Storage and Delivery Veseel for Storing GeH4, Using a Zeolitic Adsorbent

Abstract

Described are storage and dispensing systems and related methods, for the selective dispensing germane (GeH.sub.4) as a reagent gas from a vessel in which the germane is held in sorptive relationship to a solid adsorbent medium that includes a zeolitic imidazolate framework.

Claims

1. A storage and dispensing vessel enclosing an interior volume that contains zeolitic imidazolate framework adsorbent, and GeH.sub.4 adsorbed on the adsorbent, the vessel comprising: a port; a valve mounted at the port; zeolitic imidazolate framework adsorbent within the interior volume; and GeH.sub.4 adsorbed on the zeolitic imidazolate framework; the vessel being selectively actuatable to flow gaseous GeH.sub.4 from the interior volume of the vessel, through the valve, for discharge of the GeH.sub.4 from the vessel.

2. A vessel of claim 1 having an interior pressure below 760 Torr.

3. A vessel of claim 1 wherein the zeolitic imidazolate framework comprises tetrahedrally-coordinated zinc atoms connected by imidazolate linkers.

4. A vessel of claim 3 wherein the zeolitic imidazolate framework is zinc dimethylimidazolate.

5. A vessel of claim 1 containing GeH.sub.4 within the interior volume at sub-atmospheric pressure, the GeH.sub.4 comprising a portion that is adsorbed on the adsorbent and a portion that is present as condensed or gaseous GeH.sub.4 in equilibrium with the adsorbed GeH.sub.4.

6. A vessel of claim 1 capable of dispensing from the vessel at least 95 percent of the germane contained in the vessel.

7. A vessel of claim 1 capable of dispensing from the vessel at least 99 percent of the germane contained in the vessel.

8. A vessel of claim 1 capable of dispensing the germane contained in the vessel at a discharge pressure that is below 10 Torr.

9. A vessel of claim 1 wherein the amount of degradation of GeH.sub.4 to hydrogen gas (H.sub.2) is less than 1 percent of total initial adsorbed germane, over a period of 365 days, at 30 degrees Celsius.

10. A vessel of claim 1 wherein the amount of degradation of GeH.sub.4 to hydrogen gas (H.sub.2) is less than 0.1 percent of total initial adsorbed germane, over a period of 365 days, at 30 degrees Celsius.

11. A vessel of claim 1 wherein the amount of degradation of GeH.sub.4 to hydrogen gas (H.sub.2) is less than 0.01 percent of total initial adsorbed germane, over a period of 365 days, at 30 degrees Celsius.

12. A vessel of any of claim 1 wherein the adsorbent is in the form of granules, particulates, beads, or pellets.

13. A method of supplying GeH.sub.4 from a vessel as recited at claim 1, the method comprising delivering the GeH.sub.4 from the vessel interior to a vessel exterior, the GeH.sub.4 being delivered from the vessel at a pressure below 760 torr.

14. A method of claim 13 wherein the GeH.sub.4 is delivered at a pressure below 50 Torr.

15. A method of claim 13 wherein the GeH.sub.4 is delivered at a pressure below 10 Torr.

16. A method of claim 13 comprising delivering the GeH.sub.4 to a semiconductor processing device.

17. A method of claim 14 wherein the vessel contains an initial amount of GeH.sub.4 charged to the interior, and the method comprises dispensing at least 95 percent of the initial amount to the semiconductor processing device.

18. A method of claim 14 wherein the vessel contains an initial amount of GeH.sub.4 charged to the interior, and the method comprises dispensing at least 99 percent of the initial amount to the semiconductor processing device.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0015] FIG. 1 shows an example storage system of the present description.

[0016] FIG. 2 shows performance data of a storage system of the present description.

[0017] FIG. 3 shows performance data of a storage system of the present description.

DETAILED DESCRIPTION

[0018] The present description relates to novel and inventive systems that involve storing germane in a vessel that contains zeolitic imidazolate framework adsorbent, with germane adsorbed to the adsorbent, and to novel and inventive methods of using the storage systems to store, handle, and deliver germane.

[0019] A storage system as describes includes a vessel that contains zeolitic imidazolate framework (ZIF) adsorbent material at its interior. The adsorbent material is effective to contain, store, and deliver germane from the storage vessel. Germane is adsorbed on the zeolitic imidazolate framework adsorbent and is present as a gas at the vessel interior, with a portion of the germane being adsorbed by the zeolitic imidazolate framework, and another portion being in gaseous form or condensed and gaseous form and in equilibrium with the adsorbed portion.

[0020] The pressure at the interior of the vessel may be sub-atmospheric, meaning below about 760 Torr (absolute). During storage of the vessel, or during use of the vessel to dispense germane, the pressure at the interior of the vessel may be below 760 Torr, e.g., below 700, 600, 400, 200, 100, 50, or 20 Torr.

[0021] The following description relates to the use of a zeolitic imidazolate framework (“ZIF”) in an adsorbent-based storage vessel to store germane (GeH.sub.4) at sub-atmospheric pressure. The Applicant has determined that the use of a zeolitic imidazolate framework as an adsorbent can allow for useful or preferred storage capabilities of germane.

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

[0023] The example storage systems can also exhibit a useful or advantageous deliverable capacity of germane, e.g., a deliverable capacity of at least 80, 90, 95, or 99 percent, meaning that the storage vessel can dispense at least 80, 90, 95, or 99 percent of a total amount of germane stored at the vessel interior. Example storage systems may dispense germane at a pressure as low as 50, 20, 10, 5, 3, 1, or 0.5 Torr.

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

[0025] Germane, the chemical compound having the chemical formula GeH.sub.4, also known as “germanium tetrahydride” or germanomethane, is a known reagent gas used in the semiconductor industry.

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

[0027] Zeolitic imidazolate frameworks are a type of metal organic framework (MOF) that is known to be useful as an adsorbent for storing certain reagent gases, including for storage and delivery of reagent gases for use in semiconductor processing. Zeolitic imidazolate frameworks are metal organic frameworks that include a tetrahedrally-coordinated transition metal such as iron (Fe), cobalt (Co), Copper (Cu), or Zinc (Zn), connected by imidazolate linkers, which may be the same or different within a particular ZIF composition or relative to a single transition metal atom of a ZIF structure. The ZIF structure includes four-coordinated transition metals linked through imidazolate units to produce extended frameworks based on tetrahedral topologies. ZIFs are said to form structural topologies that are equivalent to those found in zeolites and other inorganic microporous oxide materials.

[0028] A zeolitic imidazolate framework can be characterized by features that include: a particular transition metal (e.g., iron, cobalt, copper, or zinc) of the framework; the chemistry of the linker (e.g., chemical substituents of the imidazolate units); pore size of the ZIF; surface area of the ZIF; pore volume of the ZIF; among other physical and chemical properties. Dozens (at least 105) of unique ZIF species or structures are known, each having a different chemical structure based on the type of transition metal and the type of linker (or linkers) that make up the framework. Each topology is identified using a unique ZIF designation, e.g., ZIF-1 through ZIF-105. For a description of ZIFs, including particular 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 (Received Apr. 6, 2009).

[0029] Pore size of a ZIF can affect the performance of a ZIF as an adsorbent. Example ZIFs can have pore sizes in a range from about 0.2 to 13 angstroms, such as from 2 to 12 angstroms or from 3 to 10 angstroms. Pore size refers to the diameter of the largest sphere that will pass through the surface of the ZIF crystal. For use as an adsorbent in a vessel of the present description, a ZIF can have any pore size that is effective to provide desired storage performance.

[0030] Useful or preferred ZIFs can be capable of providing a useful storage capacity, useful delivery capacity, and, preferably, can be used to store adsorbed germane in a storage vessel 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 vessel as described, for adsorbing germane gas in a vessel and storing the germane gas in the vessel at sub-atmospheric pressure, is referred to as “ZIF-8,” which is zinc dimethylimidazolate (a.k.a. “zinc(dimethylimidazolate)2.” This zeolitic imidazolate framework is reported to have a pore size of 3.4 angstroms. See U.S. Pat. No. 9,138,720, describing ZIF-8 among other MOFs.

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

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

[0034] At a temperature at which the vessel will be used to deliver reagent gas, the gaseous germane can be at a sub-atmospheric pressure, i.e., at a pressure of below about 1 atmosphere (760 torr), absolute. The internal pressure of the vessel may be in this range during use, and may be highest when the vessel contains a maximum amount of germane, i.e., when the vessel is “filled” with germane. During use, as germane is gradually removed from the vessel, the internal vessel pressure will gradually be reduced and may reach a pressure that is below 700, 600, 400, 200, 100, 50, 20, 10, 5, 3, 1, or 0.5 Torr.

[0035] A vessel of a storage system as described may contain zeolitic imidazolate framework adsorbent as the only type of adsorption media present at the vessel interior, or, if desired, may contain zeolitic imidazolate framework adsorbent in combination with another type of adsorption media. In certain presently preferred embodiments, adsorption media contained in a vessel may be substantially (e.g., at least 50, 80, 90, 95, or 97 percent) or entirely zeolitic imidazolate framework adsorbent as described herein, and other types of adsorption media are not required and may be excluded from the vessel interior. In other words, the total amount of adsorbent that is contained at an interior of a vessel may comprise, consist essentially of, or consist of zeolitic imidazolate framework adsorbent, particularly including the general and specific types of zeolitic imidazolate framework adsorbents described herein.

[0036] According to the present description, a composition that consists essentially of a specified material or combination of materials is a composition that contains the specified material or materials and not more than an insignificant amount of any other material, e.g., not more than 2, 1, 0.5, 0.1, or 0.05 percent by weight of any other material. For example, a description of a vessel interior that contains adsorbent that consists essentially of zeolitic imidazolate framework adsorbent refers to a vessel having an interior that contains the zeolitic imidazolate framework adsorbent and not more than 2, 1, 0.5, 0.1, or 0.05 percent by weight of any other type of adsorption media, based on total weight adsorption media at the vessel interior.

[0037] Various examples of vessel structures for storing reagent gases can be useful for storing germane, using zeolitic imidazolate framework as adsorbent, by adaptation according to the present description. Example vessels include cylindrical containers (“cylinders”) that include rigid cylindrical sidewalls that define a vessel interior and an outlet (or “port”) at an end of the cylinder. The vessel sidewalls can be made of metal or another rigid, e.g., reinforced, material, and are designed to withstand a level of pressure that safely exceeds a desired maximum pressure recommended for containing reagent gas at the interior of the vessel.

[0038] FIG. 1 shows an example of a fluid supply system (“fluid supply package”) as described, in which zeolitic imidazolate framework adsorbent is disposed for storage of and delivery of germane. As illustrated, fluid supply package 10 comprises vessel 12 that includes a cylindrical wall 14 and floor enclosing an interior volume 16 of vessel 12 in which is disposed zeolitic imidazolate framework adsorbent 18. Vessel 12 at its upper end portion is joined to cap 20, which may be of planar character on its outer peripheral portion, circumscribing upwardly extending boss 28 on the upper surface thereof. Cap 20 has a central threaded opening receiving a correspondingly threaded lower portion 26 of a fluid dispensing assembly.

[0039] Valve head 22 that is movable between open and closed positions by any suitable action such as manually operated hand wheel or pneumatically operated activator 30 coupled therewith. 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 the hand wheel 30.

[0040] The zeolitic imidazolate framework adsorbent 18 in the interior volume 16 of vessel 12 may be of any suitable type as herein disclosed, and may for example comprise adsorbent in a powder, particulate, pellet, bead, monolith, tablet, or other appropriate form. The zeolitic imidazolate framework adsorbent has sorptive affinity for the germane to allow storage of and dispensing of the germane within the vessel. Dispensing may be performed by opening valve head 22 to accommodate desorption of germane that is stored in an adsorbed form on the adsorbent, and discharge of germane from the vessel through the fluid dispensing assembly to the outlet port 24 and associated flow circuitry (not shown), wherein the pressure at the outlet port 24 causes pressure-mediated desorption and discharge of germane from the fluid supply package. For example, the dispensing assembly may be coupled to flow circuitry that is at lower pressure than pressure in the vessel for such pressure-mediated desorption and dispensing, e.g., a sub-atmospheric pressure appropriate to a downstream tool coupled to the fluid supply package by the flow circuitry. Optionally, dispensing may include opening valve head 22 in connection with heating of the adsorbent 18 to cause thermally-mediated desorption of fluid for discharge from the fluid supply package.

[0041] The fluid supply package 10 may be charged with germane for storage on the adsorbent by an initial evacuation of fluid from the interior volume 16 of vessel 12, followed by flow of germane into the vessel through outlet port 24, which thereby serves a dual function of charging as well as dispensing of fluid from the fluid supply package. Alternatively, valve head 22 may be provided with a separate fluid introduction port for charging of the vessel and the loading of the adsorbent with the introduced fluid.

[0042] Germane in the vessel may be stored at any suitable pressure condition, preferably at sub-atmospheric pressure or low sub-atmospheric pressure, thereby enhancing the safety of the fluid supply package in relation to fluid supply packages such as high pressure gas cylinders.

Examples

[0043] FIG. 2 is a table of adsorption of germane on ZIF-8 (grams germane per gram ZIF-8) in a storage vessel as described, at sub-atmospheric pressure, relative to delivery pressure. The linear shape of the line of this data indicates that a high percentage of the germane contained in the vessel is deliverable. In addition, a linear relationship between pressure and adsorption allows easy determination of the amount of GeH.sub.4 stored in a ZiF-8 filled cylinder when it is connected for use, in contrast to a more complicated relationship for a carbon filled cylinder.

[0044] FIG. 3 shows hydrogen content of germane stored on ZIF-8 over extended periods of storage.

[0045] The following table shows amounts of germane held by an amount of ZIF-8 in a storage system as described, at different pressures. Also described are amounts that may be delivered from the system, and deliverable capacity of the system.

TABLE-US-00001 ZIF-8 adsorbent storage system Grams germane per Deliverable kilogram ZIF-8 capacity full @ 550 Torr 143 stored Heel @ 20 Torr 5 stored Heel @ 10 Torr 3 stored Heel @ 5 Torr 2 stored Deliverable @ 20 Torr 138 delivered 96.5% Deliverable @ 10 Torr 140 delivered 97.9% Deliverable @ 5 Torr 142 delivered 99.3%
For this Example, relevant features of the storage vessel, germane, and packaging and testing conditions are as follows:

[0046] The initial hydrogen content of the germane when charged to the vessel: less than 10 ppmV (particles per million by volume);

[0047] Total volume of the storage vessel: 0.5 liters;

[0048] The amount (mass) of ZIF in the storage vessel: 140 grams;

[0049] Surface area of the ZIF: 1500-1600 m.sup.2/g nitrogen BET surface area;

[0050] Shape and form of the ZIF: Extrudates, 1-3 mm in diameter, 1-5 cm long;

[0051] Temperature of the storage vessel and adsorbent for charging: GeH.sub.4 was charged at 21 C in temperature controlled enclosure;

[0052] Vessel and ZIF treatment before charging: ZIF-8 was stored in a glove-box atmosphere of <10 ppm O.sub.2 and <2 ppm H.sub.2O level at all times; the storage vessel was loaded with ZIF-8 in the glovebox to prevent air impurities from adsorbing on the material; the storage vessel with ZIF-8 was heated at 150 C while pumping for 24 hours to remove adsorbed air impurities including water.

[0053] At FIG. 2, Adsorption of GeH.sub.4 on ZIF-8 was determined gravimetrically. The net amount of ZIF-8 was measured after loading and evacuating the test cylinder. Weight change was measured after the first charge of GeH.sub.4 upon and every time after withdrawal of an amount of GeH.sub.4 to reach a stable target pressure. Pressure was measured with a capacitance manometer, (MKS model 722 “Baratron”).

[0054] At FIG. 3, details of the technique and equipment used to measure H.sub.2 concentration of delivered samples of germane periodically over periods of days of storage: [0055] Storage conditions (temperature): 21 C in temperature controlled enclosure. [0056] Gas chromatography technique for measuring H.sub.2 in delivered germane: gas chromatograph with thermal conductivity detector, TCD, using Gow-Mac Series 580 GC test apparatus, Hayesep porous polymer columns, and 50 C 35 cm.sup.3/min temperature and flow rate.