WO2015187859A1

WO2015187859A1 - Enhanced capacity fluid storage transport, and dispensing apparatus

Info

Publication number: WO2015187859A1
Application number: PCT/US2015/034034
Authority: WO
Inventors: Glenn M. Tom
Original assignee: Entegris, Inc.
Priority date: 2014-06-03
Filing date: 2015-06-03
Publication date: 2015-12-10
Also published as: TW201603871A

Abstract

A fluid storage, transport, and dispensing apparatus is described, including a transport container configured to hold at least one fluid storage and dispensing vessel holding a storage medium for fluid to be stored on and desorptively dispensed therefrom, and a thermal management assembly constructed and arranged to maintain the vessel and storage medium in a chilled condition. Corresponding methods of supplying fluid are disclosed. The apparatus and methods of the disclosure enable enhanced capacity of fluid to be provided for fluids stored on and dispensed from storage media having increased capacity at decreased temperature, e.g., storage media such as solid phase physical adsorbents, ionic liquids, and reversible chemical reaction storage media.

Description

ENHANCED CAPACITY FLUID STORAGE, TRANSPORT, AND DISPENSING

APPARATUS

CROSS-REFERENCE TO RELATED APPLICATION

[0001] The benefit of priority under 35 USC 119 of U.S. Provisional Patent Application 62/007,387 filed June 3, 2013 in the name of Glenn M. Tom for "ENHANCED CAPACITY FLUID STORAGE, TRANSPORT, AND DISPENSING APPARATUS" is hereby claimed. The disclosure of U.S. Provisional Patent Application 62/007,387 is hereby incorporated by reference, in its entirety, for all purposes.

FIELD

[0002] The present disclosure relates to enhanced capacity fluid storage, transport, and dispensing apparatus and methods of supplying fluids therewith, e.g., for use in manufacturing semiconductor products, flat-panel displays, solar panels, or the like.

DESCRIPTION OF THE RELATED ART

[0002] Physical adsorbent-based gas storage and dispensing apparatus of the type disclosed in Tom et al. U.S. Pat. No. 5,518,528 has revolutionized the transportation, supply and use of hazardous gases in the semiconductor industry. Such apparatus includes a vessel holding a physical adsorbent medium such as molecular sieve, activated carbon, or other adsorbent medium having sorptive affinity for the gas that is to be stored in and selectively dispensed from the vessel. The gas is held in the vessel in an adsorbed state on the sorbent medium at reduced pressure relative to a corresponding empty (of sorbent) vessel holding an equivalent amount of gas in the "free" (unadsorbed) state, and the gas is desorbed from the sorbent medium under dispensing conditions.

[0003] In many applications in which such adsorbent-based fluid supply apparatus are employed, the fluid is stored on the adsorbent at subatmospheric pressure and may be dispensed at corresponding low pressure levels to fluid-utilizing apparatus such as semiconductor manufacturing tools that operate at subatmospheric pressure, e.g., ion implantation tools. When the fluid is maintained at subatmospheric pressure levels in the vessel during storage, transport, and use conditions, a high level of safety is realized, in relation to conventional high-pressure gas cylinders, in which fluid may for example be held at pressures up to 2000 psig (13.8 MPa) or higher.

[0004] Although such adsorbent-based fluid supply apparatus, as designed to maintain subatmospheric pressure conditions in the vessel at ambient temperatures, afford a high level of safety in storage, transport, and use, such subatmospheric pressure conditions limit the amount of fluid that can be delivered by such apparatus to a fluid end-user.

[0005] Accordingly, there is a need for improvement in the capacity of such adsorbent-based fluid supply apparatus, so that higher volumes of fluid can be economically packaged, shipped and utilized.

SUMMARY

[0006] The present disclosure relates to enhanced capacity fluid storage, transport, and dispensing apparatus and methods.

[0007] In one aspect, the disclosure relates to a fluid storage, transport, and dispensing apparatus, comprising a transport container configured to hold at least one fluid storage and dispensing vessel holding a storage medium for fluid to be stored on and desorptively dispensed therefrom, and a thermal management assembly constructed and arranged to maintain the vessel and storage medium in a chilled condition.

[0008] Another aspect of the disclosure relates to a method of supplying fluid for use, comprising packaging the fluid in a fluid storage, transport, and dispensing apparatus according to the present disclosure.

[0009] A further aspect the disclosure relates to a method of supplying fluid for use, comprising transporting the fluid in a fluid storage, transport, and dispensing apparatus according to the present disclosure.

[0010] In another aspect, the disclosure relates to a method of supplying fluid for use, comprising introducing fluid to a storage medium for storage thereon, said storage medium having increasing storage capacity with decreasing temperature, and cooling the fluid and storage medium to chilled temperature during at least one of said introducing, subsequent storage of the fluid on the storage medium, and subsequent transport of the fluid on the storage medium, wherein the fluid on the storage medium at the chilled temperature is at subatmospheric pressure.

[0011] In a further aspect, the disclosure relates to a method of supplying fluid from a storage medium on which it is stored, said method comprising providing the fluid on the storage medium at chilled temperature prior to fluid dispensing, and thereafter dispensing fluid during or subsequent to warming of the fluid and storage medium from the chilled temperature to higher ambient temperature.

[0012] Other aspects, features and embodiments of the disclosure will be more fully apparent from the ensuing description and appended claims.

BRIEF DESCRIPTION OF THE DRAWINGS

[0013] FIG. 1 is a schematic representation of a transport container in which the fluid storage and dispensing apparatus comprises a contained refrigeration source to maintain adsorbent in the storage and dispensing vessels in the container at predetermined chilled temperature conditions.

DETAILED DESCRIPTION

[0014] The present disclosure relates to enhanced capacity fluid storage, transport, and dispensing apparatus and methods, in which thermally sensitive fluid storage and dispensing media can be maintained at appropriate conditions for enhanced capacity supply of fluid.

[0015] As used herein and in the appended claims, the singular forms "a", "and", and "the" include plural referents unless the context clearly dictates otherwise.

[0016] As used herein, the term "chilled condition" refers to temperature below ambient temperature, e.g., temperature at least 10°C below ambient temperature, preferably at least 25°C below ambient temperature and not exceeding 0°C, and most preferably temperature in a range of from -50°C to -80°C.

[0017] The enhanced capacity of fluid storage, transport, and dispensing apparatus in specific embodiments comprises a transport container configured to hold at least one fluid storage and dispensing vessel(s) holding adsorbent with sorptive affinity for fluid to be stored on and desorptively dispensed therefrom, and a thermal management assembly arranged for maintaining the vessel(s) and adsorbent therein in a chilled condition.

[0018] In such fluid storage and dispensing apparatus, the thermal management assembly may comprise a refrigerant medium, e.g., dry ice or other refrigerant, disposed in a compartment or chamber of the transport container. [0019] The transport container may be configured to hold multiple fluid storage and dispensing vessels, as hereinafter described in further detail.

[0020] In specific embodiments, the thermal management assembly is actuated at the fill station where the vessel is initially charged with fluid, to chill the vessel and adsorbent, to increase the adsorbent loading relative to charging at ambient or other higher temperature. Thereafter, the vessel in the fluid storage and dispensing apparatus could be maintained at cold temperature by the thermal management assembly, e.g., during storage and transport. The vessel can be initially charged with fluid while the vessel and/or fluid is/are in a chilled condition, and the resulting fluid-containing vessel can be packed in an insulated or super-insulated transport container, optionally with supplemental refrigerant capability, such as dry ice, liquefied nitrogen as a cold source, or mechanical refrigeration, or supplemental adsorption refrigeration assembly. In this manner, the vessel and adsorbent can be maintained at chilled temperature until fluid dispensing is desired, and optionally thereafter during the dispensing operation.

[0021] By way of specific example, a 5L internal volume adsorbent-based fluid storage and dispensing vessel can be maintained at chilled temperature (for example, a temperature between - 78°C and room temperature) using dry ice (e.g., a quantity of 30-35 kg of C0₂) for a duration of 60-100 days, sufficient to accommodate transport, installation, and use requirements for the fluid storage, transport, and dispensing apparatus.

[0022] Although the storage medium for containing fluid in the broad practice of the present disclosure is primarily described herein as comprising a solid-phase physical adsorbent, it will be appreciated that the scope of applicability of the present disclosure is not thus limited, but rather extends to and encompasses use of other storage media, such as ionic liquids, reversible chemical reaction media interactive with the fluid to be stored, and other media and materials having affinity and suitability as a storage medium for the fluid, and in which the fluid loading capacity of the storage medium is increased with a temperature decrease, e.g., to a temperature below ambient (room) temperature, such as 25°C.

[0023] The storage medium when in the form of a solid-phase physical adsorbent may be of any suitable type, and may for example comprise silica, alumina, aluminosilicates, molecular sieves, carbon, macroreticulate polymers and copolymers, etc. In embodiments, the storage medium may comprise a nanoporous carbon adsorbent having porosity of suitable character for the storage of the fluid to be retained in and dispensed from the fluid storage and dispensing vessel containing such adsorbent.

[0024] Such solid-phase physical adsorbent may be in any suitable form, including particulate or granular forms, or powder forms, or monolithic forms. As used herein, "monolithic" means that the solid-phase physical adsorbent is in a unitary or block-like form, e.g., in the form of blocks, bricks, discs, boules, etc., in contradistinction to conventional finely divided forms such as beads, particles, granules, pellets, and the like, which are generally utilized in the form of a bed comprising a multiplicity of such beads, particles, granules, pellets, etc. Thus, in the bed form of multiple finely divided physical adsorbent elements, the void volume of the active sorbent is in major part interstitial, or inter-particle, in character, varying according to the dimensions, shape and packing density of the sorbent particles. By contrast, in a monolithic form, the void volume of the active sorbent is in form of porosity intrinsic to the sorbent material and voids that may have been formed in the bulk sorbent body during its processing.

[0025] In embodiments, the solid phase physical adsorbent may be in a monolithic form, comprising discs or pucks of adsorbent, e.g., a nanoporous carbon adsorbent.

[0026] The monolithic adsorbent can be formed as the pyrolysis product of an organic resin, and more generally can be formed from any suitable pyrolyzable material, such as for example polyvinylidene chloride, phenol-formaldehyde resins, polyfurfuryl alcohol, coconut shells, peanut shells, peach pits, olive stones, poly aery lonitrile, and polyacrylamide. The adsorbent can be formed in the fluid storage and dispensing vessel in which the fluid will be stored for subsequent dispensing, i.e., in situ, or the adsorbent can be formed and then introduced into the fluid storage and dispensing vessel. In one embodiment, the adsorbent has at least 20% of its porosity in pores with a diameter of less than 2 nanometers.

[0027] The fluid in the fluid storage and dispensing vessel that is sorptively retained on the adsorbent, or otherwise stored on a storage medium, and desorbed under suitable desorbing conditions for dispensing of fluid, or otherwise released from the storage medium, can be fluid of any suitable type, e.g., fluid having utility in manufacturing of semiconductor products, flat-panel displays, solar panels. Examples of such fluids include hydrides, halides and organometallic gaseous reagents, and other fluids, e.g., silane, arsine, phosphine, phosgene, diborane, boron trichloride, boron trifluoride, germane, ammonia, stibine, hydrogen sulfide, hydrogen selenide, hydrogen telluride, nitrous oxide, hydrogen cyanide, ethylene oxide, deuterated hydrides, halide (chlorine, bromine, fluorine, and iodine) compounds, germanium tetrafluoride, silicon tetrafluoride, chlorine, carbon monoxide, xenon, xenon difluoride, hydrogen, and gas mixtures including one or more of the foregoing, or isotopically enriched gases including gas species such as the foregoing (e.g., isotopically enriched germanium tetrafluoride or silicon tetrafluoride), provided as single component gases or in mixture with other gas components.

[0028] Thus, the present disclosure contemplates in embodiments a fluid storage, transport, and dispensing apparatus, comprising a transport container configured to hold at least one fluid storage and dispensing vessel holding a storage medium for fluid to be stored on and desorptively dispensed therefrom, and a thermal management assembly constructed and arranged to maintain the vessel and storage medium in a chilled condition.

[0029] The thermal management assembly in such apparatus may comprise a refrigerant medium, such as dry ice (C0₂). The transport container may be configured to hold multiple fluid storage and dispensing vessels. The thermal management assembly may be constructed and arranged to maintain the vessel and storage medium in a chilled condition for a period of at least 30 days, a period of 60 to 90 days, a period of 3 to 6 months, or other suitable duration.

[0030] The storage medium in the fluid storage and dispensing vessels may comprise a solid phase physical adsorbent, e.g., silica, alumina, aluminosilicates, molecular sieves, carbon, polymers and copolymers. A highly advantageous adsorbent comprises carbon adsorbent, which may be in a monolithic or other form. In other embodiments, the storage medium may comprise an ionic liquid or a reversible chemical reaction storage medium.

[0031] The thermal management assembly in the apparatus of the disclosure may comprise a thermal management component such as insulation, super-insulation, dry ice, liquid nitrogen, mechanical refrigeration assembly, adsorption refrigeration assembly, or combinations of two or more of the foregoing.

[0032] The fluid stored on the storage medium may be of any suitable type, and may be a fluid having utility in manufacturing of semiconductor products, flat-panel displays, or solar panels, e.g., any of hydrides, halides, organometallic compounds, silane, arsine, phosphine, phosgene, diborane, boron trichloride, boron trifluoride, germane, ammonia, stibine, hydrogen sulfide, hydrogen selenide, hydrogen telluride, nitrous oxide, hydrogen cyanide, ethylene oxide, deuterated hydrides, halide (chlorine, bromine, fluorine, and iodine) compounds, germanium tetrafluoride, silicon tetrafluoride, chlorine, carbon monoxide, xenon, xenon difluoride, hydrogen, gas mixtures including one or more of the foregoing, and isotopically enriched gases and gas mixtures including one or more of the foregoing.

[0033] The transport container in the apparatus of the disclosure may comprise an insulated box. The insulated box may contain a refrigerant receptacle including a central refrigerant compartment and partition arms radiating outwardly from the central refrigerant compartment, and defining receiving areas for the at least one fluid storage and dispensing vessel. For example, the refrigerant receptacle may have a cruciform shape in cross-section, and be configured to accommodate a single fluid storage and dispensing vessel between each of adjacent partition arms thereof. The refrigerant may comprise dry ice (C0₂). In specific embodiments, the insulated box may contain four fluid storage and dispensing vessels, each containing carbon adsorbent having fluid adsorbed thereon. The refrigerant receptacle in specific embodiments may contain 30-35 kg dry ice (C0₂).

[0034] The disclosure contemplates a method of supplying fluid for use, comprising packaging the fluid in a fluid storage, transport, and dispensing apparatus as variously described herein. The disclosure also contemplates a method of supplying fluid for use, comprising transporting the fluid in the fluid storage, transport, and dispensing apparatus as variously described herein.

[0035] In another aspect, the disclosure relates to a method of supplying fluid for use, comprising introducing fluid to a storage medium for storage thereon, the storage medium having increasing storage capacity with decreasing temperature, and cooling the fluid and storage medium to chilled temperature during at least one of the introducing, subsequent storage of the fluid on the storage medium, and subsequent transport of the fluid on the storage medium, wherein the fluid on the storage medium at the chilled temperature is at subatmospheric pressure.

[0036] Such method may further comprise cooling at least one of the fluid and storage medium prior to the introducing of the fluid to the storage medium for storage thereon.

[0037] The aforementioned method may further comprise terminating the cooling to enable the fluid to increase in pressure.

[0038] The aforementioned method may comprise dispensing at least part of the fluid from the storage medium, e.g., at superatmospheric pressure, or alternatively at subatmospheric or atmospheric pressure. The method may be carried out using the storage medium comprising a solid phase physical adsorbent, e.g., adsorbent selected from the group consisting of silica, alumina, aluminosilicates, molecular sieves, carbon, polymers and copolymers. As previously indicated, the adsorbent may comprise carbon adsorbent, e.g., in a monolithic form, or a particulate or other finely divided form. The storage medium may alternatively comprise an ionic liquid, or a reversible chemical reaction storage medium.

[0039] The cooling in the above-described method may be effected by a refrigerant medium such as dry ice (C0₂), or by a mechanical refrigeration assembly or and adsorption refrigeration assembly. The fluid, as previously described may comprise a fluid having utility in manufacturing of semiconductor products, flat-panel displays, or solar panels, such as a fluid selected from the group consisting of hydrides, halides, organometallic compounds, silane, arsine, phosphine, phosgene, diborane, boron trichloride, boron trifluoride, germane, ammonia, stibine, hydrogen sulfide, hydrogen selenide, hydrogen telluride, nitrous oxide, hydrogen cyanide, ethylene oxide, deuterated hydrides, halide (chlorine, bromine, fluorine, and iodine) compounds, germanium tetrafluoride, silicon tetrafluoride, chlorine, carbon monoxide, xenon, xenon difluoride, hydrogen, gas mixtures including one or more of the foregoing, and isotopically enriched gases and gas mixtures including one or more of the foregoing.

[0040] The cooling in the above-described method may be conducted during the introducing, and/or during the subsequent storage of fluid on the storage medium, and/or during the subsequent transport of the fluid on the storage medium.

[0041] The disclosure in another aspect relates to a method of supplying fluid from a storage medium on which it is stored, such method comprising providing the fluid on the storage medium at chilled temperature prior to fluid dispensing, and thereafter dispensing fluid during or subsequent to warming of the fluid and storage medium from the chilled temperature to higher ambient temperature. In this method, the dispensing may comprise dispensing fluid from the storage medium at superatmospheric pressure, or alternatively at subatmospheric or atmospheric pressure. The dispensing may be conducted during warming of the fluid and storage medium from the chilled temperature to higher ambient temperature, or the dispensing may be conducted subsequent to warming of the fluid and storage medium from the chilled temperature to the higher ambient temperature. The storage medium as in other embodiments may comprise a solid phase physical adsorbent, such as those previously described, e.g., a carbon adsorbent in a monolithic or other form, or an ionic liquid or a reversible chemical reaction storage medium. The fluid stored on the storage medium may be of any suitable type, including the fluid compositions previously described herein.

[0042] Referring now to the drawing, FIG. 1 is a schematic representation of an enhanced capacity fluid storage, transport, and dispensing apparatus comprising a transport container in which the fluid storage and dispensing vessels are provided together with a contained refrigeration source that is effective to maintain the adsorbent and fluid in the fluid storage and dispensing vessels in the transport container at predetermined chilled temperature conditions.

[0043] As shown in FIG. 1 , the fluid storage and dispensing apparatus comprises a transport container 10, including an upper portion 12 that is matably engageable with a lower portion 14. The specific matable engagement structure on the respective upper and lower portions 12 and 14 of the transport container may include cavities in such upper and lower portions in which the fluid storage and dispensing vessels can be reposed, so that when the vessels are installed in the transport container, with lower portions of the vessels reposed in cavities in the lower portion 14, and upper portions of the vessels reposed in cavities in the upper portion 12, the upper and lower portions are aligned in registration with one another, when the upper and lower portions of the transport container are brought into engagement with one another. [0044] In addition, the upper and lower portions 12 and 14 of the transport container may be equipped with interconnectable couplings, locking members, etc. (not shown in FIG. 1) so that the mated upper and lower portions 12 and 14 are fixedly secured to one another.

[0045] Referring to the lower portion 14 of FIG. 1, such lower portion 14 defines an interior volume 16 in which is disposed four vertically elongate fluid storage and dispensing vessels 18, 20, 22, and 24, arranged in respective sectors of the interior volume demarcated by the cruciform receptacle 26. The cruciform receptacle 26 includes four arms extending radially outwardly from a central portion of such receptacle. The arms and central portion of the receptacle define an X- shaped cross-section as shown in the perspective view of FIG. 1 , which may be open at its upper end, with the arms and central portion defining an interior volume adapted to receive a refrigerant medium at such open upper end. Alternatively, the cruciform receptacle 26 may include an upper cover that serves with a main body of the receptacle to provide an enclosed volume for containment of the refrigerant medium.

[0046] Although shown as having an X-shaped cross-section in the embodiment illustrated, it will be appreciated that the refrigerant medium receptacle may be of other forms and shapes, as adapted to hold a refrigerant medium and to provide a demarcation of the interior volume of the lower portion of the transport container in which fluid storage and dispensing vessels holding adsorbent and adsorbed fluid can be placed in a corresponding cavity or volumetric region of such lower portion.

[0047] The upper portion 12 of the transport container is shown as being provided with cavities 32, 34, 36, and 38 therein in which the upper parts of the fluid storage and dispensing vessels 18, 20, 22, and 24 are respectively positioned when the upper and lower portions of the transport container are mated with one another.

[0048] Associated with the upper portion 12 of the transport container is a module 30 that may comprise a thermal management assembly for the transport container. The module may additionally, or alternatively, comprise a compartment in which additional refrigerant medium or other refrigerant capability can be provided.

[0049] When the module 30 comprises a thermal management assembly for the transport container, such assembly may be configured to monitor the condition of the vessels in the container and/or fluid in the vessels and/or fluid storage media in the vessels. For example, the assembly may comprise one or more thermocouples or other thermal sensors that are arranged to monitor temperature of the container, vessels, and/or vessel contents, and to output thermal sensing signals. Such thermal sensing signals may be transmitted to a processor, display, or other output apparatus or medium, to effectuate the monitoring operation. [0050] In various embodiments, the signals may be transmitted to a processor, e.g., microprocessor, programmable logic controller, central processing unit, special purpose programmed computer, etc., that in turn is coupled with one or more devices or assemblies for modulating the thermal condition of or in the container or its contents (fluid storage and dispensing vessels, adsorbent or other storage media in the vessels, fluid in the vessels, or combinations thereof). Such thermal modulation may be of any suitable type and may for example include release of cryogenic vapor from a dewar, containing liquid nitrogen or other cryogen, disposed in the interior volume of the transport container, and coupled to the processor so as to maintain predetermined chilled temperature of the vessels and their contents in the transport container.

[0051] The thermal management module 30 in other embodiments may comprise a refrigeration compartment in which a refrigeration source, e.g., dry ice, liquid nitrogen, or other refrigerant medium or assembly, is disposed.

[0052] The transport container of the present disclosure enables fluid storage and transport vessels holding storage medium on which fluid is stored, wherein the storage medium capacity for the fluid is increased with decreasing temperature, to be maintained at low temperature for extended periods of time, e.g., 3-6 months. By maintaining the fluid storage medium at lower temperature, a larger inventory of fluid can be stored on the storage medium, thus increasing the cost-efficiency of the fluid storage, transport, and dispensing operation.

[0053] The transport container of the present disclosure correspondingly enables pressure modulation and control of the fluid in the fluid storage and dispensing vessel deriving from the thermal management of such fluid and storage medium on which the fluid is stored. For example, the fluid storage and dispensing vessel may be chilled during transport and subsequent storage in the transport container so that the gas inventory is held by the storage medium at subatmospheric pressure, thereby providing a high level of safety in such transport operation, relative to conventional high pressure gas cylinders. After installation of the vessel at the fluid-utilizing facility, e.g., in a semiconductor manufacturing facility, the refrigeration chilling of the vessel may be discontinued, so that the increased inventory of fluid therein upon warming may thereafter rise above one atmosphere but return to sub-atmospheric pressure during subsequent use as fluid is dispensed from the vessel. This mode of operation thus provides the enhanced safety of the fluid supply vessel during transport and storage of the vessel, accommodates subsequent rise of the fluid pressure in the vessel, e.g., to low superatmospheric pressure, after the vessel has been installed for fluid-dispensing service (for example, in a gas box of an ion implanter), with subsequent fluid-dispensing operation involving sub -atmospheric pressure in the fluid dispensing vessel.

[0054] The fluid storage and dispensing vessel and fluid storage medium therein may be chilled at the point of initial filling, and the fluid itself may be chilled so as to load the fluid storage medium with an increased loading of fluid, relative to operation in which such chilling of the vessel, storage medium, and/or fluid is not carried out.

[0055] For example, a chilled fluid storage and dispensing vessel could be maintained at chilled temperature during initial fluid charging, subsequent storage and transport, but with chilling of the vessel and adsorbent therein being terminated upon installation at an end use fluid- utilizing facility, so that the fluid storage and dispensing vessel in subsequent use warms to ambient environmental conditions, with the pressure of the dispensed gas rising as the temperature rises in the warming vessel and adsorbent.

[0056] Alternatively, the fluid storage and dispensing vessel could be charged with fluid at superatmospheric pressure, and ambient temperature, with such pressure and temperature conditions being maintained during storage and transport, and otherwise until the fluid storage and dispensing apparatus is installed at the fluid-utilization facility.

[0057] At that point of installation, the fluid storage and dispensing vessel and adsorbent therein could be chilled to provide for subatmospheric pressure dispensing, with cessation of the chilling to accommodate warming of the vessel and adsorbent during a later stage of the dispensing operation, so that subatmospheric pressure in the dispensed fluid is maintained throughout the dispensing operation, with warming during the latter stages of the dispensing operation serving to increase fluid pressure in the fluid supply vessel, to assist in dispensing of residual fluid, i.e., heels fluid, from the vessel.

[0058] The transport container of the present disclosure may be employed in container arrays of suitable character for unitary shipment of arrays. For example, four transport containers of the type shown in FIG. 1 may be provided on a 110 cm x 110 cm pallet, so that the pallet contains 16 vessels in the four containers, with cooling provided by dry ice at -78°C. Insulating plugs can be provided in the containers to control the specific extent of cooling and temperature reduction therein. In this manner, vessels can be temperature -regulated, e.g., in a temperature range of from about -20°C to -70°C, to accommodate long-duration cold storage and shipment of the fluid storage and dispensing apparatus.

[0059] In general, any suitable features and assemblies may be employed to ensure that temperature within the transport container remains low. As mentioned, temperature sensors can be employed with thermal modulation equipment or capability. Scales may be employed to measure transport container weight, to establish the nature and extent of the refrigeration capability that will be necessary to maintain a desired temperature level of the fluid supply vessels and fluid storage medium and fluid held therein. The specific design of the transport container may be varied to accommodate any suitable number of fluid storage and dispensing vessels, e.g., by partitioning, formation of receiving cavities therein, etc.

[0060] The transport container itself may be formed of any suitable materials of construction, including metals, wood, ceramics, plastics, cellulosic materials, woven or nonwoven materials, composites, etc. In various embodiments, the transport container may be formed of a suitable insulating material, such as a polymeric rigid structural foam material, to suppress or retard heat transfer from the ambient environment to the fluid supply vessels in the transport container. The transport container may display comprise insulating materials as well as non-and swimming materials, such as an outer sheet metal shell enclosing a foam insulation mass in the interior that is shaped or otherwise accommodated so that one or more fluid supply vessels can be introduced into the transport container. Super insulation materials may be employed to enhance the maintenance of low temperature in the transport container, to accommodate the duration of associated storage and transport of the fluid supply vessel before it is placed in use for dispensing fluid to a fluid-utilizing facility or tool.

[0061] The transport containers of the present disclosure may be constructed and arranged to maintain the fluid supply vessels in a chilled state for an extended period of time, e.g., a duration of 60-90 days, of 3-6 months, of at least 30 days, or of other selected duration that is appropriate for the specific fluid supply vessels, fluid storage medium therein, and fluid stored on the storage medium in such vessels. The fluid storage medium may comprise a solid-phase physical adsorbent medium, ionic liquid, reversible chemical reaction storage medium, or other storage medium for material.

[0062] Thus, the transport container containing one or more fluid storage and dispensing vessels can be flexibly tailored to specific application requirements, with temperature and pressure of fluid in the fluid supply vessels in the container being modulatable in a variety of alternative and/or additive approaches.

[0063] The features and advantages of the present disclosure are further apparent from the ensuing non-limiting example.

[0064] EXAMPLE 1

[0065] A transport container of the type shown in FIG. 1 is provided, as an insulated container defining a constant temperature box for holding for adsorbent-based gas storage and dispensing vessels, each holding adsorbent, e.g., porous carbon adsorbent that has gas adsorbed thereon. The gas may be of any suitable type, and may for example include arsine, phosphine, boron trichloride, boron trifluoride, germane, germanium tetrafluoride, silane, silicon tetrafluoride, chlorine, carbon monoxide, xenon, xenon difluoride, hydrogen, diborane, or other hydride gases, halide gases, or organometallic precursor gases, and gas mixtures including one or more of the foregoing, or isotopically enriched gases including gas species such as the foregoing, e.g., isotopically enriched germanium tetrafluoride or silicon tetrafluoride.

[0066] The cruciform receptacle 26 (see FIG. 1) is filled with dry ice (C0₂). The fluid supply vessels 18, 20, 22, and 24 are pre-chilled to a desired temperature to reduce the load of the C0₂ refrigerant. The constant temperature box may contain a polyurethane thermal insulation to assist in maintenance of the desired temperature.

[0067] The thermal insulation value for the polyurethane thermal insulation is 0.71(W*in)/(m²*°K), wherein W is Watts, ' 'in" is thickness in inches, m² is area in square meters, and °K is temperature in degrees Kelvin. Accordingly, for polyurethane thermal insulation in the transport container, having an area of 0.1 m², a thickness of 3 inches, and a temperature difference of 100°K between the fluid supply vessel and ambient environment of the transport container, the transmission of heat into the refrigerant (C0₂) in the constant temperature box will be 2.36 Watts. Since the heat of vaporization of C0₂ is 574 kJ/kg, 1 kg of C0₂ can accommodate 2.36 W (J/sec) for 1.9 x 10⁵ seconds (= 68 hours). In order to maintain this temperature for 90 days, 32 kg of C0₂ is required. To the extent that insulation can be improved, e.g., by use of greater thicknesses of insulation, augmentation with super-insulation, etc., a given amount of C0₂ can be utilized longer. For example, in the FIG. 1 transport container, the gas supply vessels may be positioned at a distance of 3 inches from the cruciform receptacle arms, with thickness of the insulation being greater than 3 inches, in which case less than 32 kg of C0₂ would be needed to maintain the desired temperature.

[0068] As mentioned, multiple transport containers of the type shown in FIG. 1 can be packaged for shipment on a single pallet, and such arrangement will further reduce heat influx on the interior walls of the respective transport containers in such arrangement (i.e., the interior walls being abutted against interior walls of adjacent transport containers, in face-to-face contact). Additionally, further layers of insulation may be applied exteriorly of the assembled array of multiple transport containers, to further suppress influx of heat from the ambient environment.

[0069] The temperature of the fluid supply vessel in the transport container at equilibrium will be related to the distance between the refrigerant chamber (the cruciform receptacle 26 in the FIG. 1 transport container) and the vessel, e.g., a linear drop in temperature from the vessel wall to the refrigerant. If it is desirable to maintain the fluid supply vessels at the temperature of the refrigerant, open channels between the fluid supply vessels and a central refrigerant chamber can be employed to effectuate such temperature maintenance. Such open channels could be provided, for example, by use of a cover for the cruciform receptacle that is perforated in character, with openings providing fluid communication between the refrigerant in the receptacle and the vessels held in the interior volume of the transport container.

[0070] The fluid supply vessel in the above -described transport container could be initially loaded to pressure of 1500Torr at room temperature, and subsequently cooled so that the vapor pressure of the gas in the adsorbent-based vessel is reduced to below 760 Torr, i.e., to a subatmospheric pressure, with the vessel thereafter being maintained at low temperatures sufficient to maintain the subatmospheric pressure of the gas in the vessel, during subsequent storage and transport of the transport container, prior to use of the fluid supply vessel therein.

[0071] At the point of use, the user will remove the fluid supply vessel from the constant temperature box and quickly connect the vessel to the fluid utilizing apparatus or tool, e.g., an ion implanter. If this hook-up operation is conducted sufficiently quickly, it can be completed with the gas in the fluid supply vessel remaining at subatmospheric pressure. Upon warming of the vessel to room temperature after it has been installed, the pressure will rise above atmospheric pressure and the user would thus be provided with an increased capacity of gas, related to the loading difference between 760 Torr, at which the vessel would be loaded with fluid at ambient (room) temperature so that pressure in the vessel subsequently does not exceed atmospheric pressure in subsequent storage and transport, in the absence of chilling of the vessel, and the 1500 Torr charging pressure in the foregoing example.

[0072] The time during which the temperature of the fluid supply vessel can be maintained at low temperature and pressure can be increased during handling for shipping or installation, by incorporating an insulating sleeve around the main body of the fluid supply vessel that is retained on the vessel after its removal from the transport container, and during subsequent installation of the fluid supply vessel at the point of use. The sleeve then may be removed from the vessel after installation, so that it does not interfere with the subsequent ability of the vessel to dispense fluid.

[0073] After fluid has been dispensed from the fluid supply vessel, it will again be at a subatmospheric internal pressure, and thus in a safe condition for subsequent shipment for refilling or other disposition.

[0074] It will be recognized that the costs associated with packaging and shipping of fluid supply vessels in the transport container of the present disclosure are relatively low in relation to the cost and value of the fluid that thereby is provided, so that the achievement of increased capacity of fluid supply vessels in the manner of the present disclosure enables a decreased cost of ownership to be realized by the fluid user, using low-cost refrigerant medium such as C0₂.

[0075] While the disclosure has been set forth herein in reference to specific aspects, features and illustrative embodiments, it will be appreciated that the utility of the disclosure is not thus limited, but rather extends to and encompasses numerous other variations, modifications and alternative embodiments, as will suggest themselves to those of ordinary skill in the field of the present disclosure, based on the description herein. Correspondingly, the disclosure as hereinafter claimed is intended to be broadly construed and interpreted, as including all such variations, modifications and alternative embodiments, within its spirit and scope.

Claims

THE CLAIMS What is claimed is:

1. A fluid storage, transport, and dispensing apparatus, comprising a transport container configured to hold at least one fluid storage and dispensing vessel holding a storage medium for fluid to be stored on and desorptively dispensed therefrom, and a thermal management assembly constructed and arranged to maintain the vessel and storage medium in a chilled condition.

2. The apparatus of claim 1 , wherein the thermal management assembly comprises a refrigerant medium.

3. The apparatus of claim 2, wherein the refrigerant medium comprises dry ice (C0₂).

4. The apparatus of claim 1 , wherein the transport container is configured to hold multiple fluid storage and dispensing vessels.

5. The apparatus of claim 1, wherein the thermal management assembly is constructed and arranged to maintain the vessel and storage medium in a chilled condition for a period of at least 30 days.

6. The apparatus of claim 1, wherein the thermal management assembly is constructed and arranged to maintain the vessel and storage medium in a chilled condition for a period of from 60 to 90 days.

7. The apparatus of claim 1, wherein the thermal management assembly is constructed and arranged to maintain the vessel and storage medium in a chilled condition for a period of from 3 to 6 months.

8. The apparatus of claim 1, wherein the storage medium in the at least one fluid storage and dispensing vessel comprises a solid-phase physical adsorbent.

9. The apparatus of claim 8, wherein the solid-phase physical adsorbent comprises adsorbent selected from the group consisting of silica, alumina, aluminosilicates, molecular sieves, carbon, polymers and copolymers.

10. The apparatus of claim 8, wherein the solid phase physical adsorbent comprises carbon adsorbent.

11. The apparatus of claim 10, wherein the carbon adsorbent is in a monolithic form.

12. The apparatus of claim 1, wherein the storage medium comprises an ionic liquid.

13. The apparatus of claim 1, wherein the storage medium comprises a reversible chemical reaction storage medium.

14. The apparatus of claim 1, wherein the thermal management assembly comprises a thermal management component selected from the group consisting of insulation, super-insulation, dry ice, liquid nitrogen, mechanical refrigeration assembly, adsorption refrigeration assembly, and combinations of two or more of the foregoing.

15. The apparatus of claim 1, further comprising a fluid stored on the storage medium.

16. The apparatus of claim 15, wherein the fluid stored on the storage medium comprises a fluid selected from the group consisting of fluids having utility in manufacturing of semiconductor products, flat-panel displays, or solar panels.

17. The apparatus of claim 15, wherein the fluid stored on the storage medium comprises a fluid selected from the group consisting of hydrides, halides, organometallic compounds, silane, arsine, phosphine, phosgene, diborane, boron trichloride, boron trifluoride, germane, ammonia, stibine, hydrogen sulfide, hydrogen selenide, hydrogen telluride, nitrous oxide, hydrogen cyanide, ethylene oxide, deuterated hydrides, halide (chlorine, bromine, fluorine, and iodine) compounds, germanium tetrafluoride, silicon tetrafluoride, chlorine, carbon monoxide, xenon, xenon difluoride, hydrogen, gas mixtures including one or more of the foregoing, and isotopically enriched gases and gas mixtures including one or more of the foregoing.

18. The apparatus of claim 1, wherein the transport container comprises an insulated box.

19. The apparatus of claim 18, wherein the insulated box contains a refrigerant receptacle including a central refrigerant compartment and partition arms radiating outwardly from the central refrigerant compartment, and defining receiving areas for the at least one fluid storage and dispensing vessel.

20. The apparatus of claim 19, wherein the refrigerant receptacle has a cruciform shape in cross- section, and is configured to accommodate a single fluid storage and dispensing vessel between each of adjacent partition arms thereof.

21. The apparatus of claim 20, wherein the refrigerant receptacle contains dry ice (C0₂).

22. The apparatus of claim 20, wherein the insulated box contains four fluid storage and dispensing vessels.

23. The apparatus of claim 22, wherein each of the four fluid storage and dispensing vessels contains carbon adsorbent having fluid adsorbed thereon.

24. The apparatus of claim 21, wherein the refrigerant receptacle contains 30-35 kg dry ice (C0₂).

25. A method of supplying fluid for use, comprising packaging the fluid in a fluid storage, transport, and dispensing apparatus according to any one of claims lto 24.

26. A method of supplying fluid for use, comprising transporting the fluid in a fluid storage, transport, and dispensing apparatus according to any one of claims lto 24.

27. A method of supplying fluid for use, comprising introducing fluid to a storage medium for storage thereon, said storage medium having increasing storage capacity with decreasing temperature, and cooling the fluid and storage medium to chilled temperature during at least one of said introducing, subsequent storage of the fluid on the storage medium, and subsequent transport of the fluid on the storage medium, wherein the fluid on the storage medium at the chilled temperature is at subatmospheric pressure.

28. The method of claim 27, further comprising cooling at least one of the fluid and storage medium prior to said introducing of the fluid to the storage medium for storage thereon.

29. The method of claim 27, further comprising terminating the cooling to enable the fluid to increase in pressure.

30. The method of claim 29, comprising dispensing at least part of the fluid from the storage medium.

31. The method of claim 30, wherein the fluid is dispensed in the dispensing, at superatmospheric pressure.

32. The method of claim 30, wherein the fluid is dispensed in the dispensing, at subatmospheric pressure.

33. The method of claim 27, wherein the storage medium comprises a solid phase physical adsorbent.

34. The method of claim 33, wherein the solid-phase physical adsorbent comprises adsorbent selected from the group consisting of silica, alumina, aluminosilicates, molecular sieves, carbon, polymers and copolymers.

35. The method of claim 33, wherein the solid phase physical adsorbent comprises carbon adsorbent.

36. The method of claim 35, wherein the carbon adsorbent is in a monolithic form.

37. The method of claim 27, wherein the storage medium comprises an ionic liquid.

38. The method of claim 27, wherein the storage medium comprises a reversible chemical reaction storage medium.

39. The method of claim 27, wherein the cooling is effected by a refrigerant medium.

40. The method of claim 39, wherein the refrigerant medium comprises dry ice (C0₂).

41. The method of claim 27, wherein the cooling is effected by a mechanical refrigeration assembly or an adsorption refrigeration assembly.

42. The method of claim 27, wherein the fluid comprises a fluid selected from the group consisting of fluids having utility in manufacturing of semiconductor products, flat-panel displays, or solar panels.

43. The method of claim 27, wherein the fluid comprises a fluid selected from the group consisting of hydrides, halides, organometallic compounds, silane, arsine, phosphine, phosgene, diborane, boron trichloride, boron trifluoride, germane, ammonia, stibine, hydrogen sulfide, hydrogen selenide, hydrogen telluride, nitrous oxide, hydrogen cyanide, ethylene oxide, deuterated hydrides, halide (chlorine, bromine, fluorine, and iodine) compounds, germanium tetrafluoride, silicon tetrafluoride, chlorine, carbon monoxide, xenon, xenon difluoride, hydrogen, gas mixtures including one or more of the foregoing, and isotopically enriched gases and gas mixtures including one or more of the foregoing.

44. The method of claim 27, wherein said cooling is conducted during said introducing.

45. The method of claim 27, wherein said cooling is conducted during said subsequent storage of fluid on the storage medium.

46. The method of claim 27, wherein said cooling is conducted during said subsequent transport of the fluid on the storage medium.

47. A method of supplying fluid from a storage medium on which it is stored, said method comprising providing the fluid on the storage medium at chilled temperature prior to fluid dispensing, and thereafter dispensing fluid during or subsequent to warming of the fluid and storage medium from the chilled temperature to higher ambient temperature.

48. The method of claim 47, wherein said dispensing comprises dispensing fluid from the storage medium at superatmospheric pressure.

49. The method of claim 47, wherein said dispensing comprises dispensing fluid from the storage medium at subatmospheric pressure.

50. The method of claim 47, wherein said dispensing is conducted during warming of the fluid and storage medium from the chilled temperature to higher ambient temperature.

51. The method of claim 47, wherein said dispensing is conducted subsequent to warming of the fluid and storage medium from the chilled temperature to higher ambient temperature.

52. The method of claim 47, wherein the storage medium comprises a solid phase physical adsorbent.

53. The method of claim 52, wherein the solid-phase physical adsorbent comprises adsorbent selected from the group consisting of silica, alumina, aluminosilicates, molecular sieves, carbon, polymers and copolymers.

54. The method of claim 52, wherein the solid phase physical adsorbent comprises carbon adsorbent.

55. The method of claim 54, wherein the carbon adsorbent is in a monolithic form.

56. The method of claim 47, wherein the storage medium comprises an ionic liquid.

57. The method of claim 47, wherein the storage medium comprises a reversible chemical reaction storage medium.

58. The method of claim 47, wherein the fluid comprises a fluid selected from the group consisting of fluids having utility in manufacturing of semiconductor products, flat-panel displays, or solar panels.

59. The method of claim 47, wherein the fluid comprises a fluid selected from the group consisting of hydrides, halides, organometallic compounds, silane, arsine, phosphine, phosgene, diborane, boron trichloride, boron trifluoride, germane, ammonia, stibine, hydrogen sulfide, hydrogen selenide, hydrogen telluride, nitrous oxide, hydrogen cyanide, ethylene oxide, deuterated hydrides, halide (chlorine, bromine, fluorine, and iodine) compounds, germanium tetrafluoride, silicon tetrafluoride, chlorine, carbon monoxide, xenon, xenon difluoride, hydrogen, gas mixtures including one or more of the foregoing, and isotopically enriched gases and gas mixtures including one or more of the foregoing.

60. The method of claim 47, as conducted in a process for manufacturing a semiconductor products, flat-panel display, or solar panel.