JPH0154659B2 - - Google Patents
Info
- Publication number
- JPH0154659B2 JPH0154659B2 JP17895184A JP17895184A JPH0154659B2 JP H0154659 B2 JPH0154659 B2 JP H0154659B2 JP 17895184 A JP17895184 A JP 17895184A JP 17895184 A JP17895184 A JP 17895184A JP H0154659 B2 JPH0154659 B2 JP H0154659B2
- Authority
- JP
- Japan
- Prior art keywords
- gas
- ultraviolet
- hydride
- ultraviolet irradiation
- hydride gas
- 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.)
- Expired
Links
- 239000007789 gas Substances 0.000 claims description 38
- 150000004678 hydrides Chemical class 0.000 claims description 24
- 239000011261 inert gas Substances 0.000 claims description 9
- 239000004065 semiconductor Substances 0.000 claims description 9
- 238000001514 detection method Methods 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 239000012141 concentrate Substances 0.000 claims description 2
- 238000000034 method Methods 0.000 description 10
- 238000005259 measurement Methods 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910000474 mercury oxide Inorganic materials 0.000 description 2
- UKWHYYKOEPRTIC-UHFFFAOYSA-N mercury(ii) oxide Chemical compound [Hg]=O UKWHYYKOEPRTIC-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910000074 antimony hydride Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- RBFQJDQYXXHULB-UHFFFAOYSA-N arsane Chemical compound [AsH3] RBFQJDQYXXHULB-UHFFFAOYSA-N 0.000 description 1
- 238000001479 atomic absorption spectroscopy Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 238000005048 flame photometry Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- SPVXKVOXSXTJOY-UHFFFAOYSA-N selane Chemical compound [SeH2] SPVXKVOXSXTJOY-UHFFFAOYSA-N 0.000 description 1
- 229910000058 selane Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- KXCAEQNNTZANTK-UHFFFAOYSA-N stannane Chemical compound [SnH4] KXCAEQNNTZANTK-UHFFFAOYSA-N 0.000 description 1
- OUULRIDHGPHMNQ-UHFFFAOYSA-N stibane Chemical compound [SbH3] OUULRIDHGPHMNQ-UHFFFAOYSA-N 0.000 description 1
- 229910000083 tin tetrahydride Inorganic materials 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/62—Detectors specially adapted therefor
- G01N30/74—Optical detectors
Landscapes
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
Description
（技術分野）
本発明は、半導体製造用水素化物ガスの検知装
置に関するものである。
（従来技術及びその問題点）
水素化物ガスを検知するための従来の技術とし
ては、(1)水素−窒素炎を用いる炎光光度法
（FPD法）、(2)紫外線をガスに照射してイオン化
し、その時発生するイオン電流からガス濃度を測
定する光イオン化法（PID法）、(3)オゾンとの反
応を利用する化学発光法、(4)赤外線の吸収を調べ
る赤外線分光光度法、(5)ガスと酸化水銀を反応さ
せ、生じた水銀蒸気から間接的に濃度を求める化
学反応・原子吸光光度法、(6)ガスに触れると発色
する試薬を浸み込ませた試験紙の透過光量の減少
から濃度を求める試験紙光電光度法、(7)ガスの電
極表面での酸化反応を利用する電気化学法（隔膜
カルバニ電池式と定電位電解式）がある。これら
の検知方法では、感度が十分でない（４，６，７
の方法）、ガス選択性が悪い（２，５，６，７の
方法）、炎という一般的に不安定なものを利用し
ているのでゼロドリフトが避けられず、しかも爆
発性のある水素炎を使用している（１の方法）、
真空ポンプやオゾン発生器を必要とする（３の方
法）、毒性の強い酸化水銀を使用している（５の
方法）等の問題がある。
（発明の課題）
本発明は、高感度・高選択性を有し、しかも危
険性のある炎や試薬を使用せず、付属部品も紫外
線ランプ以外必要としない、半導体用水素化物ガ
ス検知装置を提供することをその課題とする。
（課題を解決するための手段）
本発明によれば、半導体用水素化物ガスサンプ
ルを濃縮分離するカラムと、該濃縮分離された水
素化物ガスに紫外線を照射する不活性ガスのパー
ジされた紫外線照射室と、該紫外線照射室から得
られた該水素化物ガスの紫外線照射生成物に紫外
線を照射するとともに、該紫外線照射生成物から
発する光を検知し、これを電気信号に変換する検
出器を備えたことを特徴とする半導体製造用水素
化物ガスの検知装置が提供される。
（実施例）
次に本発明の実施例を図面に基づいて説明す
る。
図面において、１は紫外線照射室で、その室内
には、紫外線ランプ２と、その外側に紫外線ラン
プ２を包囲するように設置されたサンプルガスの
流通する石英製らせん管３を有している。紫外線
ランプとしては、水銀ランプやキセノンランプ等
が用いられる。紫外線ランプ２は定電圧電源４に
より点灯され、一定強度の紫外線が発生するよう
になつている。また、紫外線照射室１には、紫外
線が酸素により吸収されるのを防ぐために、不活
性ガスでパージする必要があり、不活性ガスは導
管５から導入され、導管６から排出される。この
不活性ガスは、紫外線ランプを空冷する作用も有
する。さらに、紫外線照射室は、紫外線を有効に
利用し得るように光の反射率のよいアルミニウム
金属等で構成するのが好ましい。
水素化物ガスの濃縮カラム７は、通常のガスク
ロマトグラフ（GC）のカラム（GCカラム）を用
いることができ、その充填剤としては、シリカや
アルカミナ等の慣用の吸着剤が用いられる。８は
カラム７の温度を調節するための温度コントロー
ラである。
本発明で用いる検出器は、石英製測定セル１
０、光を電気信号に変換する光電子増倍管１３及
び紫外線ランプ１４からなる。１５は定電圧電
源、１６はレンズであり、１１及び１２は光学フ
イルターであり、特定波長範囲（150〜400nm）
の光を透過させる。１８は光電子増倍管に接続す
る高圧電源であり、１９は光電子増倍管に接続す
るアンプ及び２０はアンプ１９に接続する指示計
である。
本発明の装置を用いて半導体製造用水素化物ガ
スを検知測定するには、先ず、水素化物ガスを含
むサンプルガスをライン２１からGCカラム７に
導入し、また、不活性ガス（窒素、アルゴン又は
ヘリウム）の入つたボンベ２２からの不活性ガス
をライン２３を介してキヤリヤーガスとして流通
させる。不活性ガスの一部は、ライン２４を介し
て紫外線照射室１に導入する。
なお、本明細書でいう半導体製造用水素化物ガ
スとは、半導体製造に用いられている如き各種の
水素化物ガスを意味し、このような水素化物ガス
には、アルシン（AsH3）、ホスフイン（PH3）、
スチビン（SbH3）、セレン化水素（SeH2）、水素
化スズ（SnH4）等が包含される。
GCカラム７において水素化物ガスが吸着され
ると、次に、バルブ２５を閉じ、ガスコントロー
ラ２６のバルブを開くとともに、温度コントロー
ラー８によりGCカラム７の温度を上昇させて吸
着した水素化物ガスを脱着させ、これを紫外線照
射室１に不活性ガスとともに一定速度で導入す
る。
紫外線照射室１に導入された水素化物ガスは、
ここで紫外線ランプ２によつて紫外線照射を受
け、検出部で光検知可能な生成物に変換された
後、測定セル１０に導入される。
測定セル１０に導入された水素化物ガスの紫外
線照射生成物に対しては、紫外線ランプ１４から
の紫外線を照射するとともに、その水素化物ガス
の紫外線照射生成物からの光を光電子増倍管１３
により電気信号に変換する。この電気信号は、サ
ンプルガス中の水素化物ガス濃度と相関するもの
で、アンプ１９により増幅された後指示計２０に
送られてその濃度が表示される。この場合の濃度
は、標準ガスを用いた場合に得られるシグナルと
の強度比で表示される。測定セル１０を通過した
ガスは吸着器１７で吸着処理され、無害化された
後排気される。
次に、図面に示した装置を用いて、水素化物ガ
スを各種濃度で含むサンプルガスを測定した結果
を示す。
(Technical Field) The present invention relates to a detection device for hydride gas for semiconductor manufacturing. (Prior art and its problems) Conventional technologies for detecting hydride gas include (1) flame photometry (FPD method) using a hydrogen-nitrogen flame, and (2) irradiating the gas with ultraviolet rays. Photoionization method (PID method), which measures gas concentration from the ionic current generated at the time of ionization, (3) Chemiluminescence method, which uses reaction with ozone, (4) Infrared spectrophotometry, which examines absorption of infrared rays. 5) Chemical reaction/atomic absorption spectrometry to indirectly determine the concentration from the mercury vapor produced by reacting gas with mercury oxide, (6) Amount of light transmitted through a test paper impregnated with a reagent that develops color when it comes into contact with the gas. (7) Electrochemical methods (diaphragm carbani cell method and constant potential electrolysis method) that utilize the oxidation reaction of gas on the electrode surface. These detection methods do not have sufficient sensitivity (4, 6, 7
method), gas selectivity is poor (methods 2, 5, 6, and 7), zero drift is inevitable because flame is used, which is generally unstable, and hydrogen flame is explosive. (method 1),
There are problems such as requiring a vacuum pump or an ozone generator (method 3) and using highly toxic mercury oxide (method 5). (Problem of the Invention) The present invention provides a hydride gas detection device for semiconductors that has high sensitivity and high selectivity, does not use dangerous flames or reagents, and does not require any accessory parts other than an ultraviolet lamp. Its task is to provide. (Means for Solving the Problems) According to the present invention, there is provided a column that concentrates and separates a hydride gas sample for semiconductors, and a purged ultraviolet ray irradiation of an inert gas that irradiates the concentrated and separated hydride gas with ultraviolet rays. and a detector that irradiates ultraviolet rays to an ultraviolet irradiation product of the hydride gas obtained from the ultraviolet irradiation chamber, detects light emitted from the ultraviolet irradiation product, and converts it into an electrical signal. Provided is a detection device for hydride gas for semiconductor manufacturing, which is characterized by the following. (Example) Next, an example of the present invention will be described based on the drawings. In the drawing, reference numeral 1 denotes an ultraviolet irradiation chamber, which includes an ultraviolet lamp 2 and a quartz spiral tube 3, which is installed outside of the ultraviolet lamp 2 so as to surround the ultraviolet lamp 2, through which a sample gas flows. As the ultraviolet lamp, a mercury lamp, a xenon lamp, etc. are used. The ultraviolet lamp 2 is turned on by a constant voltage power source 4, and is designed to generate ultraviolet light of a constant intensity. Further, the ultraviolet irradiation chamber 1 needs to be purged with an inert gas to prevent ultraviolet rays from being absorbed by oxygen, and the inert gas is introduced through a conduit 5 and exhausted through a conduit 6. This inert gas also has the effect of air cooling the ultraviolet lamp. Further, the ultraviolet ray irradiation chamber is preferably made of aluminum metal or the like with good light reflectance so that ultraviolet rays can be effectively utilized. As the hydride gas concentration column 7, a normal gas chromatograph (GC) column (GC column) can be used, and its packing material is a commonly used adsorbent such as silica or alkamina. 8 is a temperature controller for adjusting the temperature of the column 7. The detector used in the present invention includes a quartz measurement cell 1
0, a photomultiplier tube 13 that converts light into an electrical signal, and an ultraviolet lamp 14. 15 is a constant voltage power supply, 16 is a lens, 11 and 12 are optical filters, and have a specific wavelength range (150 to 400 nm).
Transmits light. 18 is a high voltage power supply connected to the photomultiplier tube, 19 is an amplifier connected to the photomultiplier tube, and 20 is an indicator connected to the amplifier 19. To detect and measure hydride gas for semiconductor manufacturing using the apparatus of the present invention, first, a sample gas containing hydride gas is introduced into the GC column 7 from the line 21, and an inert gas (nitrogen, argon or An inert gas from a cylinder 22 containing helium is passed through line 23 as a carrier gas. A portion of the inert gas is introduced into the ultraviolet irradiation chamber 1 via the line 24. Note that the hydride gas for semiconductor manufacturing as used herein means various hydride gases used in semiconductor manufacturing, and such hydride gases include arsine (AsH 3 ), phosphine ( PH3 ),
Stibine (SbH 3 ), hydrogen selenide (SeH 2 ), tin hydride (SnH 4 ), and the like are included. When the hydride gas is adsorbed in the GC column 7, the valve 25 is then closed, the gas controller 26 valve is opened, and the temperature controller 8 raises the temperature of the GC column 7 to desorb the adsorbed hydride gas. This is introduced into the ultraviolet irradiation chamber 1 together with an inert gas at a constant speed. The hydride gas introduced into the ultraviolet irradiation chamber 1 is
Here, it is irradiated with ultraviolet light by the ultraviolet lamp 2, converted into a photodetectable product in the detection section, and then introduced into the measurement cell 10. The ultraviolet irradiation product of the hydride gas introduced into the measurement cell 10 is irradiated with ultraviolet light from the ultraviolet lamp 14, and the light from the ultraviolet irradiation product of the hydride gas is transmitted to the photomultiplier tube 13.
converts it into an electrical signal. This electrical signal correlates with the hydride gas concentration in the sample gas, and is amplified by an amplifier 19 and then sent to an indicator 20 to display the concentration. The concentration in this case is expressed as the intensity ratio of the signal obtained when using a standard gas. The gas that has passed through the measurement cell 10 is adsorbed in an adsorber 17, rendered harmless, and then exhausted. Next, the results of measuring sample gases containing hydride gas at various concentrations using the apparatus shown in the drawings will be shown.
【表】
（発明の効果）
本発明の装置は、光学的装置であるため、危険
な炎や試薬、オゾン発生器等を必要とせず、クリ
ーンで安定でかつ取扱いの簡単なものである。[Table] (Effects of the Invention) Since the device of the present invention is an optical device, it does not require dangerous flames, reagents, ozone generators, etc., and is clean, stable, and easy to handle.
第１図は本発明の装置系統図を示す。
１……紫外線照射室、２，１４……紫外線ラン
プ、３……石英製ラセン管、４，１５……定電圧
電源、７……カラム、８……温度コントローラ、
１０……測定セル、１３……光電子増倍管、１９
……アンプ、２０……指示計。
FIG. 1 shows an apparatus system diagram of the present invention. 1... Ultraviolet irradiation chamber, 2, 14... Ultraviolet lamp, 3... Quartz spiral tube, 4, 15... Constant voltage power supply, 7... Column, 8... Temperature controller,
10...Measurement cell, 13...Photomultiplier tube, 19
...Amplifier, 20...Indicator.
Claims (1)
るカラムと、該濃縮分離された水素化物ガスに紫
外線を照射する不活性ガスのパージされた紫外線
照射室と、該紫外線照射室から得られた該水素化
物ガスの紫外線照射生成物に紫外線を照射すると
ともに、該紫外線照射生成物から発する光を検知
し、これを電気信号に変換する検出器を備えたこ
とを特徴とする半導体製造用水素化物ガスの検知
装置。1. A column that concentrates and separates a hydride gas sample for semiconductors, an ultraviolet irradiation chamber purged with inert gas that irradiates the concentrated and separated hydride gas with ultraviolet rays, and the hydride obtained from the ultraviolet irradiation chamber. Detection of hydride gas for semiconductor manufacturing, characterized by comprising a detector that irradiates the ultraviolet ray irradiation product of the gas with ultraviolet rays, detects light emitted from the ultraviolet irradiation product, and converts it into an electrical signal. Device.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17895184A JPS6156942A (en) | 1984-08-28 | 1984-08-28 | Gas detector for semiconductor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17895184A JPS6156942A (en) | 1984-08-28 | 1984-08-28 | Gas detector for semiconductor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6156942A JPS6156942A (en) | 1986-03-22 |
| JPH0154659B2 true JPH0154659B2 (en) | 1989-11-20 |
Family
ID=16057505
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP17895184A Granted JPS6156942A (en) | 1984-08-28 | 1984-08-28 | Gas detector for semiconductor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6156942A (en) |
-
1984
- 1984-08-28 JP JP17895184A patent/JPS6156942A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6156942A (en) | 1986-03-22 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |