JPS62232848A - Mass spectrometer - Google Patents
Mass spectrometerInfo
- Publication number
- JPS62232848A JPS62232848A JP7627686A JP7627686A JPS62232848A JP S62232848 A JPS62232848 A JP S62232848A JP 7627686 A JP7627686 A JP 7627686A JP 7627686 A JP7627686 A JP 7627686A JP S62232848 A JPS62232848 A JP S62232848A
- Authority
- JP
- Japan
- Prior art keywords
- vacuum
- degree
- measurement
- sample
- parent ions
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 150000002500 ions Chemical class 0.000 claims abstract description 48
- 238000005259 measurement Methods 0.000 claims abstract description 44
- 238000001514 detection method Methods 0.000 claims abstract description 8
- 238000001819 mass spectrum Methods 0.000 abstract description 9
- 239000000523 sample Substances 0.000 description 26
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 14
- 235000011187 glycerol Nutrition 0.000 description 7
- 238000010586 diagram Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002923 metal particle Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910001111 Fine metal Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000005464 sample preparation method Methods 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Electron Tubes For Measurement (AREA)
- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
Abstract
Description
【発明の詳細な説明】
〈産業上の利用分野〉
本発明は試料をイオン化し得られた質量スペクトルから
試料分子の組成等を分析する質量分析装置の改良に関す
る。DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to an improvement in a mass spectrometer that analyzes the composition of sample molecules from a mass spectrum obtained by ionizing a sample.
〈従来の技術〉
ｌｌＣｍ分析針において難揮発性で熱的不安定な有機物
質をイオン化する場合、フラグメンテーションを起させ
ずに親イオンを発生させる方法のひとつにレーザ光を照
射する方法がある。この場合、固体試料は、水、エタノ
ール、アセトン等の適当な溶媒に溶かし、全屈等の試料
ホルダー上に滴下した後、乾燥させ、薄膜状にして用い
られる。しかし、この状態では、親イオンの生成量が微
小で、また、長時間のイオン生成は期待できない。<Prior Art> When a non-volatile and thermally unstable organic substance is ionized using an 11Cm analysis needle, one method of generating parent ions without causing fragmentation is to irradiate it with laser light. In this case, the solid sample is dissolved in a suitable solvent such as water, ethanol, acetone, etc., dropped onto a sample holder such as a full flexure, dried, and used in the form of a thin film. However, in this state, the amount of parent ions produced is minute, and ion production cannot be expected for a long time.
本出願人は、イオンの生成量を増大させ、しかもその継
続時間を長くするため、試料溶液に全屈微粒子と例えば
グリセリン等の低蒸気圧液体を添加する方法を既に提案
した。しかし、この様な試料作成法によっても、高質量
数物質においてはその親イオンの生成時間は限られてい
る。In order to increase the amount of ions produced and also their duration, the applicant has already proposed a method of adding to the sample solution total reflux microparticles and a low vapor pressure liquid such as glycerin. However, even with this sample preparation method, the time for parent ion generation in high mass number substances is limited.
〈発明が解決しようとする問題点〉
通常、飛行時間型質量分析計においては、原理的には１
回の測定で全質量スペクトルが得られるはずであるが、
高質量数イオン等の微少・イオンに対しては、何回かの
測定を積算してスペクトルを得ることが行なわれる。こ
の場合、上述のにうに親イオンの生成時間が限定されて
いると、むやみに積算回数を増大しても、親イオン以外
のフラグメントイオンや他のイオンばかり検出され、親
イオンの検出が困難になる。また、親イオンの検出がで
きても、非常にＳＮ比の悪いスペクトルしか得られない
。<Problems to be solved by the invention> Normally, in a time-of-flight mass spectrometer, in principle, 1
The entire mass spectrum should be obtained in one measurement, but
For minute ions such as high mass number ions, spectra are obtained by integrating several measurements. In this case, if the parent ion generation time is limited as mentioned above, even if you increase the number of integrations unnecessarily, only fragment ions and other ions other than the parent ion will be detected, making it difficult to detect the parent ion. Become. Furthermore, even if the parent ion can be detected, only a spectrum with a very poor signal-to-noise ratio can be obtained.
く問題点を解決するための手段〉
本発明に係る質量分析装置は、イオン源部を含む真空チ
ャンバの真空度を検出する真空度検出手段と、真空度に
応じて測定の開始と終了を制御する制御手段とを備える
。Means for Solving the Problems> The mass spectrometer according to the present invention includes a degree of vacuum detection means for detecting the degree of vacuum of a vacuum chamber including an ion source section, and a degree of vacuum detection means that controls the start and end of measurement according to the degree of vacuum. and control means.
く作用〉
本発明に係る質量分析装置は、上述の構成のもとで、真
空チャンバの真空度から親イオンの生成量が増大する時
刻を推測し、最良の時刻において測定を開始し終了する
。Effect> The mass spectrometer according to the present invention has the above-described configuration, estimates the time at which the amount of parent ions produced increases from the degree of vacuum in the vacuum chamber, and starts and ends measurement at the best time.
〈発明の原理〉
試料に金属微粒子とグリセリン等を添加するという方法
によって高質量親イオンの生成が可能であるが、その生
成時間は限られている。第５図に示すように、親イオン
強度は、試料の導入から一定の時間帯において急激に増
大し、その後は低下する。このように親イオンの生成時
間が限定される原因として、グリセリン等の低蒸気圧液
体が完全に蒸発してしまう直前すなわち半渇きの状態で
親イオンの生成量が増大することが実験事実として確認
されている。<Principle of the Invention> High-mass parent ions can be generated by adding fine metal particles and glycerin to a sample, but the generation time is limited. As shown in FIG. 5, the parent ion strength increases rapidly over a certain period of time after introduction of the sample, and then decreases. It has been experimentally confirmed that the reason why the production time of parent ions is limited is that the amount of parent ions produced increases just before a low vapor pressure liquid such as glycerin completely evaporates, that is, in a half-dry state. has been done.
そこで、試料の表面の乾燥状態をイオン源部を含む真空
チャンバの真空度によって検出し、親イオンの生成量が
増大する時間帯になったところで測定を開始する。Therefore, the dry state of the surface of the sample is detected by the degree of vacuum in the vacuum chamber that includes the ion source, and measurement is started at a time when the amount of parent ions produced increases.
〈実施例〉
第１図は本実施例のレーザイオン化質量分析装置の構成
を示す。<Example> FIG. 1 shows the configuration of a laser ionization mass spectrometer according to this example.
真空チャンバ１は、イオン源部２１分析部３並びに検出
部４を含み、図示しない真空ポンプにより真空に保持さ
れる。試料５は、試料ホルダ６上に載置されてイオン源
部２に導入される。The vacuum chamber 1 includes an ion source section 21, an analysis section 3, and a detection section 4, and is maintained in a vacuum by a vacuum pump (not shown). The sample 5 is placed on a sample holder 6 and introduced into the ion source section 2 .
測定時には、試料５に図示しないレーザ光源から励起レ
ーザ光が照射され、発生した親イオンが分析部３に導か
れる。During measurement, the sample 5 is irradiated with excitation laser light from a laser light source (not shown), and the parent ions generated are guided to the analysis section 3.
真空計７は、イオン源部２の試料５の近傍に配置される
。この真空計７としては、例えば電離真空計法が用いら
れる。真空度測定回路８は、真空計７により検出された
真空度を示す信号を出力する。ｉｊ［ｌＩ定開始／終了
真空度設定回路９は、予め設定された測定を開始すると
きの真空度と測定を終了するときの真空度を示す信号を
出力する。比較回路１０は、検出された実際の真空度と
設定された測定開始真空度および測定終了真空度との大
小比較を行ない、実際の真空度が測定開始真空度より小
で且つ測定終了真空度より大である間、測定動作制御信
号を出力する。質量スペクトル測定回路１１は、この測
定動作制御信号の入力に応じて、イオン源部２にて発生
した親イオンの質量スペクトルを測定する。The vacuum gauge 7 is placed near the sample 5 in the ion source section 2 . As this vacuum gauge 7, for example, an ionization vacuum gauge method is used. The degree of vacuum measuring circuit 8 outputs a signal indicating the degree of vacuum detected by the vacuum gauge 7. ij[lI constant start/end vacuum degree setting circuit 9 outputs a signal indicating the preset vacuum degree at the time of starting the measurement and the vacuum degree at the end of the measurement. The comparison circuit 10 compares the detected actual vacuum degree with the set measurement start vacuum degree and measurement end vacuum degree, and determines that the actual vacuum degree is smaller than the measurement start vacuum degree and is smaller than the measurement end vacuum degree. While the signal is high, a measurement operation control signal is output. The mass spectrum measurement circuit 11 measures the mass spectrum of parent ions generated in the ion source section 2 in response to the input of this measurement operation control signal.
試料ホルダ６に試料を載せずに試料ホルダ６だけをイオ
ン源部２に挿入して真空に引いた場合、真空度の変化は
第２図に示すようになり、短時間で高真空に達する。When only the sample holder 6 is inserted into the ion source section 2 without placing a sample on the sample holder 6 and the ion source section 2 is evacuated, the degree of vacuum changes as shown in FIG. 2, and a high vacuum is reached in a short time.
一方、金属微粒子とグリセリンを添加した試料５を試料
ホルダ６に載せてイオン源部２に挿入して真空に引いた
場合、第３図に示すように高真空になるまでに長時間を
要する。これは、グリセリンが蒸発するので、高真空に
なるには試料５を乾燥させてしまう必要があり、これに
時間がかかるからである。On the other hand, when the sample 5 to which metal fine particles and glycerin have been added is placed on the sample holder 6, inserted into the ion source section 2, and evacuated, it takes a long time to reach a high vacuum as shown in FIG. This is because the glycerin evaporates, so it is necessary to dry the sample 5 to achieve a high vacuum, which takes time.
親イオンの生成は、この試料５の乾燥の過程のある時間
帯に起る（第５図）。そして、この時間帯は、試料５が
半渇きの状態になるときであり、試料の種類にもある程
度依存するが、試料、金属微粒子、グリセリンの量を一
定にすると、はぼ同じ真空度で生成イオン量のピークを
与える。なぜなら、真空度はグリセリンの蒸発量すなわ
ち試料の乾燥度を反映しているからである。Generation of parent ions occurs during a certain period of time during the drying process of sample 5 (FIG. 5). During this time period, sample 5 is in a half-dry state, and although it depends to some extent on the type of sample, if the amounts of sample, metal particles, and glycerin are constant, the product will be generated at approximately the same degree of vacuum. Gives the peak of ion content. This is because the degree of vacuum reflects the amount of evaporation of glycerin, that is, the degree of dryness of the sample.
そこで、生成イオン量がピークになる時間帯から、第４
図に示すように測定を開始する真空度と終了する真空度
とを予め設定する。そして、測定開始／終了真空度設定
回路９にてこの測定開始真空度と測定終了真空度を示す
信号を出力し、真空度測定回路８が出力する実際の真空
度を示す信号と比較回路１０にて比較し、実際の真空度
が測定開始真空度と測定終了真空度の範囲内にあるとき
に出力される測定動作制御信号により、質量スペクトル
測定回路１１は質量スペクトルの測定を行なう。Therefore, from the time period when the amount of generated ions peaks,
As shown in the figure, the degree of vacuum at which the measurement begins and the degree at which it ends are set in advance. Then, the measurement start/end vacuum level setting circuit 9 outputs a signal indicating the measurement start vacuum level and the measurement end vacuum level, and the signal indicating the actual vacuum level output from the vacuum level measurement circuit 8 and the comparison circuit 10 are output. The mass spectrum measurement circuit 11 performs mass spectrum measurement using a measurement operation control signal that is output when the actual degree of vacuum is within the range of the measurement start vacuum degree and the measurement end vacuum degree.
なお、この実施例ではレーザイオン化質量分析装置につ
いて説明したが、本発明はＦＡＢやＳＩＭＳのような液
体マトリックスを用いる他のイオン源を有する質量分析
装置にも適用できる。Although the laser ionization mass spectrometer has been described in this embodiment, the present invention can also be applied to mass spectrometers having other ion sources that use liquid matrices, such as FAB and SIMS.
また、上述の実施例では真空計をイオン源部の試料の近
傍に配置したが、イオン源の状態に真空度があまり左右
されないような位置に他の真空計を配置し、その検出値
を基準にして測定の開始時刻と終了時刻を決定するよう
にしてもよい。In addition, in the above embodiment, the vacuum gauge was placed near the sample in the ion source section, but other vacuum gauges were placed in a position where the degree of vacuum was not affected much by the state of the ion source, and the detected value was used as the reference. Alternatively, the start time and end time of the measurement may be determined.
〈発明の効果〉
以上説明したように本発明においては、測定時間を長く
して親イオンの検出を行うのではなく、親イオンの生成
量が増大する時間帯を真空チャンバの真空度から検出し
、この検出情報に基づいて最良のタイミングで測定を開
始できるようにしたので、親イオンの検出が確実に行な
われ、測定の信頼度が増す。また、不要なスペクトルを
積算することがないため、ＳＮ比の良い測定ができる。<Effects of the Invention> As explained above, in the present invention, instead of detecting parent ions by increasing the measurement time, the time period in which the amount of parent ions produced increases is detected based on the vacuum degree of the vacuum chamber. Since the measurement can be started at the best timing based on this detection information, parent ions are reliably detected and the reliability of the measurement is increased. Furthermore, since unnecessary spectra are not integrated, measurements with a good signal-to-noise ratio can be performed.
さらに、測定時間を短縮できるとともに、試料の消費量
が少なくて済む。Furthermore, measurement time can be shortened and the amount of sample consumed can be reduced.
第１図は本発明の実施例の構成を示す図、第２図、第３
図並びに第４図は本発明の実施例の真空度の時間変化を
示す図、第５図は質量分析針における親イオン強度の時
間変化を示す図である。
１−・真空チャンバ ２・・・イオン源部３−分析
部 ４−・検出部
５・−試料 ６・・−試料ホルダ７−・・
−真空計 ８・・・真空度測定回路９−測定
開始／終了真空度設定回路
１〇−比較回路
１１・−・質量スペクトル測定回路
特許出願人 株式会社島津製作所代 理 人
弁理士 西１）新
築１図
第２図
第３図
第４図
第５図FIG. 1 is a diagram showing the configuration of an embodiment of the present invention, FIG. 2, and FIG.
4 and 4 are diagrams showing changes over time in the degree of vacuum in the embodiment of the present invention, and FIG. 5 is a diagram showing changes over time in parent ion intensity in a mass spectrometer needle. 1--Vacuum chamber 2--Ion source section 3--Analysis section 4--Detection section 5--Sample 6--Sample holder 7--
- Vacuum gauge 8... Vacuum level measuring circuit 9 - Measurement start/end vacuum level setting circuit 10 - Comparison circuit 11... Mass spectrum measuring circuit Patent applicant Shimadzu Corporation Agent
Patent Attorney Nishi 1) New construction Figure 1 Figure 2 Figure 3 Figure 4 Figure 5
Claims (1)
たがってより分ける質量分析装置において、上記イオン
源部を含む真空チャンバの真空度を検出する真空度検出
手段と、上記真空度に応じて測定の開始と終了を制御す
る制御手段とを備えたことを特徴とする質量分析装置。A mass spectrometer that sorts parent ions generated in an ion source according to the mass/charge ratio, comprising: a degree of vacuum detection means for detecting the degree of vacuum of a vacuum chamber including the ion source; A mass spectrometer characterized by comprising a control means for controlling the start and end of measurement.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61076276A JPH0756790B2 (en) | 1986-03-31 | 1986-03-31 | Mass spectrometer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61076276A JPH0756790B2 (en) | 1986-03-31 | 1986-03-31 | Mass spectrometer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62232848A true JPS62232848A (en) | 1987-10-13 |
| JPH0756790B2 JPH0756790B2 (en) | 1995-06-14 |
Family
ID=13600740
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61076276A Expired - Lifetime JPH0756790B2 (en) | 1986-03-31 | 1986-03-31 | Mass spectrometer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0756790B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102842481A (en) * | 2012-08-30 | 2012-12-26 | 昆山禾信质谱技术有限公司 | Rapid high-accuracy continuous control method for buffer gas in mass analyzer of mass spectrometer |
| CN103890902A (en) * | 2011-10-20 | 2014-06-25 | 株式会社岛津制作所 | Mass spectrometer |
| CN106571286A (en) * | 2016-11-07 | 2017-04-19 | 中国科学院广州地球化学研究所 | Full automatic control device for improving vacuum degree of sample chamber of secondary ion mass spectrometer |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5746459A (en) * | 1980-09-02 | 1982-03-16 | Toshiba Corp | Mass spectrometer |
-
1986
- 1986-03-31 JP JP61076276A patent/JPH0756790B2/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5746459A (en) * | 1980-09-02 | 1982-03-16 | Toshiba Corp | Mass spectrometer |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103890902A (en) * | 2011-10-20 | 2014-06-25 | 株式会社岛津制作所 | Mass spectrometer |
| CN102842481A (en) * | 2012-08-30 | 2012-12-26 | 昆山禾信质谱技术有限公司 | Rapid high-accuracy continuous control method for buffer gas in mass analyzer of mass spectrometer |
| CN106571286A (en) * | 2016-11-07 | 2017-04-19 | 中国科学院广州地球化学研究所 | Full automatic control device for improving vacuum degree of sample chamber of secondary ion mass spectrometer |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0756790B2 (en) | 1995-06-14 |
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