WO1996004064A1 - Procede et appareil d'extraction d'hydrures gazeux - Google Patents

Procede et appareil d'extraction d'hydrures gazeux Download PDF

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Publication number
WO1996004064A1
WO1996004064A1 PCT/JP1995/001553 JP9501553W WO9604064A1 WO 1996004064 A1 WO1996004064 A1 WO 1996004064A1 JP 9501553 W JP9501553 W JP 9501553W WO 9604064 A1 WO9604064 A1 WO 9604064A1
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WO
WIPO (PCT)
Prior art keywords
gas
hydride
nickel
hydride gas
fluoride
Prior art date
Application number
PCT/JP1995/001553
Other languages
English (en)
Japanese (ja)
Inventor
Tadahiro Ohmi
Original Assignee
Tadahiro Ohmi
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Tadahiro Ohmi filed Critical Tadahiro Ohmi
Priority to KR1019970700655A priority Critical patent/KR970704501A/ko
Priority to JP50640096A priority patent/JP3801201B2/ja
Publication of WO1996004064A1 publication Critical patent/WO1996004064A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • B01D53/04—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/8671—Removing components of defined structure not provided for in B01D53/8603 - B01D53/8668
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/755—Nickel

Definitions

  • the present invention relates to a method and an apparatus for removing a hydride gas, and more particularly to a method and an apparatus for removing a dangerous and toxic hydride gas used in a semiconductor manufacturing process.
  • Hydride gases such as silane, phosphine, diborane, and arsine, used in the semiconductor manufacturing process are self-combustible and toxic. Therefore, it is necessary to completely remove unreacted gases to make them harmless before discharging them to the atmosphere.
  • gas removal methods include a dry removal method in which gas is removed through a packed column in which a porous carrier and an oxidizing agent are supported (Japanese Patent Laid-Open Publication No. 3-137917), and a liquid removal method.
  • a dry removal method in which gas is removed through a packed column in which a porous carrier and an oxidizing agent are supported
  • a liquid removal method There are known wet removal methods of absorbing by gas-liquid contact, neutralizing and decomposing and removing (JP-A-4-59017 and JP-A-4-310215). You.
  • silane gas is decomposed into a solid powder such as Sio 2 , so that there are many problems in management and maintenance, such as clogging of a packed tower.
  • various methods and devices have been proposed to solve this obstacle, but none of these methods is sufficient, and the devices have been complicated and large.
  • Another problem with the dry removal method is that it is not possible to remove all hydride gases because of its selectivity for removal.
  • the present invention provides a method and an apparatus for removing a hydride gas capable of completely removing a mixed gas containing a plurality of hydride gases and rendering the mixture harmless with a simple configuration without clogging due to powder generation.
  • the purpose is to do.
  • the hydride gas removing method of the present invention comprises removing a hydride gas by bringing a mixed gas containing at least two or more hydride gases into contact with nickel fluoride and nigel to decompose or adsorb the mixed gas. It is characterized by.
  • the hydride gas is a hydride gas of an element belonging to Group IV, IV, or V of the periodic table.
  • the hydride gas is preferably decomposed and removed by heating the nickel fluoride and the nickel, and more preferably the nickel fluoride and the Nigel are heated to different temperatures. ,.
  • the method for removing a hydride gas of the present invention is characterized in that a hydride gas of a Group III element or a Group V element of the periodic table is brought into contact with nickel to decompose and / or adsorb the hydride gas. Is removed. Further, it is preferable that the hydride gas be decomposed and removed by heating the nickel.
  • the hydride gas removing device of the present invention has at least one container having an inlet and an outlet for a mixed gas containing at least two or more hydride gases, and contacts the mixed gas in the container.
  • the nickel fluoride and the nigger are separately arranged so that the nickel fluoride and the nigger are separately arranged, and a heating means for heating the nickel fluoride and the nigger is provided.
  • the heating means is configured to heat the nickel fluoride and the nickel gel to different temperatures.
  • the hydride gas removing apparatus of the present invention includes: a container having an inlet and an outlet for a mixed gas containing a hydride gas of a Group III element or a Group V element of the periodic table; Nickel is provided so as to be in contact with the battery, and a heating means for heating the nickel is provided. Action
  • the present inventor has found that, among various materials, nickel fluoride, in particular, exhibits excellent decomposition characteristics with respect to silane. Silane can be decomposed at a low temperature. As a result, it is possible to remove silane by installing a pipe coated with nickel fluoride on the upstream side of the vacuum pump, preventing powder generation and adhesion inside the pump, and maintaining the entire equipment. It became very easy.
  • a gas such as phosphine, arsine, or diborane is introduced simultaneously with silane in order to control conductivity. All ⁇ ⁇ gaseous gases in these gas mixtures are dangerous and highly toxic, and must be completely removed and exhausted. However, if the treatment of the mixed gas of silane and phosphine is to be removed with the above nickel fluoride, it is necessary to heat to a high temperature of 300 ° C. or more in order to decompose phosphine by 100%.
  • i F 4 ends up occurring in a mixed gas type secondary Kkerufu' to use a product may see that there is a limit ivy o
  • the present inventors have conducted intensive studies to solve this problem, and as a result, the metal Ni has a high adsorption capacity for hydride gas of the group III element and the group V element of the periodic table and decomposes. It has a high accelerating effect.
  • phosphine can be decomposed 100% at a low temperature of about 50 ° C.
  • the present invention has been completed based on these findings, and uses nickel fluoride and Nigel to remove a mixed gas of two or more hydride gases at a low temperature. It becomes possible to do.
  • the amount of hydride gas treatment per nickel fluoride or nickel unit surface area is considered to be the amount by which elements such as Si, P, and B generated by decomposition cover the nickel fluoride and nickel surface. In fact, much more hydride gas can be processed than this amount. The reason for this is not clear at present, but it is presumed that even if Si, P, B, etc. cover the surface, Ni diffuses to the surface and the decomposition ability is maintained.
  • Ni has a high ability to adsorb hydride gases of Group III and V elements of the Periodic Table, and by using this characteristic, Ni can adsorb and remove trace hydride gases in various gases. Thus, the gas can be highly purified.
  • hydride gas removal pipes (1Z 4-inch pipes with a length of lm) having various inner surfaces were heated to a predetermined temperature, silane gas was flown, and the decomposition characteristics were examined.
  • silane gas was flown, and the decomposition characteristics were examined.
  • a specific hydride gas is introduced into the hydride gas removal pipe 1 and processed by adjusting a mass flow controller (MFC) and a valve for various hydride gases. Then, it is sent to the cell 12 of a Fourier transform infrared spectrometer (FTIR), where the silane concentration in the gas is measured. The gas discharged from the cell 12 is sent to the gas chromatography 13 where the H 2 gas concentration is analyzed.
  • FTIR Fourier transform infrared spectrometer
  • FTIR Fourier transform infrared spectrometer
  • FTIR Fourier transform infrared spectrometer
  • the gas discharged from the cell 12 is sent to the gas chromatography 13 where the H 2 gas concentration is analyzed.
  • a heater for heating is arranged around the hydride gas removing pipe 11, whereby the gas removing pipe 11 can be heated to a predetermined temperature.
  • Fig. 1 (b) is an enlarged view of cell 2, where Ar gas is used to protect the window material (KBr).
  • Fig. 2 (a) When 100 scpm of silane gas (Ar gas dilution) is flowed through the hydride gas removal pipe 11 at 5 sccm, the change in silane concentration in the discharged gas with respect to the heating temperature is shown in Fig. 2 (a).
  • N i F 2 tubes pure N i pipe, Hasuteroi electropolished tube, SUS 3 1 6 L electropolished tube, using C r 2 0 3 tube.
  • the Ni F 2 pipe is formed by applying a fluorine gas to the inner surface of the Ni pipe to form a 0.2 ⁇ 111 1 ⁇ 1 F 2 film.
  • C r 2 0 3 tube, H. on the inner surface of the SUS 316 L electropolished tube l 0% is 0 2 50 p pm introducing A r gas containing heating oxidation at 500, that form a C r 2 0 3 unmoving film on the surface.
  • N i F 2 tubes showed the most excellent decomposition properties, C r 2 0 3 tube hardly show any activity of promoting degradation, also decrease the content of N i is a metal It was found that the decomposition characteristics deteriorated as the temperature increased.
  • FIG. 1 (b) the results of the H 2 gas concentration in the exhaust gas was analyzed by Gasuku port Matogurafi 3 having the heat conduction type detector (TCD). Hydrogen 'Minatodo As shown in FIG reached 200 p pm at a temperature range of, silane was found to generate a completely decomposed to equivalents of H n gas. When heated to higher temperatures, the silane concentration in the exhaust gas remained at zero, although the hydrogen gas flow was reduced (the reason is currently unknown). In the case of a N i F 2 tube, FT IR measurement results show that heating to about 220 ° C or more generates S i, and when using Ni F 2 , a temperature of 200 ° C or less Need to be
  • N i tube As is apparent from chart or table, having a decomposition characteristic N i tube is excellent, especially PH. AsH 3 or the like degrades completely PH 3 at a low temperature of 50 ° C for gas, extremely with high decomposition It has been found to have properties. Further, for example, N i F Pho must be heated above 300 ° C and you'll decompose and remove in 2 tube and generating a S i F 4 in this temperature as described above, N i F 2 alone in was found that not suitable for removal of a gas mixture of S i and PH 3.
  • the Ni tube has a higher adsorption capacity for B 2 H 6 and PH 3 gas than other tubes, and can adsorb and remove the gas for a long time. Therefore, it is possible to purify other gases containing a small amount of hydride gas, and this is an extremely useful purification method especially when the gas is thermally unstable.
  • the nickel fluoride used in the present invention is preferably Ni F 0 having a stoichiometric ratio from the viewpoint of the ability to decompose hydride gas, but is not limited thereto.
  • Nigel pure nickel is preferable, but an alloy containing nickel may be used.
  • the piping and the container itself should be used as a method of arranging these Nigel and nickel fluoride in contact with a hydride gas. It is possible to introduce a hydride gas into the inside of the container by arranging it in the container as a tube, mesh, fiber, or pellet having a small diameter.
  • the inner surface of a stainless steel pipe, vessel, or the like may be coated with a nickel fluoride film, or may be coated on a solid surface of another material of the above-mentioned shape.
  • a solid F e, N i, C r, SUS , etc.
  • Various metals, other alloys, A 1 o0 3, AIN, S i C such as a ceramic or the like is preferably used.
  • Examples of a method of coating a fluoride on a nickel or nickel fluoride film with a solid include a plating method, a sputtered film, and vapor deposition.
  • the nickel fluoride one obtained by fluorinating nickel is particularly preferably used.
  • Ni tube or this is subjected to Ni-P (nickel-phosphorus) plating of about 10 / m thickness by an electroless plating method, and fluorine gas is applied to the plating film at 350 ° C.
  • fluorine gas is applied to the plating film at 350 ° C.
  • a NiF 2 film of about 0.2 / zm may be formed.
  • heating temperatures are: hydride type, flow rate, pressure, contact area of nigel and nickel fluoride gas, nickel and nickel fluoride It is appropriately optimized depending on the arrangement and the like, but when nickel and nickel fluoride are arranged at the same place, the temperature is preferably 85 to 200 ° C. It is more preferable to place nickel and nickel fluoride in different places and heat them to their respective optimum temperatures. The preferable temperature at this time is 50 to 300 for nickel. C, nickel fluoride is 85 ⁇ 200 ° C.
  • a method of coating the surface of a pellet-like granular solid with nickel or nickel fluoride, filling the pellets or the like into a packed tower, and subjecting the pellets or the like to the treatment is performed. Is effective.
  • Examples of the hydride gas to which the present invention is applied include a hydride gas of a Group III element such as B 2 H 6 , a hydride gas of a Group V element such as PH 3 and As H 0 , and S i H ⁇ . S i 2 H 6, G e H 4 group IV elements of the hydride gas and mixed gas, etc., such as are exemplified up. BRIEF DESCRIPTION OF THE FIGURES
  • FIG. 1 is a conceptual diagram showing an experimental apparatus for examining the hydride gas removal ability of the present invention.
  • Figure 2 is a graph showing the effect of temperature on silane decomposition and H 2 gas generation for various materials.
  • Figure 3 is a graph showing the relationship between the decomposition of diborane and the temperature for various materials.
  • Figure 4 is a graph showing the relationship between phosphine decomposition and temperature for various materials.
  • FIG. 5 is a graph showing the phosphine adsorption ability of various materials.
  • FIG. 6 is a graph showing the diborane adsorption capacity of various materials.
  • FIG. 7 is a conceptual diagram illustrating an arrangement of the removing device according to the first embodiment.
  • FIG. 8 is a conceptual diagram illustrating an arrangement of the removing device according to the second embodiment.
  • FIG. 9 is a conceptual diagram illustrating an arrangement of the removing device according to the third embodiment.
  • FIG. 10 is a graph showing the relationship between the decomposition rate of arsine and temperature for various materials.
  • FIG. 7 shows a first embodiment of the present invention.
  • FIG. 7 shows an example in which the removing device is arranged between the reaction chamber of the semiconductor manufacturing apparatus and the vacuum pump.
  • 74 is a turbo-molecular pump
  • 75 is a rotary pump
  • 76 denotes a heater.
  • the hydride gas remover is a 4 mm diameter cylindrical vessel with a diameter of 40 cm in order to facilitate hydride catalytic decomposition and minimize equipment resistance.
  • n + polysilicon (5% S i H 4 1 s 1 m, 0. 5% PH 3 2 s 1 m, A rl O slm) 4 0 0 nm of deposition and PSG (5% S i H 4 (N 2 dilution) 800 sc cm, 5% PH 3 (N 2 dilution) repeatedly performed 1 60 sccm, Oo800 sc cm) deposition of 200 nm, the decomposition of the gas by the detector there between removal device outlet confirmed.
  • the removal device was heated to 90 eC . Even after repeated 30 times the film formation, S i H 4. PH 3 is not detected at all, the removal device of the present real ⁇ has been found to be practical.
  • the hole diameter and length of the honeycomb may be appropriately determined depending on the pressure and flow rate of the hydride gas used, but the hole diameter is usually several mm. It is preferably used.
  • FIG. 8 shows a second embodiment of the present invention.
  • FIG. 9 shows a third embodiment of the present invention.
  • This embodiment is an example in which a removing device is provided on the downstream side of the exhaust system similarly to the conventional exhaust gas treatment device.
  • 91 is a special gas inlet
  • 93 is a heater
  • 94 is a gas detector
  • 95 is a washing tower
  • 96 is a water circulation tank
  • 97 is a water circulation pump.
  • two packed towers are arranged in parallel, and only one of them is used. Attach a gas detector to the gas outlet of the packed tower to monitor the status of the removal equipment during operation. When the capacity of the packed tower is lost, switch to the other packed tower. The discharged gas may be sent to a scrubber for gas discharged from other semiconductor manufacturing equipment.
  • the mixed gas of the hydride gas can be effectively removed, and furthermore, since the gas can be installed on the upstream side of the exhaust pump, maintenance of the exhaust system and the like is remarkably facilitated.
  • the operation rate can be greatly improved.
  • no powder solids are generated, clogging does not occur in pumps, packed towers and other devices, and the removal can be performed extremely stably.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Environmental & Geological Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Biomedical Technology (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Treating Waste Gases (AREA)

Abstract

Procédé et appareil d'extraction d'hydrures gazeux permettant de détoxiquer un mélange gazeux en éliminant complètement les différents hydrures qu'il contient, grâce à une structure simple et sans produire des corps pulvérulents qui provoqueraient l'engorgement de l'appareil. Ce procédé se caractérise en ce qu'un mélange gazeux contenant au moins deux types d'hydrures gazeux est mis en contact avec du fluorure de nickel et du nickel pour soumettre les hydrures à décomposition et/ou adsorption, ce qui permet de les éliminer. Ce procédé se caractérise également en ce qu'on élimine un hydrure gazeux d'un élément du groupe III ou V du tableau périodique en mettant le gaz en contact avec du nickel de manière à soumettre le gaz à décomposition et/ou adsorption, ce qui permet de l'éliminer.
PCT/JP1995/001553 1994-08-05 1995-08-04 Procede et appareil d'extraction d'hydrures gazeux WO1996004064A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
KR1019970700655A KR970704501A (ko) 1994-08-05 1995-08-04 수소화물가스의 제거방법 및 제거장치(hydride gas removing method and apparatus)
JP50640096A JP3801201B2 (ja) 1994-08-05 1995-08-04 水素化物ガスの除去方法及び除去装置

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP6184951A JPH09239232A (ja) 1994-08-05 1994-08-05 水素化物ガスの除去方法及び除去装置
JP6/184951 1994-08-05

Publications (1)

Publication Number Publication Date
WO1996004064A1 true WO1996004064A1 (fr) 1996-02-15

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PCT/JP1995/001553 WO1996004064A1 (fr) 1994-08-05 1995-08-04 Procede et appareil d'extraction d'hydrures gazeux

Country Status (3)

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JP (2) JPH09239232A (fr)
KR (1) KR970704501A (fr)
WO (1) WO1996004064A1 (fr)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6068034A (ja) * 1983-09-14 1985-04-18 Nippon Paionikusu Kk 有毒成分の除去法
JPS60125233A (ja) * 1983-12-08 1985-07-04 Mitsui Toatsu Chem Inc 排ガスの高度処理方法
JPH01139536A (ja) * 1987-09-24 1989-06-01 Labofina Sa 軽オレフイン含有炭化水素原料からアルシンを除去する方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6068034A (ja) * 1983-09-14 1985-04-18 Nippon Paionikusu Kk 有毒成分の除去法
JPS60125233A (ja) * 1983-12-08 1985-07-04 Mitsui Toatsu Chem Inc 排ガスの高度処理方法
JPH01139536A (ja) * 1987-09-24 1989-06-01 Labofina Sa 軽オレフイン含有炭化水素原料からアルシンを除去する方法

Also Published As

Publication number Publication date
JP3801201B2 (ja) 2006-07-26
KR970704501A (ko) 1997-09-06
JPH09239232A (ja) 1997-09-16

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