JP2009008265A5 - - Google Patents

Description

Fluid storage and transport system consisting of high capacity physical adsorbent

The present invention relates to storage for selectively dispensing fluid from a container or storage container that holds fluid components in a sorption relationship with a solid sorption medium and for releasably releasing the sorption medium during a dispensing operation. As well as a dispensing system.

  A wide variety of industrial methods and applications require reliable process fluid feedstocks.

  Areas of such methods and applications include semiconductor manufacturing, ion implantation, flat panel displays, medical participation and treatment, water treatment, first aid equipment, welding operations, transport of liquid and gas space utilization, etc.

  As of May 17, 1988, Carl O. U.S. Patent No. 5,057,037 issued to Knollmueller describes storage of arsine followed by contacting arsine with a zeolite having a pore size ranging from about 5 to about 15 angstroms at a temperature of about -30 ° C to about + 30 ° C. The arsine is adsorbed onto the zeolite by heating and then the zeolite is heated to a high temperature of up to about 175 ° C. for a time sufficient to release the arsine from the zeolitic material, and heated and dispensed.

  The method disclosed in the aforementioned Patent Document 1 of Knormüller is a method for heating a zeolite material that needs to be constructed and arranged so as to heat the arsine previously adsorbed to a temperature sufficient to adsorb the zeolite in a desired amount. It is disadvantageous in that it needs to be installed.

  The use of a heating jacket or other means outside the vessel holding the arsine-supported zeolite is problematic in that the vessel typically has a significant heat capacity and thus introduces significant wasted time into the dispensing operation. Furthermore, the heating of arsine causes its decomposition, resulting in the generation of hydrogen gas that can lead to explosion hazards to the processing system. Moreover, such heat-mediated degradation of arsine can significantly increase the pressure of the gas present in the treatment system and can be extremely disadvantageous from the standpoint of safety concerns as well as the service life and work efficiency of the system.

  Providing the zeolite bed itself with an internally arranged heating coil or other heating element uses such means to uniformly heat the zeolite bed to achieve the desired uniform release of the desired arsine gas. Is a problem because it is difficult.

Its storage container carrier gas stream is heated and passed through the zeolite bed, although it overcomes the aforementioned drawbacks, but the temperature required to achieve adsorption of the heated carrier gas arsine, arsine gas end use since the unsuitable at high or other conditions, to undesirably, cooling or other treatment is required to be in a state that meets the end use of the dispensing and gas.

Next, on May 21, 1996, Glen. M.M. Tom and James. V. Patent Document 2 issued in the name of McManus discloses a gas storage and dispensing system, which overcomes the disadvantages of the gas supply method disclosed in Patent Document 1 described above. The gas storage and distribution system of Patent Document 2 is for storage and distribution of gas, for example, a gas selected from the group consisting of hydrogenated gas, halogenated gas, and organometallic group V compound, A storage and dispensing container constructed and arranged to hold the adsorbing medium in the storage and dispensing container at a container internal pressure , and to selectively flow into and out of the container, and the storage and dispensing container A solid-phase physical adsorption medium disposed in the gas storage medium and connected to the storage and dispensing container in gas flow communication and supply a pressure less than the internal pressure outside the dispensing container to solid and desorption from-phase physical adsorbent medium, becomes a gas flow of desorbed gas configured to pass inside, the adsorption and desorption apparatus and a placement the dispensing assembly, before Solid phase physical adsorption media such as water, metals and oxidized transition metal species (eg oxides, sulfites and / or nitrates) that otherwise decompose the sorbent gas in the storage and dispensing containers It is characterized by no trace components.

By removing such trace components from the solid physical adsorption medium, a very low level after one year, the decomposition and pressure conditions at a temperature 25 ° C. of the sorbate gas, for example of the sorbate gas 1 - 5 Less than % weight can be maintained to be degraded.

The storage and dispensing container of the aforementioned patent document 2 can thus embody a practical advantage over the use of high pressure gas cylinders according to the prior art. Similar to leaks from pressure reducing valve assemblies where conventional high pressure gas cylinders are damaged or degraded, bursting when internal decomposition of the gas rapidly increases the internal pressure of the cylinder, and cylinder bursting Or it is also sensitive to mass release of gases from other undesirable cylinders.

  The gas storage and dispensing container of Patent Document 2 lowers the pressure of the stored sorbate gas by back-adsorbing the gas onto a carrier adsorption medium such as zeolite or activated carbon material. Other objects and advantages of the invention will become more fully apparent from the ensuing disclosure and appended claims.

  As the technology is in constant demand for the identification and use of improved adsorbent materials in fluid storage and transport systems of the type described above, the object of the present invention is to provide significant advantages in cost, ease of use and performance characteristics. It is in the provision of a fluid storage and dispensing system that utilizes the high efficiency adsorbent material provided.

Other objects and advantages of the invention will become more fully apparent from the ensuing disclosure and appended claims.
U.S. Pat. No. 4,744,221 US Pat. No. 5,518,528

The present invention contemplates sorbed fluids, for example fluid mixture and a gas containing a single component fluid, vapor, liquid, system for storage and dispensing of such multiphase fluid.

Fluid storage and dispensing system of the present invention, to hold a solid-phase physical sorbent medium having a sorptive affinity sorption fluids, also so as to selectively flow into and flow out of the sorption fluid configuration, Consists of arranged storage and dispensing containers. The solid-phase physical sorbent medium having a sorptive affinity for the fluid, is physically adsorbed fluid the storage and placed in a dispensing vessel in internal pressure of the container to the solid-phase physical sorbent material. A dispensing assembly is connected in gas flow communication with the storage and dispensing container. The dispensing assembly is external to said storage and dispensing vessel, by supplying a pressure less than the internal pressure, and desorption of the fluid from the solid-phase physical sorbent medium, desorbed fluid to the dispensing assembly cause a Re through Ru flow. Alternatively, the storage and the dispensing system, and means for causing the desorption from the solid-phase physical sorbent medium fluid to selectively heat the sorbent material, during thermal desorption, the desorbed fluid, configured to receive the fluid flow to pass the dispensing assembly, the arranged storage and dispensing vessel and the gas and flow communication with concatenated dispensing assembly may be both be configured. As another example, the storage and dispensing system of the present invention can be constructed and arranged to combine differential heat and differential pressure desorption of fluid from a solid phase physical sorption medium.

The dispensing assembly, as appropriate for the particular end use of the fluid storage and dispensing assembly of the present invention, any type of conduit as long as a suitable tube, tube, passage, valving, total It can also be beneficially constructed from a device, monitoring means, flow regulator, pump, blower, aspirator or the like. The present invention can be constructed in any suitable configuration or size of storage and dispensing containers, such as containers having an internal volume of about 0.01 liters to about 20 liters.

In certain embodiments, the present invention is directed to a fluid storage and dispensing system that utilizes a carbon sorbent material as a solid phase physical sorption medium in the manner described above. A wide variety of carbon sorbents can be used as effective sorption media in the storage and dispensing systems of the present invention.

In one embodiment, the present invention relates to a fluid storage and dispensing system that can be used in a small, portable point of use that includes fluid that is physically adsorbed at an internal pressure of less than 1200 Torr on a high performance sorption medium.

  The term “raw material storage and dispensing system that can be used in a small, portable place of use” as used herein is a system that has been extensively described as described above, and the contents of its storage and dispensing containers. The product has a volume of about 0.01 to about 20 liters.

  The present invention has the greatest technological advancement in providing just a small low-pressure fluid source and uses all conventional types of gases, such as welding gas, anesthetic gas, oxygen or oxygen-enriched lifesaving gas, The ability to sufficiently replace the cylinders for high-pressure fluids that have been used in various applications that require semiconductor manufacturing gas, inert sealing gas, such as nitrogen for combustion or chemical reaction suppression, can be achieved.

  Especially in the case of semiconductor production where the amount of reagent gas for industrial use, for example, ion implantation, doping, etc. is very small, and the secondary processing equipment for semiconductor production is extremely small and the installation area is premium. The installation of a low pressure gas source is a major improvement over the entire use of high pressure gas cylinders with various current drawbacks.

The internal pressure in the container containing the sorbent of the low pressure storage and dispensing system of the present invention is less than about 1200 Torr. The pressure is preferably 800 torr, most preferably less than 700 torr. By supplying the decompressed sorption fluid to the storage and dispensing container, the danger of the absorbed fluid leaking into the surrounding environment or being dispersed in large quantities is a constant danger that the high-pressure storage of the fluid will not end. In contrast to the inevitably associated safety measures and processing problems, they can be prevented.

In another particular embodiment, the present invention relates to a fluid storage and dispensing system of the kind broadly described above, comprising a high work capacity sorbent material.

Performance characteristics to adapt to sorbent applied to the storage and dispensing of the present invention, the sorption loading capacity (amount of sorbate fluid which is stored in the sorbent per unit weight of sorbent material), Osamu per unit volume of the cover material, the sorption working capacity is defined as the weight of sorbate, which is initially charged to a sorbent material that can be removed from the sorbent medium in the fluid dispensing work at a predetermined pressure and temperature conditions Cw including. That is, Cw = [weight of sorbent−weight of sorbent remaining after desorption] / [volume of adsorbent]

The weight of the sorbent as well as the weight remaining after desorption is measured in grams and the volume of the sorbent material is measured in liters. Volume of sorbent material used in such measurements is the volume of the bed of sorbent material. This sorbent material is typically supplied in pellets, particles, extrudates, granules or other segments, so the volume in the measurement of work capacity takes into account the packing density and the void volume of the sorbent material Put in.

Another measure of the efficacy of a sorbent material that can be used generally usefully in the broad implementation of the present invention is that the sorbent material is initially charged at a pressure of 760 torr and then the pressure is reduced to 10 torr at 25βC. It is the “ratio of sorbable sorption quality” of the sorbent material defined as the ratio of sorbate gas that can be desorbed only by desorption. Ie:
Desorbable sorption quality ratio = {(weight of sorption quality−weight of sorption quality remaining after desorption) / (weight of sorption quality)} × 100%
The ratio of the detachable sorption quality is at least about 15%, preferably at least about 25%, more preferably at least about 50%, most preferably at least about 60%.

Further sorbent material employed in the practice of the present invention, advantageously, the sorbate fluid appropriately readily sorbed at a high efficiency as a first example, (1) the inner volume of the storage and dispensing vessel When the differential pressure between the lower pressure outside of, and / or (2) the storage and reaction to the heat, the sorbent during dispensing work on any fluid dispensing system sorbed fluids, rapid It has the characteristic to discharge accordingly .

Useful Preferred sorbent materials in fluid storage and dispensing system of the present invention, 1g per about 0.1 to the range of about 5.0 cm ³ of sorbent material, preferably from about 0.5 to about per sorbent material 1g Includes materials with a pore volume in the range of 2.0 cm ³ (cumulative pore volume).

The sorbent material preferably has a major portion of the pore volume , i.e. , more than 50% of the pore volume, preferably more than 80% , and most preferably almost all diameters of the pore volume range from about 2 angstroms to 100 angstroms. It consists of the pores .

Preferred materials are in the range the average pore diameter of about 2 to 20 angstroms, the main part of the air holes, and more preferably the portion exceeding 80%, and most preferably in the range substantially all of said diameter of pore volume It contains some sorbent .

High performance sorbents useful in the broad practice of the present invention, measured at a pressure of 40 Torr and 650 Torr arsine gas, sorbent material per liter of at least 50, preferably at least 100, more preferably at least 150 and, Most preferably, including those having a “ sorbent capacity, Cw” of at least 200 g, measured as follows:
Cw = (weight indicated by a pressure 650 torr, of arsine gas for one liter of sorbent at a temperature 25 ℃ g) - (weight indicated by the pressure 40 torr, the arsine gas for one liter of sorbent at a temperature 25 ° C. g)
[Wherein arsine is the reference fluid for such Cw characteristics, and the liter criteria for the sorbent is the liter volume in the bed configuration of the bed of sorption media including voids or interstitial spaces as described. ]
In this regard, it should be noted that increasing work capacity is possible by reducing the pressure to a low value of 1 Torr.

Sorptive materials useful in the fluid storage and dispensing system of the present invention include beads, granules, pellets, tablets, powders, particles, extrudates, cloth or web-like materials, honeycomb matrix monoliths and ( sorbents and others Of any suitable size, shape and form, including composite materials (as well as pulverized or crushed shapes) which take the form of the sorption materials described above.

Sorptive materials include polymers (eg microporous Teflon®, large network polymers, glassy domain polymers, etc.), phosphosilicate aluminum (ALPOS), clays, zeolites, porous silicon, honeycomb matrix materials, It can be made of any suitable material including carbon materials.

The most preferred sorbent material comprises a zeolite sorbent material and a carbon sorbent . Among the preferred carbon sorbents are bead activated carbon materials having a highly uniform spherical shape and a diameter in the range of about 0.1 mm to 1 cm, more preferably a diameter of about 0.25 to about 2 mm. Is the most preferred.

In yet another embodiment, used as a reference gas to characterize arsine, useful sorbent materials in fluid storage and dispensing system of the present invention was measured in g of adsorbed arsine sorbent per liter , Composed of a material with an arsine gas adsorption isotherm at a temperature of 25 ° C. as a function of the pressure shown in Torr and having the following adsorption filling properties:
Pressure (torr) Minimum filling amount (g of arsine per liter of sorbent)
25 30
50 62
100 105
200 145
300 168
400 177
500 185
550 188
650-192

While it is generally preferred that the sorption material used in the storage and dispensing system of the present invention has significant filling properties for sorption fluids that are stored and subsequently dispensed from the sorbent , High sorbent filling capacity can be disadvantageous from a sorption heat standpoint in some cases with respect to storage and dispensing systems. Sorption of the sorbing fluid on the sorbent is typically exothermic. For gases such as arsine and phosphine, the calorific value is inevitably accompanied by a temperature increase of about 100βC or more depending on the filling rate of the gas on the sorbent . Thus, during the initial filling of the sorption medium with a fluid that will be stored in the sorbent for subsequent dispensing, it has a high sorption capacity in the range without significant heat of adsorption. It is preferred to use a sorption medium.

Thus, a sorbent material useful in the practice of this invention is measured by the number of grams of arsine adsorbed per liter of sorbent and is the isothermal adsorption of arsine gas at a temperature of 25 ° C. measured as a function of the pressure in Torr. It includes a material having a line that is within the isotherm bounded by curves G ₁ and G ₀ in FIG. Such sorption materials have the following adsorption and filling properties.

Pressure (torr) Filling amount (g of arsine per liter of sorbent)
25 30-106
50 62-138
100 105-185
200 145-232
300 168-263
400 177-288
500 185-308
550 188-315
650 192-330

Sorbent used in the fluid storage and dispensing system of the present invention is preferably a sorbent characterized by any combination or permutation if appropriate sorbent characteristics stated various above be able to.

Suitable carbon sorption materials for the fluid storage and dispensing system of the present invention are, for example, those having the following adsorption packing characteristics at a temperature of 25 ° C.
Pressure (torr) Minimum filling amount (g of arsine per liter of sorbent)
25 35-60
50 75-100
100 100-115
200 160-175
300 200-220
400 225-245
500 240-260
550 250-275
650 260-300

A highly preferred carbon sorbent material useful for the broad practice of the present invention is the arsine gas at a temperature of 25 ° C. as a function of the pressure in Torr, measured as grams of arsine adsorbed per liter of sorbent . 1 includes a material having an adsorption isotherm having the characteristic of curve A in FIG. 1 (adsorption isotherm characteristic refers to the actual shape of the adsorption isotherm in FIG. This is because it moves in the x and y directions with the change of, but the overall shape is virtually the same).

Carbon sorbent can be used for gas storage and dispensing system of the present invention comprises a sorbent characterized by any combination or permutation if appropriate in the various stated sorbent properties .

In one embodiment, the present invention contemplates a fluid storage and dispensing adsorption and desorption device for use in a small and portable use location for fluid storage and dispensing:
Solid-holds-phase physical sorbent medium, the sorbent medium selectively flows, adapted to flow out, and the storage and dispensing vessel is arranged;
A sorption material charged to the storage and dispensing container at a fluid pressure in the container of less than 1200 Torr;
- physically adsorbed sorbate fluid to the sorption materials;
The storage and is connected through dispensing vessel and a gas flow communication, after the differential heat and / or the difference圧脱deposition of fluid from the sorbent material, so that it can be dispensed in response to selectively request the desorbed fluid A configured and arranged dispensing assembly;
The dispensing assembly comprises:
(I) to the outside of the storage and dispensing vessel, wherein the pressure of less than the internal pressure was supplied to desorb the fluid from the sorbent material, also said fluid such that the flow of desorbed fluid through the dispensing assembly flow carded from the container; and / or (II) includes a heating means for heating the sorbent material to desorb the sorbed fluid, thermal desorption fluid is thermally desorbed as to flow from the container into the dispensing assembly fluid cormorant'll flow, configuration, characterized in that it is disposed.

In another embodiment, the present invention relates to an adsorption / desorption apparatus for gas storage and dispensing,
A storage and dispensing container configured, arranged to hold solid phase physical sorption media and selectively allow gas to flow in and out;
A sorption material placed in said storage and dispensing container at container internal pressure ;
- physically adsorbed sorbate fluid to the sorption materials;
- the storage and linked through dispensing vessel and a gas flow communication, and after the difference between the fluid heat and / or differential pressure medium through desorption from the sorbent material, in accordance with the selective request desorbed fluid metering A dispensing assembly configured and arranged to dispense;
The dispensing assembly comprises:
(I) to the outside of the storage arrangement dispensing vessel, fluid is desorbed from the sorbent material by supplying the pressure below the internal pressure and the fluid to flow desorbed fluid through the dispensing assembly flow carded from the container; a sorptive fluid desorbing includes a heating means for heating and / or (II) the sorbent material, desorbed fluid is thermally desorbed as to flow from the container into the dispensing assembly fluid It is characterized in that it is configured and arranged so as to flow .

The sorption material should be avoided from those selected from the group consisting of trace components such as water, metals and oxidized transition metal species (eg oxides, sulfites and / or nitrates) and sorbed in the storage and dispensing containers. It is preferable that the fluid is sufficiently concentrated to decompose the fluid.

In the storage and dispensing apparatus of the present invention, (relative to the weight of sorbent material) concentration of the sorbent material of trace components selected from the group consisting of water and oxidized transition metal species 1 year at temperatures preferably 25 ° C. after 5% greater than degradation prior Symbol pressure in a yield Chakushitsu fluid, it is that it is preferably insufficient to decompose more than 1% by weight. Such constraints on the sorbent are fluids such as hydride gases such as arsine, phosphine, etc., in the presence of water, metals and oxidative transition metal species (eg oxides, sulfites and / or nitrates). Ensures that the adsorbate fluid, which is sensitive to decomposition, is maintained without substantial exposure to such species to prevent substantial levels of decomposition of the sorbate gas and consequent pressure build-up problems. To do.

Preferably, the concentration of the minor component selected from the group consisting of water, metal and transition metal species relative to the weight of the sorbent material is an internal pressure after one week at a temperature of 25 ° C. in the storage and dispensing container, As a result, the sorbate fluid is insufficient to cause degradation of more than 25%, preferably more than 10%.

Carbon sorbent material advantageously used in the practice of the present invention is less than 350 ppm by weight of trace components selected from the group consisting of water and oxidized transition metal species, preferably less than 100 ppm by weight, more preferably, less than 10 ppm by weight , And most preferably carbon material comprising less than 1 ppm by weight relative to the weight of the sorption medium.

Preferred carbon sorbents in the practice of the present invention can also be defined as conditions in terms of their ash content. Preferred carbon less than about 7%, and preferably less than about 5%, and most preferably contains from about 0.1% ash. The ash content of various carbon sorbents is as high as 15%. Ash content can vary widely depending on the specific source of carbon material.

Ash contains components such as silica that can be detrimental to applications that require sorbent fluids that irreversibly chemisorb to these types of compounds, such as hydrogen fluoride and boron trifluoride. It is an inorganic material. Such chemisorption is extremely disadvantageous because it results in the loss of the chemisorbing compound. Therefore, low ash carbon sorbents are particularly preferred in practice.

The problems that are likely to occur with the use of high ash carbon sorbents discussed above are particularly severe in the case of fluorides. Absorption of fluoride by high ash carbon sorbents is actually due to the internal pressure in the storage and dispensing container where the reaction product between the sorbent and impurities in the high ash sorbent is a non-volatile product. Decreases with generation.

Preferably, the concentration of the minor component selected from the group consisting of water, metal and transition metal species relative to the weight of the sorbent material is the result of an internal pressure after one week at a temperature of 25 ° C. in a storage and dispensing container. As such, the sorbate fluid is insufficient to cause degradation exceeding 25%, preferably exceeding 10%.

Sorbent material advantageously used in the practice of the present invention is less than 350 ppm by weight of trace components selected from the group consisting of water and oxidized transition metal species, preferably less than 100 ppm by weight, more preferably less than 10 ppm by weight, and Most preferably, it comprises a carbon material containing less than 1 ppm by weight relative to the weight of the sorption medium.

While the fluid storage and dispensing system of the present invention is described below primarily in relation to dispensing by the differential pressure of fluid from the container, the storage and dispensing system of the present invention is also based solely on the differential pressure desorption of the sorbate fluid, and it will be appreciated that enables the dispensed from the sorbent material sorbed described above the fluid in the same manner by thermal desorption. As another example, desorption of a sorbent fluid from a filling sorbent medium can be usefully performed in combination with a differential pressure and heat-mediated release from the sorbent sorbent medium.

Selection of special style conditions of the method (differential pressure contact and / or difference thermionic) desorption and accompanying therefor is sorbent material, special sorbate fluid, and in particular based on the final application using a desorption fluid It can be easily selected and examined by one skilled in the art without unnecessary experience.

When the fluid storage and dispensing system of the present invention is constructed and arranged to allow thermal desorption from the sorbent material in the fluid container, the heating means is operatively disposed in relation to the storage and dispensing container. Thus, the sorbent gas can be thermally enhanced and desorbed from the sorbent material. This heating means is located on the sorption bed of the electrical resistance heating element, extended heat transfer surface member, radiant heating member, or storage and dispensing container, or otherwise heat transfer to the sorbent material or on-site It includes other thermally actuated heating means arranged for heating, is carried out with increase in the temperature of the sorbent, the desorption of the sorbate fluid.

The sorption material used in the practice of the present invention is properly processed or treated to ensure that it lacks components or contaminants, such as the minor components discussed above, which are sorbent quality. It adversely affects the performance of gas storage and dispensing systems for fluid sorption and desorption. For example, the sorbent can be washed using hydrofluoric acid so that it is sufficiently free of trace components such as metals and transition metal species.

Sorbent material may be further variously treated to enhance the sorption capacity and / or other performance characteristics of the sorbent. For example, the surface of the sorbent treatment or sorbent, (1) when filling the initially fluid that will sorbent is subsequently dispensed, sorption on the sorbent medium of a particular fluid, And / or (2) make the sorbent easier or more functional with chemical components that facilitate or enhance fluid desorption when in a processing condition for storing and dispensing fluid from a container for dispensing. be able to.

In addition, the treatment can improve the purity of the desorbed material. For example, reductive treatment of surface oxides can be used to reduce the amount of CO, CO ₂ and hydrocarbon impurities in the desorbate.

  Still further, various temperature ranges can be used during the degassing process. As a typical example, the carbon material can be degassed at a maximum of 500 ° C., although further temperature treatment can be applied.

Special additional modifications method sorbent material, including the application of the sorbent reinforced material on the surface including the inner pore surfaces of the material, can be variously used in the broad practice of the present invention. For example, the adsorption enhanced liquid, solid or semi-solid material, for example Carbowax (Carbowax) subjected to the sorbent, and physical sorption of the fluid of the solid sorption sites on the surface of the sorbent, the sorbent Sorption on the adsorption enhancing material itself applied to the surface of the agent or solubilization within itself can be facilitated.

Storage and dispensing system of the present invention further chemical sorption comprising a sorbent material that has entered the storage and dispensing vessel, contaminants entering the sorbate gas into the container, the affinity for example degradation products Comes with materials. Such chemical sorbent comprises a solid sorbent composition having a chemisorbent affinity for non-reducing atmosphere gas.
Examples of potentially suitable chemisorbent materials are:
(A) a non-covalently bonded support associated therewith and a compound effective to supply an anion reactive in the presence of said contaminant to remove such contaminant ,
(I) a carbanion source compound wherein the corresponding protonated carbanion compound has a pKa value of about 22 to about 36;
(Ii) a scavenger selected from one or more of the group consisting of an anion source compound formed by reaction of the carbanion source compound with a sorbent gas;
(B)
(I) an inert support having a surface area in the range of about 50 to about 1000 m ² per gram and thermally stable up to a temperature of at least about 250 ° C .;
(Ii) on the support, present in a concentration of about 0.01 to about 1.0 mole per liter of support, of a group IA metal selected from sodium, potassium, rubidium and cesium and mixtures and alloys thereof; A scavenger comprising desorption on a support and an active scavenging species formed by its thermal decomposition on the support;
A scavenger selected from the group consisting of:

As a further example, the chemisorption material is advantageously from a scavenger component selected from the group consisting of trityl lithium and potassium arsenide.

To the use for contaminant removal of sorbate fluid In such a chemisorption material to be dispensed, it is also available to any of the wide variety of scavengers or chemisorbent materials, 1988 to it August 2nd Glen. M.M. U.S. Pat. No. 4,761,395 issued to Tom et al. And Glen. M.M. Tom and James. V. A scavenger composition in the form disclosed and claimed in US patent application Ser. No. 08 / 084,414 in the name of McManus.

The above disclosure is incorporated herein by reference.
When chemical sorption material using the same, the availability through bed and fluid flow communication with the sorbent material as a separate bed, or alternatively, the storage and dispensing vessel a chemical sorbent, sorbent The bed of material can be distributed randomly or selectively.

The present invention further contemplates a method of supplying a fluid reagent and comprising the following steps:
Providing a storage and dispensing container comprising a sorption material that physically has a sorption affinity for said fluid reagent;
- fluid reagent generating a sorbent material that the fluid reagent is filled with the sorbate fluid filled to physically sorbed sorbent materials;
- a step of vacuum (pressure difference) the sorbate fluid by heating desorption and / or sorbent material to desorb the sorbate fluid from the sorbent material filled;
· The desorbed fluid from the storage and dispensing vessel and a step of dispensing;
Consists of.

In further preferred embodiments, the sorbent material is in any particular form (eg, beads, granules, pellets, powders, extrudates, etc.) and has the sorbent properties described above in various ways. is there.

Fluids that can be usefully stored and subsequently dispensed in the storage and dispensing system of the present invention can be any type of fluid that has a sorption affinity for the sorbent material, such as gas, vapor, Also included are liquids, multiphase fluids, and fluid mixtures. Examples include acidic and hydride gases, halide gases, water vapor phase organometallic compounds, oxidizing gases, and the like.

Specific examples of sorbate gas species that can be usefully stored and dispensed in the practice of the present invention are silane, germane, arsine, phosphine, phosgene, diborane, germane, ammonia, stibine, hydrogen sulfide, hydrogen selenide. Hydrogen telluride, nitrous oxide, hydrogen cyanide, ethylene oxide, deuterated hydride, halide (chlorine, bromine, fluorine and iodine) compounds such as F ₂ , SiF ₄ , Cl ₂ , ClF ₃ , GeF ₄ , SiF ₄ , Compounds such as borohydrides, and metal organometallic compounds such as aluminum, barium, strontium, gallium, indium, tungsten, antimony, silver, gold, palladium, gadolinium and the like.

In yet another specific embodiment, the present invention is of the general form described above and relates to a storage and dispensing system consisting of boron trifluoride as the sorbent fluid. The boron trifluoride dispensed from the system is contacted with a hydrogenating agent to convert the boron trifluoride gas to diborane. The hydrogenating agent is useful for carrying out such a conversion and can comprise any suitable hydrogenation reactant such as magnesium deuteride.

The present invention in another embodiment relates to the adsorption and desorption apparatus for the storage and dispensing of sorption can be fluid carbon sorbent material. The device is:
- holding the carbon sorbent material, selectively configured so as to flow out the flow and from the vessel to the vessel the flow body, and arranged storage and dispensing vessel;
· Before Symbol storage and carbon sorbent material, which is charged to the dispensing vessel;
Physically adsorbed sorbate fluid-carbon sorbent materials in;
- the storage and through dispensing vessel in fluid flow communication linked, and the storage and to supply the pressure below the pressure outside the dispensing vessel, the sorbate gas the carbon sorbent material or al is desorption, configured to gas flow of desorption the gas therethrough, and arranged dispensing assembly;
- coupled to the dispensing assembly, and a pressure of desorbed gas, and discharge the cryopump of pressurized gas as a result;
Consists of.

In a further method aspect, the present invention relates to a method for storing and dispensing a fluid sorbable on a carbon sorbent material and relates to the following steps: a storage and dispensing container holding the carbon sorbent material. Preparing the step;
- the fluid and adsorbing the carbon sorbent material;
- the outside of the storage and dispensing vessel, by generating a pressure of less than the internal pressure, the sorbate fluid is desorbed from the carbon sorbent material, is caused to flow out the storage and dispensing vessel or al desorption fluid Process and;
· The desorbed fluid from the storage and dispensing vessel, a step of the cryopump at a predetermined pressure higher than the pressure of the fluid desorbed that drained from the storage and dispensing vessel;
Consists of.

The storage and dispensing system of the present invention includes ion implantation, silicon semiconductor manufacturing, compound semiconductor manufacturing, flat panel display manufacturing, gas supply to organic synthesis, metering of sterile gas such as ethylene oxide, fumigation and pest management. Anesthesia gas delivery, treatment of water and other fluids that require gas-liquid contact, welding, horticultural and crop protection formulations, cooking gas supplies, space-borne applications, bulk chemicals and It can be applied to a wide variety of uses, including gas delivery, life-saving oxygen supply and application of O ₂ reagent.

  Other embodiments, features and examples of the invention will become more fully apparent from the ensuing disclosure and appended claims.

  Disclosure of International Patent Application No. PCT / US95 / 13040 (International Publication No. 96/11739) filed on October 13, 1995, with the United States designated as the designated country, and on October 13, 1994 Disclosure of US Patent No. 5,518,528 issued May 21, 1996 to filed US Patent Application No. 08 / 322,224, and US filed May 20, 1996 The disclosure of patent application No. 08 / 650,634 (US Pat. No. 5,704,965) and US patent application Ser. No. 08 / 650,633 filed May 20, 1996 (US Pat. No. 704,967) is incorporated herein by reference.

The present invention provides a new low pressure storage and delivery system as a fluid source means used in applications such as hydride and halide gas and organometallic group V compound ion implantation. The foregoing illustrative examples are arsine, phosphine, germane, chlorine, NF ₃ , BF ₃ , BCl ₃ diborane (B ₂ H ₆ and its deuterium analog B ₂ D ₆ ), HCl, HBr, HF , HI, tungsten hexafluoride, and (CH ₃ ) ₃ Sb. The present invention provides a new low pressure storage and transport system as a fluid source means that is more compact and can be used in portable locations.

  As used herein, the term “low pressure” refers to a pressure that is essentially not greater than 1 atmosphere, such as a pressure equal to or less than 1.25 atmospheres, more preferably equal to or less than 1 atmosphere, Most preferably, it refers to a pressure in the range of about 0.15 to about 0.8 atmospheres.

  While the storage and dispensing system of the present invention can be operated at higher pressures than in the low pressure certain types described above in a broad implementation of the present invention, such a storage and dispensing system allows the fluid to be evacuated at reduced pressure. It has a special use effect in the application to be used, for example, ion implantation. In such end use, the device of the present invention allows for low pressure storage and dispensing of fluids.

  With such low pressure operation, the system of the present invention eliminates the need for a number of previously used applications such as for prior art high pressure liquid containers. The use of a high pressure vessel increases the risk of leakage and damage to people and / or property, especially when hazardous gases are involved, whereas the low pressure system of the present invention allows the fluid medium to be at about atmospheric pressure. It can be stored at a level and dispensed quickly and freely.

The fluid source system of the present invention consists of a leaktight container, for example a gas cylinder that contains fluid to be dispensed and adsorbed on a sorbent material consisting of a physical adsorbent material. In the case of gaseous sorbents, such as arsine and phosphine, the sorbent reduces the vapor pressure of the sorbent gas until it is less than or equal to 1 atmosphere.

Although the present invention will be discussed below primarily in terms of storage and transport of arsine and phosphine gases, the effectiveness of the present invention is not limited in this way, rather it is liquid, gas-like, as with a wide variety of other gases. It will be appreciated that liquid mixtures and the like are also included. Illustrative examples are silane, diborane, arsine, phosphine, phosgene, chlorine, BCl ₃ , BF ₃ , B ₂ D ₆ , tungsten hexafluoride, hydrogen fluoride, hydrogen chloride, hydrogen iodide, hydrogen bromide, germane Ammonia, stibine, hydrogen sulfide, hydrogen cyanide, hydrogen selenide, hydrogen telluride, deuterated hydride, halide (chlorine, bromine, iodine and fluorine) gaseous compounds such as NF ₃ , ClF ₃ , GeF ₄ , SiF ₄ , Organic compounds as well as organometallic group G compounds such as (CH ₃ ) ₃ Sb.

The novel means and method of the present invention that the storage and transport equal to or less than the pressure of the liquid body to 0 psig, it is possible to greatly reduce the risk posed by the fluid. The inventive One technique is especially adsorbed on a carbonaceous physical adsorbent the fluid. Fluid can be lowered by adsorbing to the carbonaceous solids physical sorbent, the vapor pressure of the fluid that is less than or equal pressure to 0 psig. The release potential from this system is greatly reduced as the pressure driving force is eliminated.

The sorbent used in the broad practice of the present invention may be any suitable sorbent affinity for the fluid to be stored and dispensed from the sorbent used in the practice of the present invention. It does not matter even if it is in such a form. For example, the sorbent is porous silicon material, aluminum phosphate, clay, zeolite, polymer (including porous Teflon (registered trademark), large network polymer and glassy domain polymer), phosphosilicate aluminum, carbon material, etc. Consists of.

Preferred sorbent materials for the practice of this invention include zeolite and carbon sorbent .

Preferred types of carbon sorption materials are carbon, cellulose charcoal, charcoal, natural material sources such as coconut shell, pitch, wood, formed by pyrolysis of synthetic hydrocarbon resins such as polyacrylonitrile, sulfonated polystyrene-divinylbenzene, etc. , Including activated carbon formed from petroleum, coal, etc.

Carbon sorption materials are well known per se, and also deal with VOC reduction due to sorption of VOCs from an effluent stream into a very large bed of carbon, for example in a wide variety of industrial methods such as the semiconductor industry. Nevertheless, there has never been a storage and dispensing system that initially supplies fluid reagents and process gases based on carbon sorbent materials. Therefore, the present invention utilizes a carbon sorbent material that is readily available in the market in a wide variety of dimensions, shapes, surface areas, and compositions, and is subject to the prior art of supplying process gases and fluid reagents from pressurized cylinders, By providing an effective fluid supply system that can eliminate disadvantages and disadvantages in advance, it provides technically significant advantages.

  The prior art has extensively utilized gas cylinders for supplying welding gases, anesthetic gases, oxygen chemical process reagent gases, and the like, and has used extremely thick cylinder containers to contain the associated high pressures. This is because the supply capacity of the cylinder (the amount of fluid that can be dispensed) is a function of the pressure level in the cylinder, and the increased pressure level matches the increased cylinder dispensing capacity.

Sorption medium, i.e. the present invention by using a carbonaceous sorbents problems in process (risk of high pressure gas cylinder rupture, the overpressure by the gas decomposition in situ danger, as well as monitoring of the very high pressure of gas And in the case of hazardous gases, including problems requiring special safety and processing measures that are proportional to the associated hazard). The sorbent media of the present invention allows for rapid storage of fluids and differential pressure and / or thermal desorption metering that can be easily effected.

Here it used related to the physical sorbent material of the present invention have the term "carbonaceous" means that the sorbent material consists of carbon element as a major component in the sorbent material. Preferred types of carbon sorption materials are synthetic hydrocarbon resins such as polyacrylonitrile, sulfonated polystyrene divinylbenzene, carbon formed by pyrolysis, cellulose charcoal, charcoal, natural source materials such as coconut shell, pitch, wood, petroleum, Includes activated carbon formed from coal.

Preferred carbon sorbent material is of high sorption of the carbon forms produced by heat activated carbon, i.e. the particulate charcoal at elevated temperatures. Most preferred is the so-called bead carbon form of activated carbon, in which case beads of spherical particles of very uniform diameter have a diameter of about 0.1 to about 1 cm, preferably about 0.25 to about It is in the range of 2 mm.

Carbon sorbent materials available on the preferred market for wide implementation of the present invention include US. New York. Kureha from New York. Corporation. of. Bead carbon materials designated as “BAC-MP”, “BAC-LP” and “BAC-G-70R” to become commercially available in the United States; Pennsylvania. Philadelphia Rohm. and. Hearth. Become commercial Cie in carbonaceous sorbent "Ambersorb ^(R)", "Ambersorb ^(R) 563" as a brand, "Ambersorb ^(R) 564", "Ambersorb ^(R) 348F", "Ambersorb ^(R) 575 "," Ambersorb ^(R) 572 "and" Ambersorb ^(R) 1500 ", and Calgon. carbon. There is a carbon sorption material of “CollonFiltorsorb 400 ^(R) ” and “BPLGAC” commercially available from the Corporation. Elkrat Bullher. Game. M. B. Includes commercially available bead activated carbon sorption materials from Her. Among the carbon sorbent described above, "Ambersorb" material has a significant pore volume greater than 50 angstroms in pore, also typically a material having such a large pore, no greater than about 40 Å pore Less preferred than those with.

The sorbent used in the storage and dispensing system of the present invention may be of any size, shape and form that is appropriate for the end use and the specific sorbate fluid species required. Good. Sorptive materials can be, for example, beads, granules, pellets, tablets, powders, particles, extrudates, cloth or web-like materials, honeycomb matrix monoliths, composites (of sorbent and other components) or fines of the aforementioned form. It can be ground or crushed.

Collectively, the storage and delivery system of the present invention, and the standard gas cylinders contain carbon sorbent material, linked cylinder valve or other flow dispensing assembly (pressure regulating valve to the bomb, the monitoring device, the detector , Flow directing means, pressure controller, flow rate controller, piping, valve adjustment, instrumentation, automatic starting and shut-off device). After filling the sorbent into the storage and dispensing vessel, filled with sorbate fluid in a bomb at a pressure less than one atmosphere if example embodiment, to produce the result storage and dispensing system.

In use, the fluid flow using differential pressure desorption from the storage and dispensing system of the present invention is the result of the pressure in the internal volume of the storage and delivery system and the relatively low pressure external to the container containing the sorbent . It can be easily caused by using the differential pressure between them.

For example, a vessel containing a sorbent can hold a reagent gas such as phosphine for use in an ion implantation process at reduced pressure, eg, 600 Torr, where an ion implantation chamber for phosphorus component implantation is maintained under vacuum conditions. Or as another example maintained at a low pressure, eg, less than 100 torr, and less than the pressure of the internal volume in the storage and dispensing container. As a result, phosphine gas will desorb from the sorbent in the vessel and between the storage and dispensing vessel and an ion implantation chamber including a yield Chakushitsu phosphine gas Ru communicates gas flow, sorbate phosphine gas There flowing to the ion implantation chamber. The storage and dispensing system thus generates a flow of phosphine gas through the connecting piping, valve regulation and instrumentation and can be easily controlled at the desired flow rate. Device, for example the use of flow controller, the pressure of the sorbent container is decreased with unbroken dispensing work, Ru obtained constant flow.

In addition, or alternatively, the fluid dispensing assembly of the storage and dispensing of the present invention, it is possible to heat the sorbent material the sorbate fluid from the sorbent material comprises Netsuda' Chakusuru means. Such heating means heats efficiently sorbent material and operatively associated with the sorbent material, were applied to the thermal desorption of the sorbate from the intake Chakuzairyo, what heat transfer or heat exchange There may be a device, component or device. Thus, the present invention contemplates that the sorbate fluid from the adsorption agent is thermally and / or pressure-mediated dispensing.

Referring now to the drawings, FIG. 1 shows a plot of arsine loading measured in grams of arsine per liter of sorbent material as a function of pressure measured in torr, as well as illustrative carbon for arsine. sorbent (curve a, data point symbols △) for each of, and zeolite 5A molecular sieve (curve B, data point symbols ■) is a graph of the adsorption isotherm for. The carbon sorption material is a “BAC-G-70R” carbon material from Kureha, with the following specifications detailed in Table 1 below:

Relates ahead, by heating the originally supplied in the market carbon exhaust, like the moisture bead carbon material is further reduced to a low level of 0.01% or less, be noted that. Such pretreatment of the carbon sorbent is also effective in other impure product adsorbed undesirably in the carbon material during availability.

FIG. 2 shows the cumulative pore volume, expressed in cm ³ per gram, as a function of pore size expressed in angstroms, first for the bead carbon sorbent material of Table 1 (curve C), and for a wide range of practice of the invention. FIG. 2 is a plot shown for some specific illustrative commercial activated carbon sorbents (curves D, E and F). The beaded carbon material of curve C shown has a cumulative pore volume of about 0.3 to about 0.7 over a range of pore sizes of 10 to 10,000 angstroms. The other carbon sorption materials of curves D, E and F have a relatively wide cumulative pore volume.

In general, a significant portion of the air holes, preferably utilizes a sorbent material in the range of size of at least 50% to about 10 to 1000 angstroms. More preferably, the sorbent material comprises a major portion of its pore volume, i.e. more than 50%, preferably more than 80%, most preferably almost all of which have pores with a diameter in the range of about 2 angstroms to 100 angstroms. That is.

A preferred sorbent material includes a sorbent having an average pore diameter in the range of about 10 to 20 angstroms, and the majority of the pore volume is preferably greater than 80%, most preferably nearly all of this. It is in the range of such a diameter .

Preferred sorbent is to include a material having a pore volume in the range of sorbent material 1g per 0.2 to about 2.0 cm ³ (cumulative pore volume).

The internal pressure in the container containing the sorbent of the low pressure storage and dispensing system of the present invention is less than about 1200 Torr. Preferably the pressure is less than 800 torr and most preferably less than 700 torr. The sorbed fluid in the storage and dispensing vessel by the reducing the pressure, never endures high pressure storage of fluids, and a significant danger, as in the prior art with a safety and disposal problems corresponding thereto In contrast, leakage of the sorbent fluid into the surrounding environment as well as the risk of mass dispersion can be prevented.

Further In the alternative embodiment, the present invention is already above broadly described the kind of high adsorption loading capacity, high-rate ratio of the desorption sorbate and fluid storage and dispensing system comprising a high sorption work capacity, It is about.

  This percentage of desorbable sorbate is desirably at least about 15%, preferably at least about 25%, more preferably at least about 50%, and most preferably at least about 60%.

The sorbent material preferably easily sorbate fluid in the first example, also suitably sorption at high speed, (1) storage and between the inner volume and low pressure outside the dispensing vessel differential pressure, and / or (2) it is provided with a feature of the storage and correspondingly release heat dispensing system fluid metering work industry during the sorbent and reacts to the sorbed fluid in a rapid way It is.

Preferred sorbent materials useful in the fluid storage and dispensing system of the present invention have a pore volume per gram of sorbent material in the range of about 0.1 to about 5.0 cm ³ , preferably from about 0.5 to about 2. including the .0cm a ³ in the range of pore volume (cumulative pore volume) material.

Highly preferred materials have an average pore diameter in the range of about 2 to about 20 Angstroms, a portion of the pore volume within the range, more preferably greater than 80%, and most preferably substantially all of the pore volume is Having a sorbent that is within range.

High performance carbon sorbents useful in the broad practice of the present invention are at least 50 g, preferably at least 100 g, more preferably at least 150 g, and most preferably at least 200 g of arsine gas (as reference fluid) per liter of sorbent . Including those with sorption work ability measured at pressures of 40 Torr and 650 Torr. The percentage of desorbable sorbate is desirably at least about 15%, preferably at least about 25%, more preferably at least about 50%, and most preferably at least about 60%.

A bead activated carbon material having a very uniform sphere shape and a particle size in the range of about 0.1 mm to 1 cm, more preferably in the range of about 0.25 to about 2 mm diameter is very advantageous for the practice of the present invention. . The particle size of the sorbent, the distribution of the shape and pore size and implemented individually and not significantly change the of the present invention, to adjust the packing density in the bed of filler and sorbent material particles sorbent.

Sorptive materials useful in the fluid storage and dispensing system of the present invention are generally of any suitable size, shape and form, such as beads, granules, pellets, tablets, powders, particles, extrudates, fabrics. Alternatively, it may be in the form of a web form material, a honeycomb matrix monolith, and a composite material (of sorbent and other components), as well as the above-described sorbed material form.

The sorption material can be any suitable material such as a polymer (eg, microporous Teflon (registered trademark), large network polymer, glassy domain polymer, etc.), aluminum phosphate, clay, zeolite, porous silicon, It may contain a honeycomb matrix material, a carbon material, or the like.

The most preferred sorbent material comprises a zeolite sorbent material and a carbon sorbent . Among the preferred carbon sorbent materials, bead activation having a very uniform sphere shape and a particle size in the range of about 0.1 mm to 1 cm, more preferably about 0.25 to about 2 mm. Carbon materials are most preferred.

A sorbent material that is also used here as a reference gas for characterization, and is particularly useful in the fluid storage and dispensing system of the present invention, is measured in grams of arsine adsorbed per liter of sorbent and is expressed in torr. It is made of a material having an arsine gas adsorption isotherm at a temperature of 25 ° C. as a function of pressure, and has the following adsorption filling characteristics.

Pressure (torr) Minimum filling amount (g of arsine per liter of sorbent)
25 30
50 62
100 105
200 145
300 168
400 177
500 185
550 188
650 192

The sorption material used in the storage and dispensing system of the present invention preferably has the highest possible filling properties for the sorption fluid to be stored and subsequently dispensed from the sorbent. In some cases, the high adsorption packing capacity may be disadvantageous from the standpoint of sorption heat in terms of storage and manufacturing of the dispensing system. The sorption of the sorbent fluid to the sorbent is typically exothermic, and for gases such as arsine and phosphine, the calorific value is 100βC or more due to the filling rate of the gas into the sorbent. This is accompanied by a temperature increase of the order of magnitude. Therefore, utilizing a sorbent comprising a KoOsamuchaku capacity within a range without large amounts of heat by adsorption performed while the filling fluid will be stored on the sorbent for continued dispensing after Is preferred.

Thus, for arsine gas sorbent material useful in the practice of the present invention, measured as g number of arsine sorbed sorbent per liter, adsorption at a temperature of 25 ° C. as a function of the pressure of torr display A material whose isotherm is within the adsorption isotherm range enclosed by curves G ₁ and G ₀ in FIG. 1 can be included. Such a sorption material has the following adsorption filling properties.
Pressure (torr) Filling amount (g of arsine per liter of sorbent)
25 30-106
50 62-138
100 105-185
200 145-232
300 168-263
400 177-288
500 185-308
550 188-315
650 192-330

A preferred carbon sorbent material in the fluid storage and dispensing system of the present invention has an arsine gas adsorption isotherm at a temperature of 25 ° C. measured in grams of adsorbed arsine per liter of sorbent It has the following adsorption filling characteristics.
Pressure (torr) Minimum filling amount (g of arsine per liter of sorbent)
25 35
50 75
100 100
200 160
300 200
400 225
500 240
550 250
650-300

A suitable carbon sorption material has the following adsorptive packing properties, for example at a temperature of 25 ° C .;

Pressure (torr) Filling amount (g of arsine per liter of sorbent)
25 35-60
50 75-100
100 100-115
200 160-175
300 200-220
400 225-245
500 240-260
550 250-275
650 260-300

A highly preferred carbon sorption material useful in the wide practice of the present invention has an isotherm of arsine gas at a temperature of 25 ° C., measured in grams of arsine adsorbed per liter of sorbent , It contains the material it has as a function of pressure and has the adsorption isotherm characteristic of curve A in FIG.

The sorbent pore size, pore volume and surface area characteristics vary widely over a wide range of implementations of the present invention, and the skilled person can determine the appropriate adsorption characteristics for a given end use of the storage and dispensing system of the present invention. For example, mercury porosimetry techniques and storage of specific candidate sorbent materials, as well as specific fluid affinity studies that require dispensing from it It will be accepted that it can be easily determined.

Referring again to FIG. 1, the sorption material isotherm and the specific sorbent gas are generally useful in predicting the amount of sorbent that can be removed at a constant pressure. This is due to the reversibility of the adsorption / desorption process for physisorbed fluid species. For example, with respect to the bead carbon sorbent material of the curve A, when desorbing sorbent causes sorbed arsine fluid from a pressure of 650 torr to 100 torr pressure, the sorbent material per liter of arsine 140g (275g-135g = 140 g) should be desorbed there. In contrast, zeolite 5A molecular sieves show desorption of only 87.5 g of sorbate fluid (215 g-127.5 g = 87.5 g) when desorbing at the same differential pressure.

In this way, the amount of sorbate that can be recovered in the storage and dispensing system from Oite carbon sorbent of the present invention is performed at a pressure desorption ranging specific pressure range of 650 Torr to 100 Torr, the prior art 60% more than the zeolite 5A material of the storage and dispensing system. Accordingly, the performance of the carbon sorbent material of curve A in FIG. 1 is representative of the ability of the sorbent fluid to desorb from the sorbent material dispensed as representative of the performance of the carbon sorption media used in the broad practice of the present invention. Proves an amazing and surprising improvement.

  FIG. 3 is a schematic diagram of a storage and dispensing system according to one embodiment of the present invention.

The storage and transportable Okushi stem by schematic diagram shown in FIG. 3, the gas can be filled with suitable physical adsorbent material, e.g. further bed 17 types of bead activated carbon physical sorbent medium as detailed above A storage cylinder 10 can be provided.
The gas cylinder 10 comprises physically adsorbed gas component, for example, the surface adsorbed arsine or phosphine (pores and including an outer surface of similarly adsorbed medium).

Upstream of a gas cylinder isolation valve 16 that connects the cylinder 10 to the fluid conduit 12 and can be selectively activated to communicate with the fluid conduit 12 by disposing the cylinder valve 14 therein and closing the cylinder 10. The gas is discharged from the cylinder 10 in a controllable manner.

The fluid conduit includes a branch mount 18 therein, whereby the fluid conduit 12 is connected in gas flow communication with a branch purge line 20 having an inert gas purge isolation valve 22 therein, thereby The fluid conduit can be purged with an inert gas prior to active operational delivery of gas from the cylinder 10.

The fluid conduit downstream from the mount 18 contains two successive filters 28 and 30 with a pressure transducer 32 in the middle, for example, having a pressure working range of about 0 to about 25 psia.

The fluid conduit 12 is connected downstream of the gas filter 30 with a branch attachment 34, to which is connected a bypass conduit 36 having a bypass isolation valve 38 therein. The fluid conduit 12 downstream of the attachment 34 includes a gas flow on / off valve 40 therein with a flow controller 42 disposed downstream thereof to control the flow rate of gas dispensed through the fluid conduit 12. adjust. Downstream of the flow controller 42, the fluid conduit 12 is connected by a coupling 44 to a discharge line 46 containing a flow control valve 48 therein and in gas flow communication with the bypass conduit 36 via a coupling 50. Connect. The discharge line 46 is joined to the ion source generating means as shown in the schematic diagram as an element 52 as shown. The other end 54 of the discharge line 46 can be connected in gas flow communication with other gas dispensing means as desired or required for a given end use of the storage and transfer system apparatus of FIG.

As an optional feature of the storage and dispensing cylinder 10 in the embodiment of FIG. 3, there is shown a heat exchange passage 11 extending vertically up through the bed 17 of sorption material. This heat exchange passage is joined to the heat exchange fluid supply inlet line 13 and the heat exchange fluid discharge / discharge line 15 at the lower end and the upper end, respectively. This heat exchange fluid supply inlet line 13 works in sequence with a burner, resistance heater or other heating means to assist in the selective heating of the bed 17 of sorbent material when dispensing of fluid from the container 10 is preferred. Can be joined to a suitable source (not shown) of heat exchange fluids that can be associated with each other. Netsuda' deposition (although not for example shown by means reservoir and pump) recirculating through the thus suitable heat exchange fluid in the heat exchange circuit supply inlet conduit 13 for the heat exchange passages 11 and the fluid discharge This can be done by a passage through the discharge line 15. The function of such a heating means heats the sorption medium in the bed 17 to a sufficiently high temperature to allow heat-assisted desorption.

The arrangement shown schematically in FIG. 3, the heat grants desorption and dispensing of the sorbate fluid, as an alternative to differential pressure medium through the dispensing of the sorbate fluid, or in combination with differential hydraulic mediated dispensing, Selection of a particular desorption mode can be readily selected and / or determined without undue experimentation by those skilled in the art.

In the manufacture of the storage and dispensing system of the present invention, the storage and dispensing vessel is washed if necessary, the vessel followed by the wall inside the vessel may adversely affect the storage and dispensing operations carried out using to ensure without a slight contamination or species, including the removal temper species. Therefore, out baked, in a solvent degreasing or another way, the container and washing the inner surface, subjected removal or treatment step, preferably right NiKiyoshi Kiyoshisu Rukoto container for sorbent material which is subsequently charged.

Later, filled with sorbent material into the interior volume of the storage and dispensing vessel, and sealed assembled container eventually. In order to maximize the sorption capacity of the sorbent medium may be charged sorbent material for cleaning or processing and Teka RaHiroshi device. Properly in another way also, the sorptive media wash Kiyoshia Rui and field processing, for example, the out baked container comprising a sorbent with sufficient high temperature, also the sorbate species sorbent material foreign desorption Ru can be maximized reliably sorption ability by performing a sufficient period of time to wash. For example, the container for a long time, for example during 48 hours, an appropriate high temperature, exhaust (degassing) using a suitable vacuum pump or other evacuation means, for example 200 to 400 ° C. can be Rukoto. After evacuation, the container is allowed to cool to room temperature for a suitable time, for example 6-12 hours.

After the evacuation / degassing procedure, the evacuated sorbent container is connected to a sorbent fluid-filled fluid conduit . Sorption of fluid species, since with significant heating value for the heat of adsorption, after maintaining the container and the sorbent material at a suitable temperature and sorbed The first sorption material, such thermal action It is preferable to prevent the sorbent fluid from desorbing.

  In order to maintain an approximate isothermal condition, the cylinder is immersed, for example, in a hot ballast solution such as an aqueous ethylene glycol mixture maintained at a constant temperature of 25 ° C.

The sorbate fluid fill fluid conduit to dispense the sorbate fluid from the exhaust appropriate low pressure, for example less than 10 ^-3 Torr, removing non-condensable gases present in the flow path of the fill fluid conduit To do. After such evacuation, the container containing the carbon sorbent is filled at a suitable rate until the sorbate fluid reaches the desired pressure level. To improve efficiency, it is desirable to monitor the vessel pressure during the filling operation using a suitable pressure monitor or other detection means (eg, provided in the transducer).

  During the filling process, the container temperature and thermal ballast tank are individually trimmed for process control along with the sorbent fluid temperature. The pressure is monitored to determine the end point of the filling process.

  Preferably, the container is filled with sorbent fluid step by step and the device is equilibrated to dissipate the temperature effect at least partially to the ambient environment or to a heat transfer medium, such as the thermal ballast liquid described above.

Alternatively, it may be appropriate to fill the container to a certain pressure and then allow the container to cool to the final temperature and pressure conditions of the sorbent bed and associated container.

Therefore, the sorbent fluid is metered or continuously filled, and the sorbent fluid is introduced into the container and absorbed and absorbed by the sorbent material therein. Following the filling operation, after disconnecting the container from the Filling fluid conduit, the vessel is placed or product unloading, storage, or dispensing situ pipe, for subsequent dispensing attached to connecting the dispensing circuit arrangement Can

FIG. 4 is a plot of toll cylinder pressure as a function of time display, showing the pressure decay of arsine gas on the carbon sorbent after the arsine filling operation in a storage and dispensing system according to the present invention. Shown in the graph. As shown, the pressure in the container containing the sorbent is attenuated to 688 torr after 10 hours from an initial pressure level of 750 torr (at time zero).

The plot of FIG. 4 shows the non-equilibrium state that exists at the end of the arsine filling operation in the container. At such point, (in comparison to the final equilibrium pressure level after cooling) heat for adsorption operation may issue a relatively high pressure. The subsequent pressure decay is due to the cooling of the sorbent bed and container after the filling operation. Therefore, following the filling process, it is appropriate to calculate the pressure level in the storage and dispensing container after the heat dissipation of the adsorption action.

  FIG. 5 is a plot of pressure decay rate expressed in Torr / hour as a function of time display for an arsine storage and delivery system according to the present invention, the pressure characteristics after filling being shown in FIG. FIG. 5 shows a decay rate curve measured as a derivative of the curve shown in FIG. The velocity curve in FIG. 5 shows that pressure fluctuations in the storage and dispensing containers settle to a stable level as the decay rate approaches zero after about 2 hours.

Furthermore, the plot of FIG. 4 and FIG. 5, the pressure in the storage and dispensing vessel has been shown to decrease without increasing after sorbate gas fill, arsine sorbate is in the container since this in may be inferred that there is no decomposition Tei remain in that state. This is significant in that the sorbent material is to sorbate gas, for example may include contaminants or trace species capable of mediating or facilitating the decomposition of arsine.

To eliminate surely unnecessary degradation of arsine or other sorbate gas species, the carbon sorbent medium definitive in the practice of the present invention, minor components such as water, metals and oxide transition metal species (e.g. oxide, sul selected from the group consisting of fit and / or nitrate), it is desirable that the minor component having a concentration of enough to decompose the sorbate fluid is not contained at all in the storage and dispensing vessel.

In the storage and dispensing system of the present invention, (the weight of the carbon sorbent material to) concentration in the carbon sorbent material of trace components selected from the group consisting of water and oxidized transition metal species, after one year, the 25 ° C. at a temperature between the internal pressure, more than 5% by weight of the sorbate fluid, it is desirable that the insufficient concentration to preferably decomposition of more than 1 wt% results.

This reference, water, metal and oxide transition metal species (e.g. oxides, sulfites and / or nitrates) susceptible hydride gas effects in other respects to degradation in the presence of, for example arsine sorption of phosphine quality fluid, the species can be reliably maintained without exposing virtually which makes it possible to prevent a significant degradation of the sorbate gas, the problems of the pressure due to it.

The concentration of the minor component selected from the group consisting of water , metal and oxidized transition metal species with respect to the weight of the carbon sorption material is 1 week after storage in a container for storage and dispensing at an internal pressure of 25 ° C. %, preferably more than 10%, preferably insufficient concentration to degradation occurs of the sorbate fluid.

The carbon sorbent material advantageously used in the practice of the present invention is less than 350 ppm by weight, preferably less than 100 ppm by weight of a minor component selected from the group consisting of water and transition metal species relative to the weight of the carbon sorption medium. More preferably less than 10 ppm by weight, most preferably less than 1 ppm by weight.

FIG. 6 is a plot of the arsine adsorption isotherm plotted as a function of pressure as a function of the storage and dispensing vessel torr of packing of arsine in g / liter on bead carbon sorbent . From this adsorption isotherm having substantially the same shape as the arsine adsorption isotherm of FIG. 1 (curve A), measured against arsine gas at a pressure of 40 torr and 650 torr, and
Cw = (weight of arsine gas expressed in grams on 1 liter of sorbent at a pressure of 650 torr and a temperature of 25 ° C.) − (G on a liter of sorbent at a pressure of 40 torr and a temperature of 25 ° C. weight of arsine gas on screen), measured sorbed work capacity as, Cw is
(278-70 = 208 g arsine per liter of sorbent )
It becomes.

As described above, the preferred carbon sorption medium in the practice of the present invention has a shape corresponding to the shape of the adsorption isotherm characteristic of curve A in FIG. 1 which is the shape of the adsorption isotherm shown in FIG. including the measurement was used as a gas sorbate species) sorbent with arsine adsorption isotherm.

  FIG. 7 is a schematic perspective view of a storage and dispensing system 200 according to another embodiment of the present invention.

As shown, a storage and dispensing system 200 comprises a storage and dispensing container 204 joined at its top to a valve head 206, said valve head comprising a valve head manual actuator 208 on the cylinder. Consists of part of assembly. The valve head is coupled by 210, the pressure transducer 214 by a fluid conduit 212 disposed therein, an inert purge device 216 for purging the dispensing assembly with inert gas, and a fluid conduit 212 during the dispensing operation. Joined to a flow controller 220 that maintains a constant flow rate and a filter 222 that removes particles from the dispensed gas and then discharges it from the dispense assembly.

The dispensing assembly further comprises a coupling 224 that engages the dispensing assembly with other components associated with downstream piping, valving or desorbed fluid location.

FIG. 8 is a method system 300 including a gas delivery storage and dispensing device using a dispensed gas for ion implantation according to one embodiment of the present invention.

As shown, the device includes a storage and dispensing container 302 joined at its upper end to a valve head 304 connected to a manual valve actuator wheel 306. The valve head is coupled to a VCR filtration gasket 308, connecting it to the flow body conduit 312 in order. Flow body conduit 312 and pressure transducer 310, it communicates to the same manner with the check valve 314 and nitrogen purge inlet. The nitrogen purge inlet is used for the introduction of nitrogen or other purge gas into the gap of the dispensing assembly flow path and the subsequent dispensing of gas from the container 302.

Flow body conduit 312, the flow control valve 307, a span gauge 320, a flow controller 322 was further disposed a flow control valve 309 therein. The flow body conduit 312 is further contacted with the circuit formation relationship flows bypass conduit 325 having therein a bypass valve 324. The flow body conduit 312 with the right hand end shown, is joined to the gas box manifold conduit 326. A conduit 326 includes a valve 311 disposed therein and has a coupling 330 for connection to the ion implantation chamber of the storage and dispensing system, relative to the end communicating with the gas box manifold.

During operation, gas from the sorbent bed (not shown) of the storage and dispensing container 302 can be controlled in the fluid conduit 312 and the gas box manifold conduit 326 to be controlled by the flow controller 322. Flow into the ion implantation chamber at a moderate speed. The pressure transducer 310 is operatively connected in the flow circuit in conjunction with the flow controller 322 and other elements, such as valves, so that gas for ion implantation can be dispensed in any suitable manner.

  FIG. 9 is a cross-sectional perspective view of the storage and dispensing container 302 of FIG. 8, showing the internal structure of such a container.

As shown, the container 302 comprises a wall 346 that surrounds the interior volume 352 of the container and encloses the particulate sorbent material 350 therein. At the upper end of the vessel, the inlet valve head 304 is joined, the inlet is not the solid particles in other words or having a porous central tube 360 or other small holes are entrained in a gas that is dispensed from the bed of sorbent material It is characterized by a gas permeable structure that serves as such.

  FIG. 10 is a schematic perspective view of a cryopump storage and transfer system apparatus according to a further embodiment of the present invention.

Fluid storage and dispensing system of the present invention, the desorbed sorbate gas to use location of the low pressure dispensing in vacuum or very low pressure level applications, be, for example, ion implantation, the effect of using the present invention Not only so limited, but also includes applications where the storage and dispensing container needs to supply a sorbent gas to a downstream point of use at a pressure above atmospheric pressure.

In applications where it is desirable to supply a gas to be used at a pressure higher than the discharge pressure from a container containing the sorbent of the storage and transport system, various pressure generating circuits, pressurizing devices or other means or methods can be advantageously used. .

For example, a venturi pump can be provided to raise the pressure of the supplied gas to a selected pressure level that exceeds the pressure of the cylinder head (of the cylinder containing the sorbent that binds the gas to be dispensed). Such venturi pump device generates a relatively high pressure level to the selected dispensed with gas, nevertheless, because it is entrained in a gas that is dispensed from the cylinder to the carrier gas, like this The device entails dilution of the gas to be dispensed with a carrier gas.

  The carrier gas dilution effects may be satisfactory in some applications, however, in some uses these dilution effects may be applied to an overall method system, such as high purity raw gas supplied from a storage and dispensing system. Significant restraint can be shown when it is preferable. Although mechanical pumps can be used in place of venturi pump means, mechanical pumps inevitably involve a significant number of moving part disadvantages and entrain the lubricant in the particle formation and / or gas flow in the pump. It can cause related problems. Again, these can be an acceptable side effect in some applications, but in other applications it is necessary to maintain the supplied gas in high purity and free of particles or other foreign substances.

  If the gas supplied by the storage and dispensing system needs to be supplied in a high pressure, high purity, raw state, installation of the cryopump assembly in a storage and transfer device can be advantageous.

  FIG. 10 is a schematic perspective view of a cryopump storage and transfer system apparatus 400 according to a further embodiment of the present invention.

In the this cryopump system, the main cylinder 402 contains subsequently Hama charging a suitable sorbate gas to be dispensed the suitable carbon sorbent material (not shown). The cylinder 402 is fitted with a valve head assembly 404 with a main cylinder isolation valve 406 in the “off” position at the beginning of the dispensing method.

The valve head 404 is connected to a conduit 408 containing an isolation valve 410, a flow controller 412, an isolation valve 414 and a cryopump 416. Conduit 408 is in turn connected to a conduit that includes product dispensing regulator assembly 430 with outlets 434 that can be connected to isolation valves 418 and 422 and a downstream process system. The conduit 409 is connected to the intermediate pressure cylinder 420.

  The cryopump 416 connected to the conduit 408 is provided with a liquid nitrogen (or other suitable cryogenic liquid or fluid) inlet 428 and a liquid nitrogen outlet 426, and a cryogenic liquid flow path intermediate the inlet 428 and outlet 426. As shown in the figure, the heating element 424 limits the arrangement. The cryopump cryogenic liquid inlet and outlet may be suitably connected to a cryogenic air source or a cryogenic cylinder source of liquid nitrogen or other refrigerant as long as the embodiment relates to a cryogenic liquid source. Thereby, the cryopump forms a cryotrap device. When the isolation valve 422 is provided at the outlet of the cryopump in this way, the intermediate pressure cylinder 420 can be isolated by the isolation valve 422.

  A pressure transducer 411 is disposed in the conduit 408 and is connected to the cylinder 402 in a pressure monitoring relationship to monitor the pressure in the cylinder and adjust the isolation valve 418, respectively.

The operation of the storage and transfer system shown schematically in FIG. 10 consists of silane as a gas sorbed on a carbon sorbent contained in a cylinder 402 and transferred at an appropriate elevated pressure, and a cryopump. The nitrogen as a low temperature source to be used as the working fluid in 416 will be specifically described below. Silane has a boiling point of -111.5 ° C and a melting point of 185 ° C, and nitrogen has a boiling point of -198.5 ° C.

  Silanes are transported at moderate pressures (compared to other hydrides such as arsine, which has a relatively high boiling point and freezing point, and therefore can be cryopumped easily and requires less cryogenic cooling). It was chosen for explanation because it was difficult.

  When valves 410, 414, and 406 are first opened, while valves 418 and 422 are closed and depressurized, and the temperature in the cryogenic pump is lowered to the temperature of liquid nitrogen, the silane is within the cryopump, even if Even if a relatively low internal pressure is present in the supply cylinder 402, solidification freezing occurs.

A flow controller 412 allows an accurate measurement of the amount of gas transferred to the cryopump 416. Such an accurate measurement is important because over-pressurization of the cryopump is preferably prevented. Under such working conditions, silane can exceed its critical temperature and the extreme temperature in the cryopump can be quite high.

  After the correct amount of gas has been transferred to the cryopump 416, the valves 410 and 414 are closed. The condensed silane is then heated to near ambient temperature. This heating is performed by a heating element 424 comprising a band heater, although any heating element suitable for such applications as shown in the examples can be used. The silane gas must thereby be heated to a high temperature and the stability of the product gas that is to be dispensed as this heating causes the silane glass to collapse, which adversely affects its purity and further stability. Purity is increased.

  The pressure of the silane gas is significantly higher after heating with a cryopump without being exposed to a mechanical pump with multiple moving parts that would otherwise contaminate the product gas. Effectively, the gas is thereby compressed to a high purity state.

There is very little residual gas at this point throughout the system, with most of the silane remaining in the sorbent vessel, or cylinder 402, at low pressure.

  When the valve 418 is opened, gas flows into the intermediate pressure cylinder 402. That is, if valve 422 is opened, then product silane gas can flow through outlet 434 downstream as monitored by monitoring means (eg, flow pressure) associated with regulator assembly 430. This regulator assembly 430 is associated with a pressure transducer 432, which can be operatively connected with other valves and cryopump components throughout the system to carry product gas at a selected pressure and volumetric flow rate. .

Correspondingly, various valves, flow controllers, cryopumps, converters and regulators are operatively interconnected in any suitable manner, eg with a cycle timer or method safety system, silane or other The transport based on the demand for the sorbate gas can be controlled and can be easily performed by a reproducible method.

Thus, over time, it is desirable to prevent disruption in the downstream process flow, as is preferred for the operation of the system shown schematically in FIG. Signals entering the cryopump and medium pressure tank from the flow controller and pressure transducer can be used in an automated process system. The cryopump circulates gas from the storage and transfer system to an intermediate pressure cylinder 420 to maintain a constant pressure at the outlet of the regulator.

FIG. 11 is a schematic diagram of a transport measurement device for evaluating the performance of a storage and dispensing system 502 according to the present invention. This storage and dispensing system 502 is arranged with a storage and dispensing container 504 containing a sorption material (not shown), a cylinder valve 506, a gas cylinder isolation valve 508 and as shown (0 to 1000 torr). A fluid dispensing assembly comprising a discharge flow line 512 with a pressure transducer 510.

Line 512 is a connecting line having a T-shaped connector 516 connected to an inert gas purge line 518 including an inert gas purge isolation valve 520 connected to an inert purge gas source 514 by suitable connector means. 522 is connected. Line 512 further includes a flow controller 524 to maintain a constant pressure and a constant flow rate in connecting line 522. A gas on / off valve 526 in line 512 serves to selectively flow gas through line 522 to line 530 connected to line 522 by connector means.

  Line 530 is connected at one end to a vacuum device 538 and at its relative end to a receiving vessel 534 cooled with liquid nitrogen. Valves 536 and 532 are positioned as shown in the middle of each end.

The transport measurement apparatus shown in FIG. 11 causes the sorbent fluid to flow from the storage and dispensing container 504 at a rate controlled by the flow controller 524. Then the gas desorbed and dispensing is a liquid nitrogen cooling receiving vessel 534, after flow through the conduit 512, 522 and 530 by closing / opening setting appropriate valves of the various conduits of the entire system, it is collected .

At the temperature of liquid nitrogen, the vapor pressure of the sorbate gas is approximately 0 torr, allowing the desorption of the sorbate fluid from the carbon sorption medium even at low storage and dispensing vessel pressures. The experiment is typically continued until the test vessel 504 is at a pressure of about 50 Torr or less. As a typical example at such time, there is a differential pressure that is insufficient to maintain an appropriate flow rate (5 sccm or less) by the flow rate controller.

The amount of sorbate fluid that flows from the container 504 into the cooling receptacle 534 is measured by the individual sum of the flow rates (using the flow controller 524) and before and after the storage and dispensing container 504 is desorbed. Can be measured.

In an illustrative experiment using the transport measurement system of FIG. 11, arsine gas is dispensed from a storage and dispensing container containing a carbon material having the properties of Table 1 herein as a sorbent .
The results of this experiment are shown in Table 2 below.

  The above adsorption / desorption capacity data reflects a more than twofold improvement over the corresponding storage and transport system using typical molecular sieve adsorbent materials, such as 5 angstrom molecular sieves, and is a considerable and anticipated improvement over the prior art of the present invention. Prove further the characteristics that do not.

FIG. 12 shows a storage and delivery system consisting of a 5 angstrom molecular sieve as sorption material (curve M, data point symbol Δ) and a storage and dispensing system consisting of bead activated carbon as sorption material (curve N, data point symbol □). ), And the pressure in the toll display storage and dispensing container as a function of time during operation, expressed as a flow rate of 1 standard cm ³ arsine per minute. These curves show that at a constant flow rate of 1 sccm dispense of arsine, storage consisting of bead activated carbon (curve N) as well as providing an improved dispense useful life that the dispense system reaches 2000 hours, storage of curve M and Indicates that the dispensing system has a dispensing life span of 1000 hours.

The storage and transport system apparatus and method of the present invention provides a highly safe alternative to high pressure gas cylinders for current use for sorbent gas storage and dispensing. The present invention provides the ability to transport, store and transport sorbent fluids from cylinders or other containers at 0 psig pressure.

In the practice of the present invention, a so-called in by heat subsidized conveyed by really low levels of heating of the sorbent material, to increase the conveying speed of the desorption gas, it is possible to easily achieve a flow rate of more than 5 00sccm. Nevertheless, in the embodiment using the adiabatic operation of the present invention (thermal or heat energy without adding auxiliary to sorbate filled sorbent medium) extensive sorbent container and, outside the dispensing location, for example a semiconductor or other High gas transport rates can be achieved with only the differential pressure that exists between industrial or manufacturing process equipment such as ion implantation chambers, molecular beam epitaxy equipment or chemical vapor deposition reactors.

The device of the present invention can be easily arranged in the form of a unitary device, such as one or more storage and dispensing systems of the present invention placed in a gas cabinet. In such gas cabinets requiring multiple sorbent containers, each of the containers is branched together for selective transport of sorbate gas from one or more such containers. The cabinet may further comprise individual thermocouples and other temperature sensing / monitoring devices and components to prevent overheating of the container and / or other components of the gas cabinet during its use.

Such gas source cabinets include a soluble link heater element for selective incremental heating of the container and the sorbent contained therein, a sprinkler system, an exhaust heat detector, and operation of the device when toxic gases are detected. Specially equipped with a toxic gas monitor to effect the shutdown, a scrubber or mass sorption device, and surplus pressure and temperature control means. With such a storage and transport system apparatus, a transport rate of 500 sccm of gas at 15 psig pressure can be easily achieved.

In a preferred practice of the invention, the solid phase carbon physical sorption medium is composed of water, metal, and oxidized transition metal species at a concentration insufficient to decompose the sorbate fluid in the storage and dispensing containers. contains no more trace components selected group of. In this regard, the presence of a small amount of water, metal or transition metal oxide in the sorbent material tends to promote an undesirably high level of decomposition of the sorbate gas.

The solid phase carbon physical sorption medium in the preferred practice of the invention is therefore less than 350 ppm by weight, preferably less than 350 ppm by weight, based on the weight of the physical sorption medium, of minor components selected from the group consisting of water and transition metal species. less than 100 ppm by weight, more preferably less than 10 ppm by weight, of minor components and most preferably selected from the group consisting of oxidized transition metal species and water, relative to the weight of the physical sorbent medium, by including the following 1 ppm by weight is there.

Correspondingly, the solid-phase carbon physical sorption medium concentration of a minor component selected from the group consisting of water and an oxidized transition metal species (eg, oxide, sulfite and nitrate) is relative to the weight of the physical sorption medium. One year later, it is preferably insufficient for decomposition exceeding 5% by weight of the sorbent gas at a temperature of 25 ° C. and internal pressure conditions.

  The features and advantages of the invention are more fully shown by the following non-limiting examples.

  74.7 g (130 ml) of Kureha carbon was loaded into a clean 150 ml hook stainless steel sample cylinder. The cylinder was fitted with a Nupro DS series diaphragm valve. The valve inlet was modified to attach a 30 micron “Mott Metallurgical” sintered metal polymer filter. This polymer filter helped the carbon particles get inside the sample cylinder.

The cylinder was then evacuated (degassed) at a temperature of 300 ° C. over 48 hours. The vacuum pump used for degassing (Alcatel Molecular Drag Pump) had an extreme pressure of 1 × 10 ⁻⁶ Torr. After the degassing period, the cylinder was kept at room temperature within 6 hours. Cooled down.

  The general properties of the Kureha carbon used are shown in Table 1 above.

  The results of the degassing procedure are shown in Table 3 below:

After degassing procedure in Example 1, evacuated carbon sample cylinder was connected to an arsine filling portion of an arsine fill fluid conduit. In order to maintain near isothermal conditions, the cylinder was immersed in a dewar flask containing the ethylene glycol mixture held constant at 25 ° C. The fluid was circulated through a dewar flask using a Neslab RTE-100 circulating constant temperature bath.

All fluid conduits were then evacuated to a pressure of less than 10 ⁻³ Torr to remove non-condensable gas. After evacuation, the carbon sample was filled with arsine at a rate of 25 sccm until the pressure reached 760 torr. The pressure was monitored using a MKS 0-1000 Torr Baratron pressure transducer. During the filling process, the dewar flask temperature, carbon cylinder pressure and ambient hood temperature (in the hood environment where the filling takes place) were monitored and measured using a Fluke electronic data self-measuring instrument.

The packing speed of 25 sccm was selected to shorten the time taken to measure the adsorption capacity.
However, the true isotherm could not be achieved due to the heat of adsorption. Although the cylinder was immersed in a constant temperature fluid, the rate of heat exchange between the fluid and the adsorbent was not fast enough, resulting in artificially creating high pressure during the filling process. This is shown in FIG. 4 and demonstrates the non-equilibrium state after filling.

  The cause of this pressure decay was the cooling of the adsorption bed after the arsine flow was over. The heat released to the bed during the filling process was due to heat from adsorption. As a typical example, the true isotherm is obtained when the adsorption process reaches equilibrium before reaching the pressure data point. FIG. 5 shows the derivative of the curve from FIG. 4, which produces the pressure decay rate. The velocity curve shows that the pressure fluctuation settles to a stable level as the decay rate reaches zero in about 2 hours. Of critical importance is the lack of increased pressure to prove that arsine has not degraded.

  An approximate isotherm is constructed and shown in FIG.

The adsorption capacity was measured by integrating the flow rate of arsine over the duration of the experiment. The end point of the adsorption measurement was taken as a pressure of 760 Torr or 1 atmosphere. The adsorption capacity was also demonstrated by the mass by taking the difference between the weight of the unfilled cylinder and the cylinder filled with arsine filling at 760 torr. The results of the adsorption capacity measurement are shown in Table 4.

Based on the adsorption of arsine on zeolite molecular sieve sorbent, prior art in the arsine storage and dispensing system technology due, it was demonstrated hydrogen production rate per day to about 5 Torr. In contrast, the present invention may be distinguished from the zeolite molecular sieve material on the composition and functionally, and using the carbon sorbent material showing Oite high stability and freedom of decomposition of the sorbate species Yes.

Accordingly, an improved working capacity of the storage and dispensing system of the present invention, the desorption Oyo by other functional properties of beauty-carbon sorbent, the system of the present invention, the storage and dispensing was zeolite with base It is clear that significant progress has been made over the practice of dispensing gaseous materials from systems and prior art from high pressure cylinders.

Storage and dispensing system of the present invention, metering for the use of the dispensed gas can any be both downstream processes operatively connected if appropriate. For example, the storage and dispensing system is in a flow supply relationship, including ion implantation chambers, silicon semiconductor processing plants, compound semiconductor processing plants, flat panel display manufacturing facilities, organic synthesis facilities, drug manufacturing facilities, and small dose masks for anesthetic gases. And any other suitable downstream means or method equipment for end-use of air treatment or water pollution elimination equipment, range or burner in the case of cooking gas, or gas dispensed from the storage and dispensing system of the present invention Connect to anything.

The storage and dispensing system of the present invention can be implemented using a wide variety of sorbents in a wide variety of pore sizes, porosity, morphology and chemical composition.

The storage and dispensing system of the present invention can be used to transport liquids, gases, vapors, multi-component and multi-phase fluid streams, and the like. The storage and dispensing system further may also be used for dispensing of sublimable solids, and the dispensing fluid by connecting the reaction vessel to the storage and dispensing system in an intermediate product or a final product It helps to react against. For example, a storage and dispensing system dispenses borane trifluoride gas into a downstream hydrogenation chamber, where borane trifluoride is contacted with a hydrogenating agent such as magnesium hydroxide under suitable reaction conditions. Diborane is produced for subsequent use, such as ion implantation, doping or other uses.

  Ion implantation is a particularly preferred application of the storage and dispensing system of the present invention and is preferred for dispensing diborane, germane, silicon tetrafluoride and antimony containing gases.

For thermal Grant desorption of the sorbate fluid from the sorbent bed in the storage and dispensing vessel can be used an appropriate energy source, it is RF, IR and UV radiation, Ultrasonic and Micro Wave irradiation and other direct or indirect means and methods, such as electrical resistance heating, heating by spreading a heat transfer surface or heat exchange passage in a sorbent bed.

  The present invention has utility in the manufacture of semiconductor materials and devices as well as other gas consuming process operations, including gases such as hydride gases, halogenated gases, gaseous organometallic group V compounds such as silane, diborane, germane, fluorine, Reliable, including ammonia, phosphine, arsine, stibine, hydrogen sulfide, hydrogen selenide, hydrogen telluride, bromine trifluoride, tungsten hexafluoride, chlorine, hydrogen chloride, hydrogen bromide, hydrogen iodide and hydrogen fluoride Provide a gas source that can be supplied on demand.

Gas safely held at relatively low pressure while being sorbed carbon sorbent material, then, provides an economical and reliable source of gas that is easily dispensed using location gas Thus, the present invention can prevent the dangers associated with the use of conventional high pressure gas cylinders and the problems of gas handling.

The adsorption isotherm for arsine as a plot of arsine loading showing arsine per liter of sorbent material in grams, for carbon sorbent (curve A) and for zeolite 5A (curve B). FIG. 5 is a graph showing with isotherm zones G ₀ and G ₁ as a function of pressure in Torr, further distinguishing the isotherm mode for implementation in one embodiment of the present invention. FIG. 4 is a graphical plot of cumulative pore volume in cm ³ per gram as a function of pore size for several exemplary activated carbon sorbents useful in the broad practice of the present invention. 1 is a schematic diagram of a storage and transport system according to one embodiment of the present invention. The bomb pressure indicated by the torque units, as a function of time indicated by the hour, the plot of pressure decay after the end of the arsine filling operation of arsine gas sorbed on the carbon sorbent in the storage and dispensing system according to the embodiment of FIG. 3 it is the graph. Related to arsine storage and delivery system according to the present invention, as a function of time indicated by the hour, a graph plotting the pressure decay rate indicated by Torr / time unit, pressure characteristics after the filling is shown in Figure 4 The FIG. 5 is a graphical representation of the arsine adsorption isotherm, plotted as a function of storage and dispensing container pressure, expressed in g / liter, sorbing to bead carbon sorbent material, expressed in g / liter . FIG. 3 is a schematic perspective view of a storage and dispensing system according to another embodiment of the present invention. 1 is a schematic perspective view of a method system comprising a gas delivery storage and dispensing system for use in ion implantation of a dispensed gas according to one embodiment of the present invention. FIG. FIG. 9 is a perspective cross-sectional view of the storage and dispensing container of FIG. 8 showing the internal structure of the container. FIG. 5 is a schematic perspective view of a cryopump storage and transfer system according to still another embodiment of the present invention. 1 is a schematic view of a transport measurement device for performance evaluation of a storage and dispensing system according to the present invention. Storage and delivery system consisting of 5A molecular sieve as sorbent material (curve M, data point symbol Δ) and storage and dispensing system consisting of bead activated carbon as sorbent material (curve N, data point symbol □) FIG. 5 is a graph showing the performance of the storage and the storage and metering vessel pressure shown in Torr as a function of working time at a flow rate of 1 standard cm ³ arsine per minute.

10 Gas storage cylinder
11 Heat exchange passage
12 fluid conduit
13 Inlet pipeline
14 Cylinder valve
15 Discharge pipe
16 Cylinder isolation valve
17 beds
20 Branch purge line
22 Purge isolation valve
30 Gas filter
32 Pressure transducer
34 Branch mounting body
36 Bypass conduit
38 Bypass isolation valve
40 Gas flow on / off valve
42 Flow controller
44 coupling
46 Discharge pipe
48 Flow controller
50 coupling
52 elements
54 other end
200 Storage and dispensing system
204 Storage and dispensing containers
206 Valve head
208 Manual actuator
210 coupling
212 fluid conduit
214 pressure transducer
220 flow controller
222 Filter
224 coupling
300 Storage and dispensing system
302 Storage and dispensing containers
304 valve head
306 Manual actuator wheel
307 Flow control valve
308 VCR filtration gasket
309 Flow control valve
310 Pressure transducer
311 valve
312 flow body conduit
314 Check valve
320 Span gauge
322 Flow controller
324 Bypass valve
325 Bypass conduit
326 Manifold conduit
330 coupling
346 Wall
350 sorption material
352 volume
360 porous center tube
400 Cryo-pump storage and transfer system
402 cylinder
404 valve head assembly
406 Isolation valve
408, 409 conduit
410 Isolation valve
412 Flow controller
414 Isolation valve
415, 416 cryopump
418 Isolation valve
420 Medium pressure cylinder
422 Isolation valve
424 Heating element
426 Liquid nitrogen outlet
428 entrance
430 Product dispensing regulator assembly
434 outlet
502 Storage and dispensing system
504 Storage and dispensing containers
506 cylinder valve
508 Gas cylinder isolation valve
510 pressure transducer
512 flow line
514 Inert purge gas source
516 T-shaped connector
518 Inert gas purge line
520 Gas purge isolation valve
522 Connection pipeline
524 flow controller
526 Gas on / off valve
530 pipeline
532, 536 valves
534 Cooling container
538 Vacuum equipment

Claims (16)

An adsorption / desorption device for storing and dispensing sorbent fluid,
A storage and dispensing container configured and arranged to hold a carbon sorbent and selectively allow fluid to flow into or out of the container;
- Before SL it is charged to the storage and dispensing vessel, sorptive fluid suitable for physical adsorption to the carbon adsorbent of the sorption fluid to sorbed carbon sorbent in vessel pressure, the beads A carbon sorbent comprising carbon;
At least a coupling connected in gas flow communication with the storage and dispensing container and connecting the storage and dispensing container and the fluid conduit and at least a further coupling connecting downstream components a dispensing assembly; made, the dispensing assembly and supplies a pressure below the internal pressure of the container to the outside of (I) the storage and dispensing vessel, a sorptive fluid desorbed from the carbon sorbent , fluid flow to the fluid flow of desorption fluid is desorbed so as to pass through the dispensing assembly, and / or,
(II) includes a heating means for heating the carbon-containing sorbent to desorb the sorbed fluid, thermal desorption fluid is flowing fluid that is thermally desorbed so that to flow into said dispensing assembly from said container,
Constructed and arranged such that the carbon sorbent is
(1) at least 50 sorption work capacity, Cw measured at a pressure of 40 torr and 650 torr against arsine gas;
(2) the ratio of desorbable sorbate to arsine gas is at least 15%;
An adsorption / desorption apparatus characterized in that the water content of the carbon sorbent is less than 0.01%. The adsorption / desorption apparatus according to claim 1, wherein the carbon sorbent has a sorption work capacity of at least 100, Cw, measured at a pressure of 40 torr and 650 torr against arsine gas. The adsorption / desorption apparatus according to claim 1, wherein the carbon sorbent has a sorption work capacity of at least 180, Cw, measured at a pressure of 40 torr and 650 torr with respect to arsine gas. The adsorption / desorption apparatus according to claim 1, wherein the carbon sorbent has at least 200 sorption work capacity, Cw, measured at a pressure of 40 torr and 650 torr against arsine gas. The adsorption / desorption apparatus according to claim 1, wherein the carbon sorbent has a monolith structure. Wherein the carbon sorbent, adsorption and desorption apparatus according to claim 1, wherein the sorptive fluid Ru sorbed on the carbon sorbent. The sorbing fluid is silane, diborane, arsine, phosphine, phosgene, chlorine, BCl ₃ , BF ₃ , B ₂ D ₆ , tungsten hexafluoride, hydrogen fluoride, hydrogen chloride, hydrogen iodide, hydrogen bromide, Claims selected from the group consisting of germane, ammonia, stibine, hydrogen sulfide, hydrogen cyanide, hydrogen selenide, hydrogen telluride, deuterated hydride, hydride gas mixture, organo compound, and organometallic compound. 6. The adsorption / desorption device according to 6. The sorbing fluid is composed of an organometallic compound, and the organometallic compound is aluminum, barium, strontium, gallium, indium, tungsten, antimony, silver, gold, palladium, gadolinium, calcium, lithium, potassium, cesium, titanium. , Yttrium, zirconium, lead, tantalum, niobium, vanadium, platinum, thallium, bismuth, tin, tellurium, selenium, nickel, zinc, tungsten, manganese, iron, cobalt, molybdenum, magnesium, scandium, chromium, copper, cadmium, The adsorption / desorption apparatus according to claim 6, comprising a metal component selected from the group consisting of lanthanum and cerium. A method for manufacturing a fluid supply apparatus, wherein the manufacturing method is:
· Carbon sorbent to retain the, and suitable to flow out from the inflow addition vessel selectively the container of fluid, constitute the storage and dispensing vessel,
· Internal pressure of the container with sorptive fluid suitable for physical adsorption to the carbon sorbent sorbing fluid so that to sorbed carbon sorbent and the carbon sorbent containing beads carbon, said reservoir and charged to a dispensing container,
- becomes the dispensing assembly from the method of connecting the storage and through dispensing vessel and a gas flow communication, said dispensing assembly includes a coupling for connecting the storage and dispensing vessel and a fluid conduit, downstream of the Including at least a further coupling coupled to the component ;
(I) the storage and to supply the pressure below the internal pressure of the container to the outside of the dispensing vessel, the desorbed sorption fluid carbon sorbent, desorption fluid flow the dispensing assembly of the fluid Flowing said fluid through and / or
(II) desorbing sorbed fluid includes a heating means for heating the carbon sorbent, thermal desorption fluid is flowing fluid that is thermally desorbed so that to flow into the dispensing assembly from the container
Configured, it is arranged;
The carbon sorbent is:
(1) having a sorption capacity of at least 50, Cw measured at a pressure of 40 torr and 650 torr for arsine gas; and (2) the ratio of desorbable sorbate to arsine gas is at least 15%;
A method for producing a fluid supply device, wherein the water content of the carbon sorbent is less than 0.01%. A method for producing a fluid source comprising: storing the adsorption / desorption device according to claim 1; and sorbing and filling a fluid into a carbon sorbent in a container for dispensing. In the method of supplying a fluid to be used, the storage and adsorption of the adsorption / desorption device according to claim 1, the fluid pre- sorbed and filled in the carbon sorbent in the container for dispensing is desorbed, and the flow through the distribution assembly is used to remove the fluid. A fluid supply method comprising a method of dispensing a fluid desorbed from an adsorption / desorption device.   A method for manufacturing a semiconductor product using a fluid in a product, comprising a method of dispensing the fluid from the adsorption / desorption device according to claim 1 containing the fluid.   An ion implantation method using an ion implantation source fluid, comprising a method of dispensing the fluid from the adsorption / desorption device according to claim 1 including a fluid.   A method of manufacturing a flat panel display product using a fluid in a product, comprising the method of dispensing the fluid from the adsorption / desorption device according to claim 1 containing the fluid. The carbon sorbent as a function of pressure (torr) at a temperature of 25 ° C. in grams of arsine per liter of sorbent :

Pressure (torr) Filling amount (g of arsine per liter of sorbent )
25 35-106
50 62-138
100 100-185
200 145-232
300 168-263
400 177-288
500 185-308
550 188-315
650 192-330;

The adsorption / desorption apparatus according to claim 1, further comprising an adsorption isotherm for arsine gas. The carbon sorbent as a function of pressure (torr) at a temperature of 25 ° C. in grams of arsine per liter of sorbent :

Pressure (torr) Filling amount (g of arsine per liter of sorbent )
25 35-106
50 62-138
100 100-185
200 145-232
300 168-263
400 177-288
500 185-308
550 188-315
650 192-330;

The method for producing a fluid supply apparatus according to claim 9, further comprising an adsorption isotherm for arsine gas having the following characteristics.