resonant wavelength is preferably, but even non-resonant wavelength due to ionization, can be sufficient effect.

关于激光的聚光问题,什么限制也没有,可以使用通常的使光束剖面呈圆形或能够使用特殊透镜(圆柱形透镜)的平面状等各种形状的透镜。 Converging the laser light on the problem, not limit what can be used is generally circular cross section of the light beam may be used or a special lens (cylindrical lens) planar and other shaped lens.

关于激光的照射位置,最好是在分子射流受其它分子射流的影响之前的位置。 The irradiation position of the laser, preferably by the position of the jet before the jet impact molecule other molecules. 这是因为,如果分子射流之间开始交叉,则分子流发生变化,开始使分子运动,就失去分子射流的意义了,致使S/N比下降。 This is because, if you start a cross between molecular jet, the molecular flow changes, begins to molecular motion, it loses meaning of the molecular jet, resulting in S / N ratio decreased. 另外,如果分子呈离子状态,则即使与来自其它分子射流的分子多少有些相互作用,也不大会使S/N比下降。 Further, if the molecules are ionic state, even if somewhat molecules from interacting with other molecules jets Assembly nor the S / N ratio decreased. 如果附加分离器,则只取出分子流一致的有助于信号的分子,且由于使分子射流的直径收缩,分子射流之间的干扰变弱,所以激光的照射位置、形状的自由度增大。 If the additional separator, remove only the signal molecules facilitate consistent molecular flow, and since the contraction of the diameter of the jet molecules, molecular interference between the jet becomes weaker, so that the irradiation position of the laser, the degree of freedom of shape is increased.

离子化室呈高真空的结构,设有采用能使激光透过的材料作成的窗口即可。 Ionization chamber as a high-vacuum structure is provided to make use of the laser ray transmitting window made of material. 真空离子化室和质量分析仪的真空室有时连续设置而无间隔。 Ionization vacuum chamber and the vacuum chamber of the mass analyzer may continuously arranged without intervals. 这时,进行离子化的部位相当于真空离子化室的部位。 In this case, a portion corresponding to ionization of the ionization chamber portion of a vacuum.

另外,作为质量分析仪可以采用行程时间型、四重极型、双重聚束型等任何一种形式。 Further, as the mass analyzer may be employed travel time type, quadrupole type, double focusing type and the like any form.

在被隔断的分子射流喷出部分,离子化室、与其相邻的质量分析仪、以及狭缝分离器连接着油旋转泵、升压泵、油扩散泵、涡轮分子泵等,可以保持在10-6~10-8torr左右。 In the jet discharge portion is cut off molecule, the ionization chamber, adjacent thereto a mass analyzer, and a slit connected to the oil separator rotary pump, a booster pump, an oil diffusion pump, a turbo molecular pump or the like, may be maintained at 10 about -6 ~ 10-8torr.

可以采用无油的涡轮分子泵对离子化室抽真空。 Can be oil-free turbo molecular pump of the ionization chamber is evacuated.

涡轮分子泵由在圆板上倾斜地切出狭缝的旋转叶片和与狭缝的倾斜方向相反的固定叶片交替地构成,通常将吸气口配置在上部,将排气口配置在下部,而将旋转叶片的轴垂直配置。 The turbomolecular pump is constituted by alternately rotating blades cut a slit in the circular plate and the inclined direction of the slit opposite to the inclination of the stationary blade, typically arranged in an upper portion of the intake port, the exhaust port is disposed at a lower portion, and the rotary blade is disposed perpendicular to the axis. 旋转叶片以与分子的平移速度程度相同的速度高速旋转(2000~7000rpm),分子碰撞旋转叶片,向下游推进(叩き落),被送至排气口。 Translation speed rotary blade with the same degree of molecular high-speed rotation speed (7000rpm 2000 ~), molecular collision rotary blade, downstream propulsion (ki knock down), is sent to the exhaust port. 压缩比(排气压与吸气压之比)是衡量泵性能的目标,由于分子量大的碳氢化合物的压缩比大,所以能获得无油的清净的真空。 Compression ratio (ratio of discharge pressure and suction pressure) is a measure of pump performance goal, a large molecular weight hydrocarbons compression ratio, it is possible to obtain a clean oil-free vacuum. 利用涡轮分子泵,真空室内的真空度能达到10-6~10-8torr左右,选择具有与其对应的能力的泵。 A turbo molecular pump, the vacuum degree of the vacuum chamber can reach about 10-6 ~ 10-8torr, selection of pumps having a capacity corresponding thereto.

另外,质量分析仪的真空室的排气装置最好也使用涡轮分子泵。 Further, the mass analyzer vacuum chamber exhaust turbo molecular pump is also preferably used.

关于试样的导入问题,通常由于离子化室(或与其相当的部位)或使用分离器时的上述离子化室保持在10-6torr以下,所以只要呈气体状态,用常压附近的压力就足够了,能构成驱动力将其导入,所以不需要特别加压,即使直接导入高压试样也没有问题。 Introducing a sample on the problem, usually due to the ionization chamber (or equivalent parts) or the above-described ionization chamber is used 10-6torr separator is maintained at less, so long as gaseous state, near the atmospheric pressure is sufficient , and it can be introduced into the driving force, so no special pressure, even if the high pressure directly into the sample there is no problem. 另外,如众所周知的那样,如果减压,分子射流的密度就变高,有时也能提高一些灵敏度,所以这种情况也可以。 Further, as is well known, if the reduced pressure, the molecular density of the jet becomes high, sometimes some of the sensitivity can be improved, so this may be the case.

关于分子离子的质量数的确定和检测,在通常的工作状态下使质量分析仪运行即可,可以使用一般的数字示波器、记录装置进行记录。 On the determination and detection of molecular ions of mass number of the mass analyzer can be run in a normal operating state, a digital oscilloscope may be used a general recording apparatus for recording.

实施例1制作了图1所示的激光离子化质量分析装置。 Example 1 A laser ionization mass analysis apparatus 1 shown in FIG. 该装置中使用的大部分零件都是市售品,试样导入部1采用了General Valve公司制的脉冲阀(PN91-47-900(85kg/cm2)),脉冲激光振荡器2采用了使用色素激光器的Lambda Physik公司制的LPD500fs型的激光系统,质量分析仪4采用了有长为450mm的行程管的行程时间型的质量分析仪,检测器46采用了滨松ホトニクス公司制的F1094型微通道板,而且记录仪(图中未示出)采用了Lecroy公司制的9360型数字示波器。 Most of the parts used in the apparatus are commercially available products, the sample introduction section 1 uses pulsed valve (PN91-47-900 (85kg / cm2)) General Valve Corporation, a pulse laser oscillator 2 employs the use of pigment LPD500fs type laser system laser Lambda Physik Inc., the mass analyzer 4 uses long as the travel time-of-stroke tube 450mm mass analyzer, a detector 46 uses F1094 shaped microchannel Hamamatsu ホ Suites ni Irganox manufactured by plate, and the recorder (not shown) using the 9360 type manufactured by Lecroy digital oscilloscope. 脉冲阀11的喷嘴12的开口呈内径为0.8mm的圆孔。 Opening of the nozzle 12 of the pulse valve 11 was 0.8mm inner diameter of the circular hole.

质量分析仪的真空室40使用排气速度达190l/s的日本真空技术公司制的UTM150型涡轮分子泵抽真空。 UTM150 turbo molecular mass analyzer vacuum chamber 40 using the exhaust velocity of 190l / s in Japan Vacuum Technology Co., Ltd. vacuum pump. 另外,激光照射的离子化室3使用1200l/s的日本真空技术公司制的ULK-06A型的油扩散泵进行排气。 An oil diffusion pump type ULK-06A Further, the laser irradiation using the ionization chamber 3 1200l / s in Japan Vacuum Technology Co., Ltd. is exhausted.

从振荡器2发生的脉冲激光22用透镜21聚光后,从窗口31进入真空离子化室3。 2 from the pulse laser oscillator 22 occurs converging lens 21, the window 31 into the vacuum chamber 3 ionization. 另一方面,试样气体用试样导入部1的脉冲阀11间歇地导入,从喷嘴12喷射,形成分子射流13。 On the other hand, the sample gas pulsing valve 11 is a sample introduction portion introduced intermittently injected from the nozzles 12, 13 to form a molecular jet. 该分子射流13进入真空离子化室3。 The molecular ion jet 13 into the vacuum chamber 3. 于是激光22照射该分子射流13,进行离子化,然后进入质量分析仪4。 Thus irradiating a laser jet 22 of the molecule 13 to be ionized, and then enter the mass analyzer 4. 在质量分析仪4内,首先由反射电极42将分子射流的方向改变90度,其次由高压加速电极43进行加速。 4 in the mass analyzer, the first reflective electrode 42 change the direction of the jet 90 molecule, followed by a high voltage accelerating electrode 43 is accelerated. 然后通过设在隔壁41上的离子通过孔44,由离子检测器46检测各离子。 Then the partition wall 41 provided in the through hole 44 of the ions by the ion detector 46 to detect the ions. 用数字示波器测量该检测信号。 The measured detection signal with a digital oscilloscope.

用氯苯对试样气体进行了质量分析。 Mass of the sample gas was analyzed with chlorobenzene.

改变激光的脉宽及振荡波长,产生了4ns~1ps、1~1000MW的激光。 And changing the pulse width of the oscillation wavelength of the laser, it produces a 4ns ~ 1ps, the laser 1 ~ 1000MW. 波长为248nm。 A wavelength of 248nm.

使氯苯与氩气一起以一定的浓度流入,由脉冲阀以分子射流状态导入真空离子化室。 And that the argon chlorobenzene together inflow certain concentration, molecular jet vacuum valve state by a pulse introduced into the ionization chamber. 照射能量为1mJ和4mJ、最大输出功率可改变为1MW、10MW、100MW及1000MW的激光,进行了离子化。 And the irradiation energy was 4 mJ 1mJ, the maximum output power of the laser may be changed to 1MW, 10MW, 100MW and 1000MW performs ionization. 这时的激光照射时间在1ps~4ns的范围内。 The laser irradiation time period in the range of 1ps ~ 4ns. 与试样的导入同步地照射脉冲激光,所生成的离子用行程时间型质量分析仪的微通道板进行检测,用数字示波器累计200次,获得光谱。 Introducing the sample is irradiated with the pulsed laser beam in synchronization, generated ions detected by the travel time mass analyzer type microchannel plate, with a total of 200 digital oscilloscope, spectrum is obtained. 将结果示于图2。 The results are shown in FIG.

比较例1用与实施例1相同的装置,遮断毫微微秒激光部的振荡,照射能量为1mJ和4mJ、最大输出功率为100KW及400KW的脉冲激光(照射时间为10ns),除此以外进行了与实施例相同的实验。 Comparative Example 1 using the same device as in Example 1, blocking femtosecond laser oscillation section, and the irradiation energy was 4 mJ 1mJ, maximum output power of the pulsed laser 100KW and 400KW (irradiation time 10ns), except that was experimental Example the same embodiment. 图2示出了其结果。 Figure 2 shows the results.

在图2所示的测定中,未观测到碎裂离子,只观测到分子离子。 In the assay shown in Figure 2, not observed fragment ions, molecular ions observed only. 由于脉冲激光的能量为4mJ、最大输出功率为400KW的离子强度(相对值)约为0.4,能量为1mJ、最大输出功率为100KW的离子强度约为0.5,所以离子强度增加了20%以上,很明显,离子强度不是与激光能量有关,而是与最大输出功率有关。 Since the energy of 4 mJ laser pulse, the maximum output power of 400KW ionic strength (relative value) of about 0.4, energy of 1 mJ, maximum output power of 100KW ionic strength of about 0.5, the ionic strength is increased 20 % or more, obviously, is not related to the ionic strength of the laser energy, but is related to the maximum output power. 另外,由比较例可知,在脉冲激光能量相同的情况下,使最大输出功率大者测定的离子强度大,与最大输出功率一起增加。 Further, it is understood from Comparative Example, in the same pulsed laser energy, the ion intensity measured by the maximum output power is large with the increase in maximum output power.

实施例2使用了与实施例1所使用的装置相同的装置。 Example 2 used the same as used in Example 1 the means. 毫微微秒级的脉冲色素激光是用Lambda Physik公司制的LPD500fs型的激光系统产生的。 Pulsed dye laser with a femtosecond-class laser system LPD500fs type manufactured by Lambda Physik generated. 另外,波长与实施例1相同,为248nm。 Further, the same wavelength as in Example 1, was 248nm.

氯苯、溴化苯及碘化苯与氩气一起以一定浓度的超声速分子射流的形式导入高真空的离子化室,考虑到各种分子的受激寿命,照射最大输出功率和照射能量在0.2~1.5mJ之间变化的激光,照射时间为500fs、150fs,进行了离子化。 Chlorobenzene, bromobenzene, and benzene iodide with argon introduced with the high vacuum chamber of the ion in the form of a jet of supersonic molecular certain concentration, considering the life of various excited molecules, the maximum output power and the irradiation energy is irradiated at 0 .2 ~ 1.5mJ vary between laser irradiation time is 500fs, 150fs, were ionized. 因此,这时的最大输出功率为0.4~10GW。 Thus, when the maximum output power of 0.4 ~ 10GW. 用行程时间型质量分析仪的微通道板检测所生成的离子,用Lecroy公司制的9360型数字示波器累计200次,获得了光谱。 A travel time mass analyzer type microchannel plate detector generated ions, with a Lecroy 9360 digital oscilloscope manufactured by accumulated 200 times to obtain a spectrum. 将结果示于图3、图4及图5。 The results are shown in FIGS. 3, 4 and 5.

比较例2使用与实施例2相同的装置,遮断毫微微秒激光部的振荡,照射15ns的激光,除此以外进行了与实施例2相同的实验。 Comparative Example 2 Using the same apparatus as in Example 2, blocking femtosecond laser oscillation unit, the laser irradiation 15ns, except subjected to the same experiment as in Example 2. 将结果示于图3~图5。 The results are shown in FIGS. 3 to 5.

这时,氯苯的受激寿命为600ps,激光照射时间500fs、150fs、15ns,分别相当于1/1200、1/4000、25倍,溴化苯的受激寿命为30ps,分别相当于1/60、1/200、500倍,另外同样报告了碘化苯的受激寿命为400ps左右,分别相当于约1/1.3、约1/2.7、约37500倍。 At this time, stimulated chlorobenzene life of 600ps, the laser irradiation time 500fs, 150fs, 15ns, equivalent to 1/1200, 1 / 4000,25 times, respectively, brominated benzene excited lifetime of 30ps, respectively corresponding to 1 / 60,1 / 200,500 times, but also reported benzene iodide excited lifetime is about 400ps, corresponding to about 1 / 1.3 to about 1 / 2.7, about 37,500-fold, respectively. 由图5可知,确认了与受激寿命大致同样程度短的照射时间有效,从图3和图4可知,照射时间为受激寿命的1/10000时有效。 Seen from FIG 5, it was confirmed with an effective irradiation time is short excited lifetime of substantially the same degree, as apparent from FIG. 3 and FIG. 4, when the irradiation time is effectively excited lifetime 1/10000. 另外,从这些图可知,如果以受激寿命为目标,照射激光,则能获得显著地提高离子化效率的效果。 Further, from these figures, if the excited lifetime of the target, irradiated with laser light, the effect can be obtained significantly improve the ionization efficiency.

另外,实施例1、实施例2只改变了脉冲激光的振荡条件,即只改变了激光的最大输出功率、照射时间及能量,除此以外,都是使用相同的装置且在相同的条件下进行实验的,所以离子强度能用相对值进行比较。 Further, Example 1, Example 2 pulsed laser oscillation condition changes, i.e., only the changed maximum output power of the laser irradiation time and energy, in addition, are using the same apparatus and under the same conditions as in experiment, the ion intensity can be a relative value. 因此,从图2及图3可知,照射脉冲激光时,如果在不引起分子碎裂的能量范围内增加最大输出功率,则能提高离子化效率。 Thus, it is seen from FIGS. 2 and 3, the pulse laser irradiation, if the energy range that does not cause fragmentation of the molecule to increase the maximum output power, the ionization efficiency can be improved. 即,图3中的激光能量为1mJ,照射时间500fs、150fs相当于最大输出功率为2GW(2000MW)、6.7GW(6700MW)。 That is, the laser energy of 1 mJ in FIG. 3, the irradiation time 500fs, 150fs corresponds to a maximum output power of 2GW (2000MW), 6.7GW (6700MW). 这时的离子强度随最大输出功率一起增加,1000MW时变为1.4。 At this ionic strength along with the increase in maximum output power, it becomes 1.4 1000MW. 可知由于最大输出功率增加,所以提高了离子化效率。 Be seen due to the increased maximum output power, the ionization efficiency is improved.

从以上的实施例1、2与比较例1、2的比较可知,如果采用本发明,通过最大输出功率大的超短脉冲激光照射,提高了离子化效率,但由于照射时间短,照射能量不大,不会引起极端的碎裂,所以能进行高灵敏度检测,具有能降低定量(检测)的下限的效果。 It is seen from Comparative Examples 1 and 2 and Comparative Examples 1 and 2 above, if the present invention, the maximum output power of the large ultrashort pulse laser irradiation, to improve the ionization efficiency, but because of the short irradiation time, the irradiation energy is not large, does not cause extreme fragmentation, it can be detected with high sensitivity, it can be reduced with a quantitative limit (detected) results.

实施例3制作了图6所示的激光离子化质量分析装置。 Example 3 produced the laser ionization mass spectrometer shown in Fig. 该装置中使用的大部分零件都是市售品,试样导入部1采用了General Valve公司制的脉冲阀(PN91-47-900(85kg/cm2)),脉冲激光振荡器2采用了Spectra-Physics公司制的MOPO-730型的激光系统,质量分析仪4采用了长为1200mm的行程管的行程时间型的质量分析仪,检测器46采用了滨松ホトニクス公司制的F1094型微通道板,而且记录仪(图中未示出)采用了Lecroy公司制的9360型数字示波器。 Most of the parts used in the apparatus are commercially available products, the sample introduction section 1 uses pulsed valve (PN91-47-900 (85kg / cm2)) General Valve Corporation, a pulse laser oscillator 2 using Spectra- MOPO-730 type laser system Physics Corporation, the mass analyzer 4 using the travel time type, length 1200mm stroke tube mass analyzer, a detector 46 uses F1094 micro channel plate Hamamatsu ホ Suites ni Irganox manufactured by, and recorder (not shown) using the 9360 type manufactured by Lecroy digital oscilloscope. 脉冲阀11的喷嘴12的开口呈内径为0.8mm的圆孔。 Opening of the nozzle 12 of the pulse valve 11 was 0.8mm inner diameter of the circular hole.

质量分析仪的真空室40和用激光进行照射的离子化室3都使用排气速度达190l/s的、日本真空技术公司制的UTM150型涡轮分子泵抽真空。 The mass analyzer vacuum chamber 40 and the ionization chamber is irradiated with a laser speed of the exhaust gas 3 are used 190l / s of, UTM150 turbomolecular type manufactured by Japan Vacuum Technology vacuum pump.

从振荡器2发生的脉冲激光22用透镜21聚光后,从窗口31进入真空离子化室3。 2 from the pulse laser oscillator 22 occurs converging lens 21, the window 31 into the vacuum chamber 3 ionization. 另一方面,试样气体用试样导入部1的脉冲阀11间歇地导入,从喷嘴12喷射,形成分子射流13。 On the other hand, the sample gas pulsing valve 11 is a sample introduction portion introduced intermittently injected from the nozzles 12, 13 to form a molecular jet. 该分子射流13进入真空离子化室3。 The molecular ion jet 13 into the vacuum chamber 3. 于是激光22照射该分子射流13,进行离子化,然后进入质量分析仪4。 Thus irradiating a laser jet 22 of the molecule 13 to be ionized, and then enter the mass analyzer 4. 在质量分析仪4内,首先分子射流的方向由反射电极42改变90度,其次由高压加速电极43进行加速。 In the mass analyzer 4, changing the direction of the jet first molecule by the reflective electrode 42 by 90 degrees, followed by a high voltage accelerating electrode 43 is accelerated. 然后通过离子通过孔44。 Through the aperture 44 and then through the ion. 再由反射器反射,由离子检测器46检测各离子。 Then reflected by the reflector, by the ion detector 46 to detect the ions. 用数字示波器测量该检测信号。 The measured detection signal with a digital oscilloscope.

试样气体使用O-氯代苯酚,进行了质量分析。 O- sample gas using chlorinated phenols, mass were analyzed.

毫微秒级的脉冲激光的波长为278.5nm,脉宽为5ns。 Wavelength of the pulsed laser light is nanosecond 278.5nm, pulse width of 5ns. 另外,脉冲激光能量为1mJ。 The pulse laser energy is 1mJ.

将一定量的O-氯代苯酚滴入流过氩气的500ml的烧瓶中(初始浓度为200ppm左右)。 500ml flask the amount of chlorophenols added dropwise O- flowing argon (initial concentration of about 200ppm). 每20分钟滴入一次。 Drops every 20 minutes. 另外,每秒钟将连接在烧瓶出口上的上述脉冲阀打开10次,每次打开的时间为200微秒,取烧瓶中气体的一部分,以超声速分子射流的形式导入高真空离子化室。 Further, the flask is connected to every second outlet valve opening 10 of the pulse times, each time of 200 microseconds is opened, a part of the gas in the flask was introduced into the high vacuum of the ionization chamber form a jet of supersonic molecule. 同步地照射脉冲激光,用行程时间型的微通道板检测所生成的离子,由数字示波器获得光谱,记录了随时间的变化。 Pulsed laser light is irradiated in synchronization with a microchannel plate detector travel time type generated ion spectra were acquired by a digital oscilloscope, the record changes over time. 另外,最后从O-氯代苯酚的滴入结束时起,经过20分钟后,将激光停止。 Further, since the end of last O- chlorophenols from added dropwise over 20 minutes, the laser will stop. 将结果示于图7。 The results are shown in FIG.

比较例3使用与实施例3相同的装置,用1200l/s的日本真空技术公司制的ULK-06A型的油扩散泵对离子化室进行排气,除此以外,进行了与实施例相同的实验。 Comparative Example 3 Using the same apparatus as in Example 3, the ionization chamber is exhausted by ULK-06A type oil diffusion pump 1200l / s in Japan Vacuum Technology Co., Ltd., except that carried out the same as Example experiment. 将结果示于图8。 The results are shown in FIG.

比较例4脉冲阀采用将汽车用发动机的燃料喷射阀改造后的阀(开放时间为1.5ms),除此以外,用与实施例相同的装置进行了实验。 Comparative Example 4 using the pulse valve car conducted experiments in the same valve device according to the embodiment of the fuel injection valves of engine modifications (open time 1.5ms), except with. 将结果示于图9。 The results are shown in FIG.

在图7~图9中,如果将激光停止,则由于不产生激光,所以相当于零点电平,另外,振动(变化)是检测系统的噪声。 In FIGS. 7 to FIG. 9, if the laser is stopped, the laser light is not generated, the level corresponding to zero, Further, vibration (variation) is a noise detection system. 与比较例3相比较,在实施例3中,由于本底下降,同时不大量导入试样,所以变化小,噪声减少,这是显而易见的。 Compared with Comparative Example 3, in Example 3, since the background drop, without introducing a large number of samples, therefore small changes, noise reduction, it will be apparent. 即,断定能进行高灵敏度的检测。 That is, the detection can be performed to determine with high sensitivity. 其效果从原理上说,使用涡轮分子泵,如果使开放时间比通常短,理应能发现,但使开放时间在500微秒以下时才变得显著。 The effect In principle, the use of turbo molecular pump, if the opening hours are shorter than usual, should be able to find, but when the opening time becomes significant at 500 microseconds.

从以上的实施例3和比较例3、4的比较可知,如果采用本发明,则能缩短试样导入时间,另外由于使用无油泵进行离子化室的排气,所以能减少由油或残留的试样引起的本底,故能进行高灵敏度的检测,具有降低定量(检测)下限的效果。 From the above Comparative Example 3 and Comparative Examples 3 and 4 can be seen, if the present invention, the sample introduction time can be shortened, without the use of additional exhaust pump ionization chamber, it is possible to reduce the residual oil or background sample caused, it can be detected with high sensitivity, has a reduced amount (detected) limit the effect.

实施例4制作了图10~图11所示的激光离子化质量分析装置。 Example 4 produced laser ionization mass analyzer shown in FIGS. 10 to 11. 该装置中使用的大部分零件都是市售品,试样导入部1采用了General Valve公司制的脉冲阀(PN91-47-900(85kg/cm2)),脉冲激光振荡器3采用了Spectra-Physics公司制的MOPO-730型的激光系统,质量分析仪4采用了长为1200mm的行程管的行程时间型的质量分析仪,检测器46采用了滨松ホトニクス公司制的F1094型微通道板,而且记录仪(图中未示出)采用了Lecroy公司制的9360型数字示波器。 Most of the parts used in the apparatus are commercially available products, the sample introduction section 1 uses pulsed valve (PN91-47-900 (85kg / cm2)) General Valve Corporation, a pulse laser oscillator 3 using Spectra- MOPO-730 type laser system Physics Corporation of mass analyzer 4 uses a travel time type, length 1200mm stroke tube mass analyzer, a detector 46 uses F1094 micro channel plate Hamamatsu ホ Suites ni Irganox manufactured by, and recorder (not shown) using the 9360 type manufactured by Lecroy digital oscilloscope.

将图11所示的脉冲阀11安装在试样导入部上。 The pulse shown in Figure 11 the valve 11 is mounted on the sample introduction portion. 该脉冲阀11是用不锈钢制的,口径为0.2mm的两个针孔喷嘴12的中心点之间的间隔设为30mm。 The pulse valve 11 is made of stainless steel, the diameter of the center point of the interval is set between the two pin holes 12 of the nozzle of 0.2mm 30mm.

分离器14用不锈钢制成,厚度为0.8mm,孔径为0.3mm,其前端的外壁角度为55°,内壁角度为45°。 Separator 14 made of stainless steel, thickness 0.8mm, pore size of 0.3mm, the outer wall of the tip angle of 55 °, the inner wall an angle of 45 °. 分离器的位置距喷嘴为25mm。 The position of the separator from the nozzle is 25mm. 这样配置分离器,即,使由形状相同的两个喷嘴和分离器获得的分子射流在质量分析仪的反射电极的位置相交,且使分子射流彼此相交的角度为20°,使两个喷嘴与激光同步地一起工作。 Such a splitter, i.e., molecules obtained from the same jet shape and the two nozzles intersect at a position splitter reflective electrode mass analyzer, and the molecular jets intersect each other an angle of 20 °, the two nozzle laser work together synchronously.

从振荡器2发出的脉冲激光22用透镜21聚光后,从窗口31进入真空离子化室3。 2 from the pulse emitted from the laser oscillator 22 with a condenser lens 21, the window 31 into the vacuum chamber 3 ionization. 另一方面,试样气体用试样导入部1的脉冲阀11间歇地导入,从喷嘴12喷射,形成分子射流13。 On the other hand, the sample gas pulsing valve 11 is a sample introduction portion introduced intermittently injected from the nozzles 12, 13 to form a molecular jet. 该分子射流13碰撞分离室14,只有其中心部分才通过分离室14上的孔部15而进入真空离子化室3。 The molecular jet 13 collide separation chamber 14, only the central portion only through the hole portion 14 in the separation chamber 15 into the vacuum chamber 3 ionization. 于是激光22照射该分子射流16,进行离子化,然后进入质量分析仪4。 Thus irradiating a laser jet 22 of the molecule 16 to be ionized, and then enter the mass analyzer 4. 在质量分析仪4的真空室40内,首先分子射流16的方向由反射电极42改变90度,其次由高压加速电极43进行加速。 In the mass analyzer 40 of the vacuum chamber 4, the jet direction of the first elements 16 by the reflective electrode 42 is changed by 90 degrees, followed by a high voltage accelerating electrode 43 is accelerated. 然后,再由离子反射器45反射,由离子检测器46检测各离子。 Then, the ion reflector 45 reflector, each ion detected by the ion detector 46. 用数字示波器测量该检测信号。 The measured detection signal with a digital oscilloscope. 排气系统分别连接在被分离室14隔开的前室17、真空离子化室3及质量分析仪的真空室40上,使内部维持真空状态。 The exhaust system are connected to the separation chamber 14 is separated from the front chamber 17, the vacuum chamber 3 and the ionization mass analyzer vacuum chamber 40, the inside is maintained in a vacuum state.

试样气体采用氯苯,进行了质量分析。 Chlorobenzene sample gas, the mass analysis performed. 这时的激光能量为2mJ,照射时间为5ns,波长为269.8nm。 Time laser energy is 2mJ, the irradiation time is 5ns, a wavelength of 269.8nm. 氯苯与氩气一起以一定浓度的超声速射流的形式导入高真空离子化室4。 Chlorobenzene together with argon gas introduced into the high vacuum of the ionization chamber 4 in the form of a jet of supersonic certain concentration. 用微通道板检测所生成的离子,用数字示波器累计10次,获得了光谱。 A microchannel plate detector generated ions, total 10 times with a digital oscilloscope, a spectrum is obtained. 将结果示于图12。 The results are shown in FIG. 12.

比较例5 Comparative Example 5

除了使一个喷嘴不工作以外,使用和实施例4相同的装置,进行了相同的实验。 Except that a nozzle does not work outside, using the same apparatus as in Example 4, subjected to the same experiment. 将获得的结果示于图12。 The results obtained are shown in FIG. 12.

从图12可知,在实施例4和比较例5中,峰值宽度不变。 12 shows that, in Example 4 and Comparative Example 5, the peak value of constant width. 另外,在实施例4中使用两个喷嘴,与比较例5相比,导入2倍的试样,所以S/N比为2倍。 Further, in Example 4 using two nozzles, as compared with Comparative Example 5, the sample introduced into the 2-fold, so the S / N ratio was 2 times. 因此,能导入大量的试样,由于峰值宽度不扩大,所以能谋求直接与导入试样的量成正比的高灵敏度,即导入装置与其它部分相比相当小,所以意味着,在使分析装置、特别是排气系统的结构紧凑的情况下,照样能谋求高灵敏度。 Thus, a large number of samples can be introduced, since the peak width is not expanded, it is possible to achieve directly proportional to the amount of introduced sample with high sensitivity, i.e. introducing means relatively small compared to other portions, so that means that, when the analysis device , in particular in the case of compact exhaust system, still possible to achieve high sensitivity.

从以上的实施例4和比较例5的比较可知,如果采用本发明,由于不用提高质量分析仪的能力,即用廉价、紧凑的质量分析仪能导入大量的试样,所以激光离子化质量分析装置具有能在紧凑的条件下谋求高灵敏度的效果。 5 seen from Comparative Example 4 and Comparative Example above, according to this invention, since the capacity without increasing the mass analyzer, i.e. inexpensive, compact mass analyzer capable of introducing a large number of samples, the laser ionization mass spectrometry means possible to achieve the effect of having a high sensitivity in a compact condition.

实施例5制作了图13及图14所示的激光离子化质量分析装置。 Example 13 and produced 5 laser ionization mass analyzer 14 shown in FIG. 该装置中使用的大部分零件都是市售品,试样导入部1采用了General Valve公司制的脉冲阀(PN91-47-900(85kg/cm2)),脉冲激光振荡器2采用了Spectra-Physics公司制的MOPO-730型的激光系统,质量分析仪4采用了长为1200mm的行程管的行程时间型的质量分析仪,检测器46采用了滨松ホトニクス公司制的F1094型微通道板,而且记录仪(图中未示出)采用了Lecroy公司制的9360型数字示波器。 Most of the parts used in the apparatus are commercially available products, the sample introduction section 1 uses pulsed valve (PN91-47-900 (85kg / cm2)) General Valve Corporation, a pulse laser oscillator 2 using Spectra- MOPO-730 type laser system Physics Corporation, the mass analyzer 4 using the travel time type, length 1200mm stroke tube mass analyzers, the detector 46 uses F1094 micro channel plate Hamamatsu ホ Suites ni Irganox manufactured by, and recorder (not shown) using the 9360 type manufactured by Lecroy digital oscilloscope.

试样导入部的狭缝喷嘴12用SUS制成,狭缝开口部的大小为0.1mm×10mm。 Sample introduction slit nozzle portion 12 is made of SUS, the size of the slit opening portion is 0.1mm × 10mm.

制作了两种狭缝分离器14,其剖面如图15所示。 Making two slits separator 14, 15 shown in cross section in FIG. 狭缝前端中心和狭缝两面底端之间的角度,一个为40°,另一个为50°。 The angle between the slits and the slits distal the center of the bottom sides, one of 40 °, the other of 50 °. 该分离器14用铝制成,最大厚度为1.2mm,狭缝前端呈尖形,狭缝18的开口部的大小为0.2mm×12mm。 The separator 14 is made of aluminum, a maximum thickness of 1.2mm, the distal end was tapered slit, the slit size of the opening portion 18 is 0.2mm × 12mm. 该狭缝分离器14的位置设置得距喷嘴12为25mm,喷嘴12和分离器14的纵轴方向相同,而且中心一致。 The position of the slot separator 14 from the nozzle 12 is set to be 25mm, the nozzle 12 and the separator 14 in the same longitudinal direction, and coincides with the center.

从振荡器2发出的脉冲激光22用透镜21聚光后,从窗口31进入真空离子化室3。 2 from the pulse emitted from the laser oscillator 22 with a condenser lens 21, the window 31 into the vacuum chamber 3 ionization. 另一方面,试样气体用试样导入部1的脉冲阀11间歇地导入,从喷嘴12喷射,形成分子射流13。 On the other hand, the sample gas pulsing valve 11 is a sample introduction portion introduced intermittently injected from the nozzles 12, 13 to form a molecular jet. 该分子射流13碰撞分离室14,只有其中心部分才通过分离室14的狭缝18,大致呈平行的气流进入真空离子化室3。 The molecular jet 13 collide separation chamber 14, only the central portion only through the separation chamber 18 of the slot 14, substantially parallel gas flow into the vacuum chamber 3 ionization. 于是激光22照射该分子射流16,进行离子化,然后进入质量分析仪4。 Thus irradiating a laser jet 22 of the molecule 16 to be ionized, and then enter the mass analyzer 4. 在质量分析仪4内,首先分子射流16的方向由反射电极42改变90度,其次由高压加速电极43进行加速。 4 in the mass analyzer, the direction of the jet 16 of the first molecule by the reflective electrode 42 is changed by 90 degrees, followed by a high voltage accelerating electrode 43 is accelerated. 然后,再由离子反射器45反射,由离子检测器46检测各离子。 Then, the ion reflector 45 reflector, each ion detected by the ion detector 46. 用数字示波器测量该检测信号。 The measured detection signal with a digital oscilloscope. 排气系统分别连接在被分离室14隔开的前室17、真空离子化室3及质量分析仪的真空室40上,使内部维持真空状态。 The exhaust system are connected to the separation chamber 14 is separated from the front chamber 17, the vacuum chamber 3 and the ionization mass analyzer vacuum chamber 40, the inside is maintained in a vacuum state.

试样气体采用氯苯,进行了质量分析。 Chlorobenzene sample gas, the mass analysis performed. 这时的激光能量为2mJ,照射时间为5ns,波长为269.8nm。 Time laser energy is 2mJ, the irradiation time is 5ns, a wavelength of 269.8nm. 氯苯与氩气一起以一定浓度的超声速射流的形式导入高真空离子化室3。 Chlorobenzene together with argon gas introduced into the high vacuum ionization chamber 3 in the form of a jet of supersonic certain concentration. 用微通道板检测所生成的离子,用数字示波器累计10次,获得了光谱。 A microchannel plate detector generated ions, total 10 times with a digital oscilloscope, a spectrum is obtained. 将结果示于图16。 The results are shown in FIG. 16.

比较例6除了不附加狭缝分离器以外,使用和实施例5相同的装置,进行了相同的实验。 Comparative Example 6 except that no additional separators slit, and using the same apparatus as in Example 5, the same experiment was conducted. 这时的分子射流如图14中的虚线所示进行喷射。 At this dotted line 14 shown in FIG molecular jet is injected. 将获得的结果示于图16。 The results obtained are shown in FIG. 16.

从图16可知,即使使用狭缝分离器,信号强度也几乎不减小。 It is seen from FIG. 16, even if a slot splitter, the signal strength is hardly reduced. 如果使用狭缝分离器,从原理上可知,分子射流的外围部分的分子、即对信号来说无用的分子被阻止,不能进入离子化室和质量分析仪。 If the slit separator, seen from the principle, the peripheral portion of the molecule jet molecules, i.e., molecules is blocked unwanted signals, can not enter the ionization chamber and the mass analyzer. 因此,其结果,通过附加狭缝分离器,无损于灵敏度,却能抑制质量分析仪的真空度的变化,同时能提高导入相同试样量时的真空度。 Thus, as a result, by attaching the separator slit, without prejudice to the sensitivity, but it can suppress the variation of the degree of vacuum of the mass analyzer, while improving the degree of vacuum when introduced into the same amount of sample. 这意味着在有无狭缝分离器的情况下,如果将两种情况下的质量分析仪的真空度保持相同,则附加了狭缝分离器者,能导入对信号有用的分子流一致的大量的试样,能谋求高灵敏度。 This means that in the case where the presence or absence of the slits of the separator, if the degree of vacuum of the mass analyzer remains the same in both cases, the slit is added by the separator, can be introduced on the same molecule useful in a large number of flow signals samples, possible to achieve high sensitivity.

从以上的实施例5和比较例6的比较可知,如果采用本发明,由于不用提高质量分析仪的能力,即用廉价、紧凑的质量分析仪能导入大量的试样,所以,激光离子化质量分析装置具有能在紧凑的条件下谋求高灵敏度的效果。 Seen from Comparative Example 6 and Comparative Example 5 above, according to this invention, since the capacity without increasing the mass analyzer, i.e. inexpensive, compact mass analyzer capable of introducing a large number of samples, so that the laser ionization mass possible to achieve the effect analysis device having a high sensitivity in a compact condition.

工业上的应用领域如上所述,本发明的这种激光离子化质量分析装置及质量分析方法通过最大输出功率大的超短脉冲激光照射,提高离子化效率,但由于照射时间短,所以照射能量不大,不会引起极端的碎裂,所以能进行高灵敏度检测,能降低定量(检测)下限。 Industrial Application As described above, such laser ionization mass spectrometer and the mass spectrometry method of the present invention by a large maximum output power of ultrashort-pulse laser irradiation, to improve the ionization efficiency, but because of the short irradiation time, the irradiation energy so not, will not cause extreme fragmentation, it can be detected with high sensitivity can be reduced amount (detected) limit. 另外,由于试样导入时间短,且使用无油泵进行离子化室的排气,所以能降低由油或残留的试样引起的本底,故能进行高灵敏度的检测,能降低定量(检测)下限。 Further, due to the short time of sample introduction, and an oil pump using no exhaust ionization chamber, it is possible to reduce the background caused by the sample or residual oil, it can be detected with high sensitivity can be reduced quantitatively (detection) The lower limit. 另外,由于能用廉价的结构紧凑的质量分析仪导入大量的试样,所以,激光离子化质量分析装置既能保持结构紧凑,又能提高灵敏度。 Further, since the use of an inexpensive compact mass analyzer importing a large number of samples, so that the laser ionization mass spectrometer can maintain the compact, and can improve the sensitivity. 因此,适用于煤、重油等燃烧时排放的气体、城市垃圾或工业废弃物焚烧时排放的气体、塑料热解产生的气体等中含有微量的氮氧化合物、硫氧化合物、芳香族化合物、氯系列有机化合物、氯化芳香族化合物、以及卤素系列化合物等的迅速分析。 Thus, when applied to the discharge of the combustion gas coal, heavy oil, gas emission during incineration of municipal waste or industrial waste, such as plastic pyrolysis gas contains trace amounts of nitrogen oxides, sulfur oxides, aromatic compounds, chlorine quickly analyze series compounds, chlorinated aromatic compounds, and a halogen series compound and the like.

Claims (7)

1. 1. 一种激光离子化质量分析装置,其特征在于:备有:具有形成分子射流的脉冲阀的试样导入部,脉冲激光振荡器,具有使从该振荡器发出的激光通过的窗口的真空离子化室或与其相当的部位,以及分析被该激光离子化了的分子质量的质量分析仪;上述脉冲激光振荡器能发生最大输出功率为1MW以上的超短脉冲激光。 A laser ionization mass spectrometer, wherein: provided with: a sample introducing portion forming molecules pulse jet valve, a pulse laser oscillator, the laser beam having a vacuum ionization emitted from the oscillator by a window chamber or equivalent parts, and analyzing the laser light is ionized molecular mass of the mass analyzer; and the maximum output power pulsed laser oscillator can occur 1MW or more ultrashort pulse laser.
2. 2. 根据权利要求1所述的激光离子化质量分析装置,其特征在于:使上述真空离子化室排气的泵采用涡轮分子泵。 The laser ionization mass spectrometer according to claim 1, wherein: the ionization chamber so that the vacuum exhaust pump is a turbomolecular pump.
3. 3. 一种质量分析方法,其特征在于:由形成分子射流的脉冲阀将试样气体喷射到真空离子化室或与其相当的部位,形成脉冲状分子射流,用最大输出功率为1MW以上的超短脉冲激光照射该分子射流,使其离子化,分析被该激光离子化了的分子的质量。 A quality-analysis method, comprising: a pulse jet valve formed molecules injected into the sample gas ionization vacuum chamber or equivalent portions, and a pulse jet molecule, with a maximum output power of 1MW or more ultrashort pulses the molecular jet laser irradiation, and ionizing, the laser beam is mass analyzed ionized molecules.
4. 4. 根据权利要求3所述的质量分析方法,其特征在于:脉冲激光的能量为5mJ以下,照射时间为测定对象分子的受激寿命的3倍~1/10000倍。 Mass spectrometry method according to claim 3, wherein: the pulse energy of the laser is 5mJ or less, the irradiation time of the measurement of the excited molecules to life 3 times to 1 / 10,000 times.
5. 5. 一种激光离子化质量分析装置,其特征在于:备有:具有形成分子射流的脉冲阀的试样导入部,脉冲激光振荡器,具有使从该振荡器发出的激光通过的窗口的真空离子化室或与其相当的部位,以及分析被该激光离子化了的分子质量的质量分析仪;使上述真空离子化室排气的泵采用涡轮分子泵。 A laser ionization mass spectrometer, wherein: provided with: a sample introducing portion forming molecules pulse jet valve, a pulse laser oscillator, the laser beam having a vacuum ionization emitted from the oscillator by a window chamber or equivalent parts, and analyzing the laser light is ionized molecular mass of the mass analyzer; ionization chamber so that the vacuum exhaust pump is a turbomolecular pump.
6. 6. 一种激光离子化质量分析装置,其特征在于:备有:具有形成分子射流的脉冲阀的试样导入部,脉冲激光振荡器,具有使从该振荡器发出的激光通过的窗口的真空离子化室或与其相当的部位,以及分析被该激光离子化了的分子质量的质量分析仪;上述试样导入部的喷嘴由两个以上的针孔喷嘴构成。 A laser ionization mass spectrometer, wherein: provided with: a sample introducing portion forming molecules pulse jet valve, a pulse laser oscillator, the laser beam having a vacuum ionization emitted from the oscillator by a window chamber or equivalent parts, and analyzing the laser light is ionized molecular mass of the mass analyzer; the sample introduction nozzle portion consists of two or more pinholes nozzle.
7. 7. 一种激光离子化质量分析装置,其特征在于:备有:具有形成分子射流的脉冲阀的试样导入部,脉冲激光振荡器,具有使从该振荡器发出的激光通过的窗口的真空离子化室或与其相当的部位,以及分析被该激光离子化了的分子质量的质量分析仪;将上述狭缝喷嘴和真空离子化室之间隔开,设置能阻止该分子射流周围部分的分子流进入真空离子化室的狭缝分离器。 A laser ionization mass spectrometer, wherein: provided with: a sample introducing portion forming molecules pulse jet valve, a pulse laser oscillator, the laser beam having a vacuum ionization emitted from the oscillator by a window chamber or equivalent parts, and analyzing the laser light is ionized molecular mass of the mass analyzer; separating the vacuum between the slit nozzle and the ionization chamber, can prevent the molecules of the molecule is provided around the jet portion of the stream enters vacuum separator slit ionization chamber.
CN 97191457 1997-08-29 1997-08-29 Laser ionization mass spectroscope and mass spectrometric analysis method CN1206493A (en)

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Publication number Priority date Publication date Assignee Title
US7342223B2 (en) 2004-06-16 2008-03-11 Shimadzu Corporation Mass spectrometer for biological samples
CN102280347A (en) * 2010-07-06 2011-12-14 东华理工大学 Atmospheric Pressure Chemical Ionization and extracted with atmospheric pressure chemical ionization mass spectrometry was extracted
CN101281165B (en) 2008-05-15 2012-07-04 复旦大学 Method and apparatus for ionizing mass spectrographic analysis sample
CN102539513A (en) * 2010-12-09 2012-07-04 苏州生物医学工程技术研究所 Noninvasive detecting device for diseases of patients and detection method thereof
CN103560071A (en) * 2013-10-09 2014-02-05 中国科学院大连化学物理研究所 Double-valve laser sputtering reaction source

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7342223B2 (en) 2004-06-16 2008-03-11 Shimadzu Corporation Mass spectrometer for biological samples
CN101281165B (en) 2008-05-15 2012-07-04 复旦大学 Method and apparatus for ionizing mass spectrographic analysis sample
CN102280347A (en) * 2010-07-06 2011-12-14 东华理工大学 Atmospheric Pressure Chemical Ionization and extracted with atmospheric pressure chemical ionization mass spectrometry was extracted
CN102539513A (en) * 2010-12-09 2012-07-04 苏州生物医学工程技术研究所 Noninvasive detecting device for diseases of patients and detection method thereof
CN103560071A (en) * 2013-10-09 2014-02-05 中国科学院大连化学物理研究所 Double-valve laser sputtering reaction source

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