JPS61160043A - Detection and quantitative analysis of sulfur monitor - Google Patents
Detection and quantitative analysis of sulfur monitorInfo
- Publication number
- JPS61160043A JPS61160043A JP94385A JP94385A JPS61160043A JP S61160043 A JPS61160043 A JP S61160043A JP 94385 A JP94385 A JP 94385A JP 94385 A JP94385 A JP 94385A JP S61160043 A JPS61160043 A JP S61160043A
- Authority
- JP
- Japan
- Prior art keywords
- gaseous
- spectral line
- detection
- window
- light
- 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
- 238000001514 detection method Methods 0.000 title abstract description 10
- 238000004445 quantitative analysis Methods 0.000 title abstract 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title 1
- 229910052717 sulfur Inorganic materials 0.000 title 1
- 239000011593 sulfur Substances 0.000 title 1
- 230000003595 spectral effect Effects 0.000 claims abstract description 12
- 238000010521 absorption reaction Methods 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims description 10
- 238000001228 spectrum Methods 0.000 abstract description 7
- 230000001066 destructive effect Effects 0.000 abstract description 3
- 238000010438 heat treatment Methods 0.000 abstract description 3
- 230000035945 sensitivity Effects 0.000 abstract description 2
- 238000011002 quantification Methods 0.000 description 9
- 238000002835 absorbance Methods 0.000 description 7
- 238000000862 absorption spectrum Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 3
- 238000011896 sensitive detection Methods 0.000 description 3
- 238000000137 annealing Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 241000143060 Americamysis bahia Species 0.000 description 1
- 240000006829 Ficus sundaica Species 0.000 description 1
- 238000001479 atomic absorption spectroscopy Methods 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/33—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using ultraviolet light
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/314—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry with comparison of measurements at specific and non-specific wavelengths
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/71—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light thermally excited
- G01N21/74—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light thermally excited using flameless atomising, e.g. graphite furnaces
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は新規なｅの定量方法及び該方法を利用したその
場での高感度な検知定量が可能なＳモニターに関する。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a novel method for quantifying e and an S monitor capable of highly sensitive detection and quantification on the spot using the method.
本発明は日を用いる半導体製造品及び製造装置、廃棄物
処理装置等、例えばＺｎＳ、 ０（１８。The present invention relates to semiconductor products, manufacturing equipment, waste treatment equipment, etc. that use ZnS, for example, ZnS, 0(18.
Ｚｎ５ｘ８ｅｌ−ｘ等の化合物半導体のエビ成長装置（
ａＶＶ炉、ＬＰＦｉ炉等）、高圧ＨＢ炉、アニーリング
炉、Ｓ圧アニーリング炉、ＭＢＩ装置、ＭＯＣｖＤ装置
等に８検出定量高感度モニターとして利用したり、ある
いは、日を含有する合金やセラミックス、ガラス等の溶
解炉等に利用することができる。Shrimp growth equipment for compound semiconductors such as Zn5x8el-x (
(aVV furnace, LPFi furnace, etc.), high-pressure HB furnace, annealing furnace, S-pressure annealing furnace, MBI device, MOCvD device, etc. as an 8-detection quantitative high-sensitivity monitor. It can be used in melting furnaces, etc.
（従来の技術）
従来、Ｓを検出する場合に、非破壊で、系を乱さず、そ
の場でガス状Ｓを検知定量する方法は殆んど知られてお
らず、Ｓの検出は破壊検知が主である。ガス状物質の非
破壊検出・定量法としては、ガスクロマトグラフィーが
考えられるが、■測定系内に試料を導くまでに、導入管
壁に付着し、正確な定量ができない、■系内からのサン
プリングを要するため系を乱してしまう、という本質的
な問題点があるため不適であり、実用されていない。ま
た、原子吸光分析は、原子状態の試料について厳密に測
定できるが、試料を２０００℃以上の高温状態とする必
要があり、原子化温度以下の検知定量は原理的に不可能
であるに加え、用いうるホロカッ−トランプがない。(Prior art) Conventionally, when detecting S, there is almost no known method for detecting and quantifying gaseous S on the spot in a non-destructive manner without disturbing the system. is the main thing. Gas chromatography can be considered as a non-destructive detection/quantification method for gaseous substances; It is unsuitable and has not been put to practical use because it has the essential problem of disturbing the system because it requires sampling. In addition, atomic absorption spectrometry can accurately measure samples in the atomic state, but it requires the sample to be heated to a high temperature of 2000°C or higher, and detection and quantification at temperatures below the atomization temperature is theoretically impossible. There are no hollow cut lamps available.
（発明が解決しようとする問題点）
本発明は上記した現状に鑑みてなされたもので、非破壊
で、系をみださず、その場でガス状Ｓの高感度検知・定
量が可能な方法及び該方法を利用した高感度モニターの
提供を目的とするものである。(Problems to be Solved by the Invention) The present invention was made in view of the above-mentioned current situation, and enables highly sensitive detection and quantification of gaseous S on the spot without destroying the system. The object of the present invention is to provide a method and a highly sensitive monitor using the method.
（問題点を解決しようとする手段）
すなわち、本発明はガス状日に、波長２６３ｎｍ 及び
／又は２６ Ｓ、 ５ ｎｍ のスペクトル線を、入射
し、上記ガス状ｓｌｃよる上記入射スペクトル線の吸収
を測定し、各光強度のピーク高さからＳの検知・定量を
行う方法および炉またはヒータ付容器の光の進行方向に
窓部を設け、一方の窓部に２６３ ｎｍ 及び／又は２
６５．５ ｎｍ のスペクトル線発光部、他方の窓には
ヒータ付容器内のガス状日を通過した前記スペクトル線
の光強度のピーク高さから８を検知定量する受光、測光
部を接続して々る、Ｓモニターである。(Means for solving the problem) That is, the present invention injects a spectral line with a wavelength of 263 nm and/or 26 S, 5 nm on a gaseous day, and absorbs the incident spectral line by the gaseous SLC. A method of detecting and quantifying S from the peak height of each light intensity, and a method of providing a window in the direction of light propagation in a furnace or a container with a heater, and one window having a wavelength of 263 nm and/or 2
A 65.5 nm spectral line emitting unit is connected to the other window, and a light receiving and photometric unit is connected to the other window to detect and quantify 8 from the peak height of the light intensity of the spectral line that has passed through the gaseous state in the container with a heater. It is an S monitor.
以下に本発明につき詳細に説明する。The present invention will be explained in detail below.
本発明者らは、ガス状日（ガス状では”ｔｚ ”４、Ｓ
、、Ｓ、等になると考えられているが、特定されていな
い。）の吸光スペクトルを詳細に研究の結果、第１図に
示すように、波長２６５ ｎｍ 及び２６５．５ ｎｍ
に吸光のピークを有することを発見した。そしてこ
のようなピークは温度３００℃程度のＳの分子の状況の
スペクトルで得られるという知見をも得て、ガス状Ｓの
吸収による２ ６ Ｓ ｎｍ 及び２６５．５ ｎｍ
の吸光ピークを利用することにより、ガス状Ｓを高感度
でかつその場でさえ検出・定量を可能としたものである
。The inventors have determined that the gaseous day (gaseous "tz" 4, S
, , S, etc., but it has not been specified. ) As a result of detailed research on the absorption spectra of
It was discovered that there is an absorption peak at . We also obtained the knowledge that such peaks are obtained in the spectrum of S molecules at a temperature of about 300°C.
By utilizing the absorption peak of , gaseous S can be detected and quantified with high sensitivity even on the spot.
本発明は第２図に示すように１炉、ヒータ付セルあるい
は筒部１に窓２を取シ付け、発光部３において２６３
ｎｍ または２６５．５ ｎｍ のスペクトル線を
発光させ、この光を窓２から入射し、受光部４において
光強度のピーク高さを測定することにより、炉またはセ
ル中の８を検知定量するものである。この日の検知、定
量は、２６３ｎｍ または２６５．５ ｎｍ のピー
ク吸収が８濃度に比例することから求める。ピーク吸収
とＳ濃度の関係は
Ｄｃｌ：Ｃ・・・（２）
上記（１） 、 ｆ２）式で表される。ここでＴはピー
クでの吸光度（％）、ＣはＳの濃度である。As shown in FIG.
It detects and quantifies 8 in the furnace or cell by emitting a spectral line of 265.5 nm or 265.5 nm, entering this light through the window 2, and measuring the peak height of the light intensity at the light receiving part 4. be. Detection and quantification on this day is determined from the fact that the peak absorption at 263 nm or 265.5 nm is proportional to the 8 concentration. The relationship between peak absorption and S concentration is expressed by the above equation (1), f2): Dcl:C...(2). Here, T is the absorbance at the peak (%), and C is the concentration of S.
２６３ ｎｍ 及び２６５．５ ｎｍ のスペクトル発
光源としては、ホロカソードラングを用い、２６５ ｎ
ｍ 及び／又は２６５．５ ｎｍ を中心したフィル
ターを各々設けたものが使用できる。また該フィルター
は受光部に設けることもできる。Holocathode rungs were used as the 263 nm and 265.5 nm spectral emission sources, and the 265 nm
It is possible to use filters each provided with a filter centered at m and/or 265.5 nm. Further, the filter can also be provided in the light receiving section.
さらに検出結果をコンピュータ処理し、その結果を表示
するようにできる。このようにすれば、＃丘ぼ実時間で
８を定量検出できるので、その場での日の検知定量と日
の投入量Ｓ圧コントロール等を制御しうる高感度Ｓモニ
ターを実現できる。Furthermore, the detection results can be processed by computer and the results can be displayed. In this way, it is possible to quantitatively detect #8 in real time, so it is possible to realize a highly sensitive S monitor that can detect and quantify on the spot and control the daily input amount S pressure.
（実施例）
第３図（ａ）は本発明の実施例で用いた装置の概略図で
あって、１けセル、２は窓、３は発光部、４は受光部、
５は加熱手段をあられす。なお第３図（ロ）はこの装置
の温度分布を示すグラフである。(Example) FIG. 3(a) is a schematic diagram of an apparatus used in an example of the present invention, in which 1 cell, 2 a window, 3 a light emitting part, 4 a light receiving part,
5 is the heating means. Note that FIG. 3 (b) is a graph showing the temperature distribution of this device.
セル１内にＳを置き加熱手段５によりセル１内の温度を
２９８℃に一定にして保持したときのスペクトルを第４
図に示す。２６５ ｎｍ 及び２６５．５ ｎｍ を
最大のピークとした吸収スペクトルが明瞭に測定された
。The spectrum when S is placed in the cell 1 and the temperature inside the cell 1 is kept constant at 298°C by the heating means 5 is shown in the fourth figure.
As shown in the figure. Absorption spectra with maximum peaks at 265 nm and 265.5 nm were clearly measured.
一方、日の投入量と、吸光度の間には、一般的に第５図
に示す関係があることを詳細な実験に確認した。ここで
ガス状Ｓが存在するとき検知される光強度を工、ガス状
Ｓがないときの光強度を工０ とすると、吸光度Ｔ（％
）は次式（３）％式％
したがって、前記の（１）および（２）式により吸光度
から８を定量できる。なおＡ点は、温度ｔにおける飽和
点をあられしており、
を
規定される。On the other hand, it was confirmed through detailed experiments that there is generally a relationship shown in FIG. 5 between the daily input amount and the absorbance. Here, if the light intensity detected when gaseous S is present is x, and the light intensity when there is no gaseous S is x0, then the absorbance T (%
) is the following formula (3) % Formula % Therefore, 8 can be determined from the absorbance using the above formulas (1) and (2). Note that point A is the saturation point at temperature t, and is defined as follows.
第５図の関係は２６５ ｎｍ と２６５．５ ｎｍ
の夫々の吸収スペクトルについて成立するので、いずれ
のピークの測定によってもＳ量を求めることができる。The relationship in Figure 5 is 265 nm and 265.5 nm.
Since this holds true for each absorption spectrum, the amount of S can be determined by measuring any peak.
両者のスペクトルを用いれば精度が向上する。検出は０
．１ ｐｐｍオーダーまで可能である。Accuracy is improved by using both spectra. Detection is 0
．． Possible up to 1 ppm order.
（発明の効果） 本発明の効果は次のとおりである。(Effect of the invention) The effects of the present invention are as follows.
１）ガス状日の吸収による波長２６５ ｎｍ 及び２６
５、５ ｎｍ のスペクトルを利用することにより、
ガス状Ｓの高感度の検知・定量がその場で可能となった
。1) Wavelengths 265 nm and 26 nm due to gaseous absorption
By using the 5.5 nm spectrum,
Highly sensitive detection and quantification of gaseous S is now possible on the spot.
２）波長２６５ ｎｍ 及び／又は２６ Ｓ ５ ｎｍ
のスペクトルのピーク高から定量を行なうため、Ｓの
定量精度が向上する。2) Wavelength 265 nm and/or 26 S 5 nm
Since the quantification is performed from the peak height of the spectrum of S, the accuracy of quantification of S is improved.
５）本発明の高感度ＳモニターはＳ量のその場検知・定
量が可能であり、さらにコンピューター等演算装置と組
合すことくより、各スペクトルの吸光度から実時間でＳ
量を検知定量し、該演算装置の出力信号によりＳ投入量
、Ｓ圧等をその場で制御することができる。5) The high-sensitivity S monitor of the present invention is capable of on-the-spot detection and quantification of the amount of S, and can also be used to measure S in real time from the absorbance of each spectrum by combining it with a computing device such as a computer.
The amount can be detected and quantified, and the S input amount, S pressure, etc. can be controlled on the spot based on the output signal of the arithmetic device.
第１図はガス状Ｓの吸光スペクトルである。
第２図は本発明方法及びモニターの概略を示す模式図で
ある。第６図（ａ）は本発明の実施例で用いた装置の概
略図であυ、第３図（ロ）は第３図（ａ）装置における
温度分布を示すグラフでちる。第４図は本発明の実施例
で得られた波長と吸光度の関係を示すグラフ、第５図は
Ｓ量と吸光度の関係を示すグラフである。FIG. 1 shows the absorption spectrum of gaseous S. FIG. 2 is a schematic diagram showing the outline of the method and monitor of the present invention. FIG. 6(a) is a schematic diagram of the apparatus used in the embodiment of the present invention, and FIG. 3(b) is a graph showing the temperature distribution in the apparatus of FIG. 3(a). FIG. 4 is a graph showing the relationship between wavelength and absorbance obtained in an example of the present invention, and FIG. 5 is a graph showing the relationship between S amount and absorbance.
Claims (5)
５ｎｍのスペクトル線を、入射し、上記ガス状Ｓによる
上記入射スペクトル線の吸収を測定し、各光強度のピー
ク高さからＳの検知・定量を行う方法。(1) Gaseous S has a wavelength of 263 nm and/or 265 nm.
A method in which a spectral line of 5 nm is incident, absorption of the incident spectral line by the gaseous S is measured, and S is detected and quantified from the peak height of each light intensity.
け、一方の窓部に２６３ｎｍ及び／又は２６５．５ｎｍ
のスペクトル線発光部、他方の窓にはヒータ付容器内の
ガス状Ｓを通過した前記スペクトル線の光強度のピーク
高さからＳを検知定量する受光、測光部を接続してなる
、Ｓモニター。(2) A window is provided in the direction of light propagation of the furnace or container with a heater, and one window has a wavelength of 263 nm and/or 265.5 nm.
A spectral line emitting unit is connected to the other window, and a light receiving and photometering unit is connected to the other window to detect and quantify S from the peak height of the light intensity of the spectral line that has passed through the gaseous S in the container with a heater. .
を検知・定量し、それによりＳ投入量コントロール・Ｓ
圧コントロールを実時間で制御する特許請求の範囲第（
２）項記載のＳモニター。(3) Based on the peak height of light intensity by computer
Detects and quantifies S, thereby controlling S input amount and S
Claim no.
S monitor described in section 2).
範囲第（２）項記載のＳモニター。(4) The S monitor according to claim (2), wherein the light emitting section is a hollow cathode lamp.
６５．５ｎｍを中心とするフィルタを有する特許請求の
範囲第（２）項記載のＳモニター。(5) The light emitting part or the light receiving part is 263 nm and/or 2
The S monitor according to claim (2), having a filter centered at 65.5 nm.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP94385A JPS61160043A (en) | 1985-01-09 | 1985-01-09 | Detection and quantitative analysis of sulfur monitor |
| US06/816,843 US4733084A (en) | 1985-01-09 | 1986-01-07 | Method of detection and quantitative determination of sulfur and sulfur monitor using the method |
| DE8686100248T DE3682592D1 (en) | 1985-01-09 | 1986-01-09 | METHOD FOR DETECTING AND QUANTATIVE DETERMINATION OF SULFUR AND SULFUR MONITOR USING THIS METHOD. |
| EP86100248A EP0187675B1 (en) | 1985-01-09 | 1986-01-09 | Method of detection and quantitative determination of sulfur and sulfur monitor using the method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP94385A JPS61160043A (en) | 1985-01-09 | 1985-01-09 | Detection and quantitative analysis of sulfur monitor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61160043A true JPS61160043A (en) | 1986-07-19 |
| JPH0226180B2 JPH0226180B2 (en) | 1990-06-07 |
Family
ID=11487753
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP94385A Granted JPS61160043A (en) | 1985-01-09 | 1985-01-09 | Detection and quantitative analysis of sulfur monitor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61160043A (en) |
-
1985
- 1985-01-09 JP JP94385A patent/JPS61160043A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0226180B2 (en) | 1990-06-07 |
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