Storage and transport vessels for storing geh4 using zeolite adsorbents

Abstract

Described herein are storage and dispensing systems and related methods for selectively dispensing germane (GeH4) as a reagent gas from a vessel in which the germane is held in an adsorbed relationship with a solid adsorbent medium comprising a zeolitic imidazolate framework.

Description

TECHNICAL FIELD

[0001] The present invention relates generally to storage and dispensing systems and related methods for selectively dispensing germane (GeH4) as a reagent gas from a vessel in which germane is held in an adsorbed relationship with a solid adsorbent medium comprising a zeolitic imidazolate framework. BACKGROUND

[0002] Gaseous feedstocks, sometimes referred to as "reagent gases," are used in a wide range of industries and industrial applications. Some examples of industrial applications include those used in the processing of semiconductor materials or microelectronic devices, such as ion implantation, epitaxial growth, plasma etching, reactive ion etching, metallization, physical vapor deposition, chemical vapor deposition, atomic layer deposition, plasma deposition, photolithography, cleaning, and doping, among others, including those used in processes for manufacturing semiconductor, microelectronic, photovoltaic, and flat panel display devices and products.

[0003] Reliable sources of high purity reagent gases are continually needed in the manufacture of semiconductor materials and devices, as well as in various other industrial processes and applications. Examples include silane, germane (GeH4), ammonia, phosphine, arsine, diborane, stibine, hydrogen sulfide, hydrogen selenide, hydrogen telluride, and the corresponding and other halide (chloro, bromo, iodo, and fluoro) compounds. Many of these gases must be stored, transported, handled, and used in conjunction with high attention to grade and numerous safety precautions, such as storage vessels for reagent gases that are contained at sub-atmospheric pressures.

[0004] A variety of different types of containers are used to contain, store, transport, and dispense reagent gases for industrial use. Some containers, referred to herein as "adsorbent-based containers," use a porous adsorbent material contained within the container to contain a gas, with the reagent gas being stored by being adsorbed onto the adsorbent material. The adsorbed reagent gas can be contained in equilibrium with reagent gas that is also present in the container in condensed or gaseous form.

[0005] Gaseous feedstocks must be shipped for use in concentrated or substantially pure form, and must be usable in a packaged form that provides a reliable supply of the gas for efficient use of the gas in a manufacturing system.

[0006] In addition to high purity, another desirable feature of a stored gas product is a large amount of deliverable gas that can be dispensed from the stored container product. A larger amount of deliverable material in a container (a higher "deliverable gas capacity") improves efficiency in using the stored gas product and its contained gaseous feedstock in a manufacturing process because the container can be used for a longer period of time without replacement (relative to a container with a lower amount of deliverable material). If the frequency of replacing a used (e.g., empty) container with a new container is reduced, operational efficiency is increased. In addition, a reduced amount of expensive gaseous feedstock is not used, i.e., wasted, within the storage container. SUMMARY

[0007] Germane (GeH4) is used in the semiconductor processing industry for various purposes, for example, as a germane source gas for epitaxial growth of germanium. When used in semiconductor processing, germane must be provided at very high purity. In commercial product form, germane gas has been available as germane gas adsorbed on a solid adsorbent and stored in a cylinder from which the germane gas can be dispensed at high purity levels.

[0008] The purity of germane delivered from current and past adsorbent-based storage systems is sufficient for many commercial uses. In addition, there is a continuing need for ever-higher purity levels of germane for semiconductor processing. Germane is known to decompose during storage to produce hydrogen gas (H2), including when stored within adsorbent-based storage systems. A desirable or preferred germane storage system would be one that stores germane under conditions that do not cause or allow excessive degradation of the germane, for example, a system that stores germane under conditions that allow only a small amount of decomposition of the germane during storage. Thus, a desirable feature of an adsorbent-based system for storing germane is a reduced or minimal amount of decomposition of the germane that occurs during storage, and a concomitant reduced or minimal amount of hydrogen gas contained in the gaseous germane delivered from the storage system.

[0009] An example of a useful or preferred system for storing germane in a storage container that contains a zeolitic imidazolate framework adsorbent can exhibit a useful or relatively small amount of germane degradation during storage of the stored germane. For example, after storage at ambient temperature (e.g., 32°C) for 365 days, the germane stored in a storage container as described can undergo less than 1% degradation of the initial adsorbed germane, or preferably less than 0.1% decomposition, or more preferably less than 0.01% decomposition.

[0010] It can also be desirable for an adsorbent-based system for storing germane to be one that exhibits a useful storage capacity in combination with a useful or advantageously high deliverable gas capacity. A storage container that contains a zeolitic imidazolate framework as an adsorbent to contain adsorbed germane at sub-atmospheric pressure as described can exhibit a useful storage capacity in combination with a useful or advantageously deliverable capacity.

[0011] The "storage capacity" or "total storage capacity" of a storage vessel containing adsorbent and adsorbed reagent gas (e.g., germane) refers to the amount of reagent gas that can be contained in the vessel per volume of the vessel; an alternative measure of storage capacity is the total weight of reagent gas (e.g., grams) per weight of adsorbent (e.g., grams). Storage capacity is measured as the amount of gas that can be contained in a vessel containing adsorbent per total volume of the vessel. Zeolitic imidazolate framework adsorbents for storing reagent gas (e.g., germane) at sub-atmospheric pressure can inherently have lower storage capacity compared to other types of adsorbents (e.g., carbon-based adsorbents).

[0012] A different measure of performance of an adsorbent-type storage system is the "deliverable capacity" of a vessel containing reagent gas stored in a vessel with adsorbent. The "deliverable capacity" refers to the amount of stored reagent gas contained in a vessel and that can be delivered from the vessel in a useful form compared to the total amount of reagent gas contained in the vessel. Deliverable capacity can be described as the amount (percentage) of stored gas that can be delivered (vented) from a vessel compared to the total amount of stored gas within a storage vessel. It can be desirable for the deliverable capacity of gas contained in a commercial storage vessel to be at least 50% or 70% of the total amount of gas contained in the vessel.

[0013] According to exemplary storage systems described herein, a storage vessel containing zeolitic imidazolate framework adsorbent and adsorbed germane at sub-atmospheric pressure can deliver at least 80%, 90%, 95%, or 99% of the total amount of germane stored in the vessel, i.e., the storage vessel has a deliverable capacity of at least 80%, 90%, 95%, or 99% of the total amount of gas in the vessel. The vessel can be able to deliver germane gas from the vessel at a venting pressure of less than 50 Torr, 30 Torr, 20 Torr, 15 Torr, 10 Torr, 5 Torr, 3 Torr, 1 Torr, or 0.5 Torr. This high level of deliverable capacity of stored germane gas is useful or potentially advantageous compared to the deliverable capacity of other types of adsorbent materials (e.g., carbon-based adsorbents) that typically have a "heel" (gas that cannot be extracted at venting pressures as low as 5 Torr) of more than 10 (mole) % of the total adsorbed gas in a given system.

[0014] In one aspect, the present disclosure relates to a storage and dispensing vessel enclosing an internal volume containing a zeolitic imidazolate framework adsorbent and GeH4 adsorbed on the adsorbent. The vessel includes a port, a valve mounted at the port, a zeolitic imidazolate framework adsorbent within the internal volume, and GeH4 adsorbed on the zeolitic imidazolate framework. The vessel is selectively actuatable to flow gaseous GeH4 from the internal volume of the vessel through the valve to vent the GeH4 from the vessel. BRIEF DESCRIPTION OF DRAWINGS

[0015] Figure 1 An exemplary storage system of the present description is demonstrated.

[0016] Figure 2 Performance data of a storage system of the present description is demonstrated.

[0017] Figure 3 Performance data of a storage system of the present description is demonstrated. DETAILED DESCRIPTION

[0018] The present description relates to novel and inventive systems for storing germane in a container that houses a zeolitic imidazolate framework adsorbent, wherein the germane is adsorbed to the adsorbent, and to novel and inventive methods for storing, handling and transporting germane using the storage systems.

[0019] The storage system as described comprises a container that houses a zeolitic imidazolate framework (ZIF) adsorbent material inside thereof. The adsorbent material is effective for containing, storing and transporting germane from the storage container. The germane is adsorbed on the zeolitic imidazolate framework adsorbent and exists as a gas inside the container, wherein a portion of the germane is adsorbed by the zeolitic imidazolate framework and another portion is in gaseous form or condensed and gaseous form and is in equilibrium with the adsorbed portion.

[0020] The pressure inside the container can be sub-atmospheric, meaning below about 760 Torr (absolute). The pressure inside the container can be below 760 Torr, for example, below 700 Torr, 600 Torr, 400 Torr, 200 Torr, 100 Torr, 50 Torr or 20 Torr, during storage of the container or during use of the container to dispense germane.

[0021] The following description relates to the use of zeolitic imidazolate frameworks ("ZIFs") in adsorbent-based storage containers to store germane (GeH4) at sub-atmospheric pressures. Applicants have determined that the use of zeolitic imidazolate frameworks as adsorbents can allow for useful or preferred storage capacity of germane.

[0022] An example of a preferred storage system for storing germane adsorbed by a zeolitic imidazolate framework adsorbent as described can exhibit a useful storage capacity for germane, for example, a storage capacity of at least 100 g / kg or preferably 200 g / kg or more preferably greater than 300 g / kg.

[0023] An exemplary storage system can also exhibit a useful or advantageous deliverable capacity of germane (for example, a deliverable capacity of at least 80%, 90%, 95% or 99%), meaning that the storage container can dispense at least 80%, 90%, 95% or 99% of the total amount of germane stored inside the container. An exemplary storage system can dispense germane at a pressure as low as 50 Torr, 20 Torr, 10 Torr, 5 Torr, 3 Torr, 1 Torr or 0.5 Torr.

[0024] Examples of useful or preferred systems for storing germane in a storage vessel containing a zeolitic imidazolate framework adsorbent can exhibit a useful or relatively low amount of decomposition of the stored germane during storage of the stored germane. For example, germane stored in a storage vessel as described can undergo less than 1%, or preferably less than 0.1%, or more preferably less than 0.01% decomposition based on the total initial adsorbed germane capacity over a period of 365 days at ambient temperature.

[0025] Germane (a chemical compound having the chemical formula GeH4, also known as "tetrahydrogen germanium" or germanomethane) is a known reagent gas used in the semiconductor industry.

[0026] According to the present description, germane is stored in a vessel containing a zeolitic imidazolate framework adsorbent, wherein the germane is adsorbed on the zeolitic imidazolate framework adsorbent. The storage system is of the type known as an adsorbent-based storage system, which includes a vessel containing a zeolitic imidazolate framework adsorbent. Zeolitic imidazolate framework adsorbents are known and are known to be different in composition from other known types of adsorbent media, such as carbon-based adsorbent media, polymeric adsorbent media, silica, etc.

[0027] Zeolitic imidazolate frameworks are a known type of metal-organic framework (MOF) that are known to be useful as adsorbents for storing certain reagent gases, including for storing and shipping reagent gases for use in semiconductor processing. Zeolitic imidazolate frameworks are metal-organic frameworks that include tetrahedral coordinated transition metals (e.g., iron (Fe), cobalt (Co), copper (Cu), or zinc (Zn)) connected by imidazolate linkers, which can be the same or different within a particular ZIF composition or with respect to individual transition metal atoms of the ZIF structure. ZIF structures include four-coordinated transition metals linked by imidazolate units to create elongated frameworks based on tetrahedral topology. ZIFs are said to form structural topologies equivalent to those found in zeolites and other inorganic microporous oxide materials.

[0028] Zeolitic imidazolate frameworks can be characterized by characteristic properties including the particular transition metal of the framework (e.g., iron, cobalt, copper, or zinc); the chemical nature of the linker (e.g., the chemical substituents of the imidazolate units); the pore size of the ZIF; the surface area of the ZIF; the pore volume of the ZIF; and other physical and chemical properties. There are known to be many (at least 105) unique ZIF species or structures, each of which has a different chemical structure based on the type of transition metal that makes up the framework and the type of linker (or linkers). Each topology is identified using a unique ZIF name (e.g., ZIF-1 through ZIF-105). For a description of ZIFs, including the specific chemical compositions and related properties of a large number of known ZIF species, see Phan et al., "Synthesis, Structure, and Carbon Dioxide Capture Properties of Zeolitic Imidazolate Frameworks," Accounts of Chemical Research, 2010, 43(1), pp. 58-67 (incorporated April 6, 2009).

[0029] The pore size of a ZIF can affect the performance of the ZIF as a sorbent. An exemplary ZIF can have a pore size in a range from about 0.2 Angstroms to 13 Angstroms (e.g., from 2 Angstroms to 12 Angstroms or from 3 Angstroms to 10 Angstroms). Pore size refers to the diameter of the largest sphere that would pass through the surface of the ZIF crystal. To be used as a sorbent in the containers of the present description, a ZIF can have any pore size effective to provide the desired storage properties.

[0030] Useful or preferred ZIFs can be able to provide useful storage capacity, useful shipping capacity, and preferably can be used to store sorbed germane in a storage container with a relatively low amount of degradation of the stored germane.

[0031] One example of a ZIF that has been found to be useful in a container as described to sorb germane gas in the container and to store the germane gas in the container at sub-atmospheric pressure is known as "ZIF-8," which is dimethylimidazolate zinc (also known as "zinc (dimethylimidazolate)2." This zeolitic imidazolate framework is reported to have a pore size of 3.4 Angstroms. See U.S. Patent No. 9,138,720, which describes ZIF-8 as well as other MOFs.

[0032] When contained in a container for storing germane as described herein, the zeolitic imidazolate framework can be in any useful form, such as granular (particles), monolithic, or other forms. For various example embodiments, it is preferred that the zeolitic imidazolate framework can be in the form of particles, which can be easily placed (e.g., poured) into a container (such as a steel cylinder containing a relatively small opening). Also, other forms of the zeolitic imidazolate framework can also be useful or preferred for different product designs, including monolithic or block adsorbents, rods, or space-filling polyhedral adsorbents.

[0033] Within an exemplary container, at temperatures at which the container will be used to transport germane, the contained germane can be in a form that includes a portion in condensed or gaseous form (i.e., as gaseous germane) that is in equilibrium with germane adsorbed on the zeolitic imidazolate framework. The temperature of the container and the germane can be within a range of temperatures to which the container can be exposed during use (e.g., temperatures within a range from about 0 degrees Celsius to about 50 degrees Celsius). This range includes operating temperatures, which are typical temperatures that the container will maintain during controlled storage and use in an "ambient temperature" or room temperature environment, generally understood to include temperatures within a range from about 20 degrees Celsius to about 26 degrees Celsius.

[0034] At temperatures at which the container will be used to transport the reagent gas, the gaseous germane can be at sub-atmospheric pressure, i.e., at less than about 1 atmosphere (760 Torr) (absolute). The internal pressure of the container can be within this range during use, and can be highest when the container contains a maximum amount of germane (i.e., when the container is "full" of germane). During use, as the germane is gradually removed from the container, the internal container pressure will gradually decrease and can reach a pressure of less than 700 Torr, 600 Torr, 400 Torr, 200 Torr, 100 Torr, 50 Torr, 20 Torr, 10 Torr, 5 Torr, 3 Torr, 1 Torr, or 0.5 Torr.

[0035] The containers of the storage system as described can contain the zeolitic imidazolate framework adsorbent as the only type of adsorbent medium present within the interior of the container, or if desired the zeolitic imidazolate framework adsorbent can be contained in combination with another type of adsorbent medium. In particular currently preferred embodiments, the adsorbent medium contained in the container can be substantially (e.g., at least 50%, 80%, 90%, 95%, or 97%) or entirely a zeolitic imidazolate framework adsorbent as described herein, and other types of adsorbent medium are not required and can be excluded from the interior of the container. In other words, the total amount of adsorbent contained within the interior of the container can comprise, consist essentially of, or consist of a zeolitic imidazolate framework adsorbent, including in particular the general and specific types of zeolitic imidazolate framework adsorbents described herein.

[0036] According to the present description, a composition consisting essentially of a specified material or combination of materials is a composition containing one or more specified materials and no more than trace amounts of any other material (e.g., no more than 2, 1, 0.5, 0.1, or 0.05 weight percent of any other material). For example, a description of the interior of a container holding an adsorbent consisting essentially of a zeolitic imidazolate framework adsorbent refers to a container having an interior that holds a zeolitic imidazolate framework adsorbent and no more than 2, 1, 0.5, 0.1, or 0.05 weight percent of any other type of adsorbent medium based on the total weight of the interior of the container.

[0037] Various examples of container structures for storing a reagent gas can be used for the adsorptive storage of germane according to the present description using a zeolitic imidazolate framework as an adsorbent. An exemplary container includes a cylindrical containment device ("cylinder") that includes a rigid cylindrical sidewall that defines an interior of the container and an outlet (or "port") at an end of the cylinder. The container sidewall can be made of metal or another rigid (e.g., reinforced) material and is designed to withstand pressure levels that safely exceed the desired maximum pressure recommended for containing a reagent gas in the interior of the container.

[0038] Figure 1 An example of a fluid supply system ("fluid supply package") is shown as described, in which a zeolitic imidazolate framework adsorbent is disposed for storage and transport of germane. As illustrated, fluid supply package 10 includes a container 12 that includes a cylindrical wall 14 and a floor that enclose an interior volume 16 of container 12 in which a zeolitic imidazolate framework adsorbent 18 is disposed. Container 12 is joined at its upper end to a cap 20, which can have a planar feature on its outer peripheral portion, defining an upwardly extending boss 28 on its upper surface. Cap 20 has a central threaded opening that receives a corresponding threaded lower portion 26 of a fluid dispensing assembly.

[0039] Valve head 22 can be moved between open and closed positions by any suitable action, such as a hand-operated handwheel or a pneumatically-operated activator 30 coupled thereto. The fluid dispensing system includes an outlet port 24 for dispensing gaseous germane from the fluid supply system when the valve is opened by operation of handwheel 30.

[0040] The zeolitic imidazolate framework adsorbent 18 in the interior volume 16 of the container 12 can be of any suitable type as disclosed herein, and can for example include adsorbent in the form of a powder, particulate, pellet, bead, monolith, ingot, or other suitable form. The zeolitic imidazolate framework adsorbent has an adsorptive affinity for germane to allow storage and dispensing of germane within the container. Dispensing can be performed by opening the valve head 22 to regulate desorption of germane stored on the adsorbent in adsorbed form and discharge of the germane from the container through a fluid dispensing assembly to an outlet port 24 and associated flow circuitry (not shown) at the outlet port 24, where the pressure causes pressure-mediated desorption and discharge of the germane from the fluid supply package. For example, the dispensing assembly can be coupled to flow circuitry at a pressure lower than the pressure in the container to effect this pressure-mediated desorption and dispensing, e.g., one atmosphere pressure suitable for downstream tools coupled to the fluid supply package through the flow circuitry. Optionally, dispensing can include opening the valve head 22 in conjunction with heating the adsorbent 18 to cause thermally-mediated desorption of the fluid for discharge from the fluid supply package.

[0041] The fluid supply package 10 is filled with germane for storage on the adsorbent by initially evacuating fluid from the interior volume 16 of the container 12, then followed by flowing germane into the container through the outlet port 24, which thereby serves a dual function for filling the fluid as well as dispensing the fluid from the fluid supply package. Alternatively, the valve head 22 can be provided with a separate fluid introduction port for filling the container with introduced fluid and loading the adsorbent.

[0042] The germane in the container can be stored at any suitable pressure conditions, preferably at sub-atmospheric or low sub-atmospheric pressures, thereby enhancing the safety of the fluid supply package with respect to, for example, high pressure gas cylinders.

[0043] Examples

[0044] Figure 2 Table of germane adsorption on ZIF-8 in a storage container as described, relative to delivery pressure, at sub-atmospheric pressures (grams of germane per gram of ZIF-8). The linear shape of this data line indicates that a high percentage of the germane contained in the container can be delivered. In addition, the linear relationship between pressure and adsorption allows for easy determination of the amount of GeH4 stored in a ZIF-8 filled cylinder when connected for use, as opposed to the more complex relationship for carbon filled cylinders.

[0045] Figure 3 Hydrogen content of germane stored on ZIF-8 over extended storage periods is shown.

[0046] The following table shows the amount of germane held by a quantity of ZIF-8 in a storage system as described at different pressures. Also described is the amount deliverable from the system and the deliverable capacity of the system.

[0047] ZIF-8 adsorbent storage system

[0048] Grams of germane per kilogram of ZIF-8 Transportable capacity Fully charged at 550 Torr 143 stored The remaining part under 20 pallets 5. Warp Storage The remaining part under 10 3 Warp Storage The remaining part under 5 trays 2 Storage Can be transported under 20 pallets 138 transported 96.5％ Can be transported under 10 pallets 140 transported 97.9％ Can be transported under 5 pallets 142 transported 99.3％

[0049] For this example, the relevant characteristics of the storage container, germane, and encapsulation and testing conditions are as follows:

[0050] Initial hydrogen content of germane when filled into the container: less than 10 ppmV (particles per million by volume);

[0051] Total volume of the storage container: 0.5 liters;

[0052] Amount (mass) of ZIF in the storage container: 140 grams;

[0053] Surface area of the ZIF: 1500 m2 / g to 1600 m2 / g nitrogen BET surface area; 2 2

[0054] Shape and form of the ZIF: extrudates, 1 mm to 3 mm in diameter, 1 cm to 5 cm long;

[0055] Temperature of the storage container and adsorbent for filling: GeH4filled at 21 °C in a temperature controlled enclosure;

[0056] Container and ZIF handling prior to filling: ZIF-8 is always stored in a glovebox atmosphere of <10 ppm O2and <2 ppm H2O levels; the storage container is loaded with ZIF-8 in the glovebox to prevent air impurities from adsorbing on the material; the storage container with ZIF-8 is heated at 150 °C while pumping for 24 hours to remove adsorbed air impurities containing water.

[0057] At Figure 2 The adsorption of GeH4on ZIF-8 is determined gravimetrically. The net amount of ZIF-8 is measured after loading and evacuating the test cylinder. The weight change is measured after the first fill of GeH4when a quantity of GeH4is withdrawn to reach the target pressure of stability and after each time a quantity of GeH4is withdrawn to reach the target pressure of stability. The pressure is measured with a capacitance manometer (MKS Model 722 "Baratron").

[0058] At Figure 3 Details of the technique and equipment used to periodically measure the H2concentration of the shipped sample of germane over the days of storage at

[0059] Storage conditions (temperature): 21 °C in a temperature controlled enclosure. ​​

[0060] Gas chromatography technique for measuring H2in shipped germane: gas chromatograph with thermal conductivity detector (TCD), using a Gow-Mac Series 580 GC test set-up, Hayesep porous polymer column, and 50 °C, 35 cm / min temperature and flow rate. 3 / minute temperature and flow rate.

Claims

1. A storage and dispensing vessel enclosing an internal volume containing a zeolitic imidazolate framework adsorbent and GeH4 adsorbed on the zeolitic imidazolate framework adsorbent, the vessel comprising: a port; a valve mounted at the port; a zeolitic imidazolate framework adsorbent within the internal volume; and GeH4 adsorbed on the zeolitic imidazolate framework adsorbent; the vessel actuated to flow gaseous GeH4 from the internal volume of the vessel through the valve to discharge the GeH4 from the vessel, wherein the GeH4 degrades to hydrogen in an amount less than 1% of the total initial adsorbed germane over a period of 365 days at ambient temperature and the storage capacity of GeH4 is at least 100 g / kg, the internal pressure of the vessel is less than 600 Torr during storage of the vessel.

2. The vessel of claim 1, wherein the zeolitic imidazolate framework adsorbent comprises tetrahedrally coordinated zinc atoms connected by imidazole crosslinkers.

3. The vessel of claim 2, wherein the zeolitic imidazolate framework adsorbent is zinc dimethylimidazolate.

4. The vessel of claim 1, containing GeH4 within the internal volume at sub- atmospheric pressure, the GeH4 comprising a portion adsorbed on the zeolitic imidazolate framework adsorbent and a portion in equilibrium with the adsorbed GeH4 as condensed or gaseous GeH4.

5. The vessel of claim 1, capable of dispensing at least 95% of the germane contained in the vessel from the vessel.

6. The vessel of claim 1, capable of dispensing at least 99% of the germane contained in the vessel from the vessel.

7. The vessel of claim 1, capable of dispensing the germane contained in the vessel at a discharge pressure of less than 10 Torr.

8. The vessel of claim 1, wherein the amount of GeH4 degradation to hydrogen (H2) is less than 1% of the total initial adsorbed germane over a period of 365 days at 30 degrees Celsius.

9. The vessel of claim 1, wherein the amount of GeH4 degradation to hydrogen (H2) is less than 0.1% of the total initial adsorbed germane over a period of 365 days at 30 degrees Celsius.

10. The vessel of claim 1, wherein the amount of GeH4 degradation to hydrogen (H2) is less than 0.01% of the total initial adsorbed germane over a period of 365 days at 30 degrees Celsius.

11. The vessel of claim 1, wherein the zeolitic imidazolate framework adsorbent is in the form of granules.

12. The vessel of claim 1, wherein the zeolitic imidazolate framework adsorbent is in the form of microparticles.

13. The vessel of claim 1, wherein the zeolitic imidazolate framework adsorbent is in the form of small beads.

14. The vessel of claim 1, wherein the zeolitic imidazolate framework adsorbent is in the form of pellets.

15. A method of supplying GeH4 from the vessel of claim 1, the method comprising transporting the GeH4 from the interior of the vessel to the exterior of the vessel.

16. The method of claim 15, wherein the GeH4 is transported at a pressure below 50 Torr.

17. The method of claim 15, wherein the GeH4 is transported at a pressure below 10 Torr.

18. The method of claim 15, comprising transporting the GeH4 to a semiconductor processing device.

19. The method of claim 18, wherein the container contains an initial amount of GeH4 filled into the interior of the container, and the method comprises dispensing at least 95% of the initial amount to the semiconductor processing device.

20. The method of claim 18, wherein the container contains an initial amount of GeH4 filled into the interior of the container, and the method comprises dispensing at least 99% of the initial amount to the semiconductor processing device.

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