Negative pressure container for storing electronic gas

Abstract

The utility model discloses a negative pressure container for storing electronic gas. The negative pressure container comprises a bottle body and a valve, the bottle body is filled with a carrier material, and the carrier material comprises graphene; one or more gas guide pipes are further arranged in the bottle body, at least part of each gas guide pipe is surrounded by the carrier material, the top of each gas guide pipe is communicated with a valve of the negative pressure container, and a plurality of gas guide openings are formed in the side wall of each gas guide pipe and used for loading and unloading gas. According to the negative pressure container, the characteristics that the selected carrier material has a relatively high specific surface area and a relatively large pore volume are utilized, so that the negative pressure container shows excellent loading capacity for electronic gases including arsine, phosphorane, boron trifluoride and the like, the product type of the negative pressure container capable of accommodating the electronic gases is expanded, and the benign development of the negative pressure container market is ensured.

Description

Technical Field

[0001] The utility model relates to the technical field of electronic gas storage, and more specifically, to a negative pressure container for storing electronic gas. Background Art

[0002] Phosphine PH 3 , Arsenic acid AsH 3 and boron trifluoride BF 3 Gases such as phosphorus and arsenic play a very important role in the electronics industry, especially in the integrated circuit and photovoltaic industries, especially after their impurities are removed to obtain high-purity gases. The reason is that phosphorus P and arsenic As are group V elements, which are used as electron-type (n-type) doping in silicon-based semiconductors, while boron B is a group III element, which is used as hole-type (p-type) doping. Their doping allows silicon to have enough carriers to generate conductivity, and because there are two types of carriers (electrons and holes), a pn junction can be formed, which is the manufacturing basis of all silicon devices. These substances are also called electronic gases and are vital to the electronics industry. However, they all have a dangerous characteristic: they are highly toxic, and even a small amount can kill people, so they will cause great trouble in all aspects of use. Due to the great progress of the integrated circuit and photovoltaic industries in the past few decades, there will be greater development in the foreseeable future. Therefore, the use of these electronic gases will be greatly expanded. How to use them safely is an unavoidable and important issue, including production, storage, transportation and use. Among them, how to store these gases is the top priority. Since these gases have small molecular weights and weak intermolecular forces, they are all gaseous at room temperature and pressure. Considering their toxicity, relevant national departments stipulate that they need to be mixed with other gases (such as hydrogen, nitrogen, argon, etc.) to reduce their concentration during storage, that is, mixed gas, thereby reducing their toxicity. However, this will increase the volume of the gas and increase the inconvenience of storage.

[0003] Containers for storing gas are usually called packaging materials, and the most common packaging materials are steel cylinders or aluminum bottles. As the volume of the mixed gas increases, people often use high-pressure steel cylinders or high-pressure aluminum bottles to store the mixed gas. Take phosphine as an example: the state stipulates that the concentration of phosphine in the mixed gas cannot exceed 10%, and people often increase the pressure of the mixed gas to 100 atmospheres, which requires the use of high-pressure resistant seamless steel cylinders. For example, one of the common seamless steel cylinders is called a Y cylinder, which has a volume of 440 liters. The weight of the cylinder itself is about 527kg, and the total weight of the cylinder bracket is about 647kg. The phosphine that can be filled (concentration less than 10%) does not exceed 6.7kg, which means that the weight of the truly effective phosphine is only about 1%, and the storage efficiency is quite low. Due to the high gas pressure, this solution is still very difficult. It is not easy to manufacture the material and wall thickness of the seamless steel cylinder, and the requirements for the valve are also very high, which greatly increases various manufacturing costs. In addition, the increase in weight and the transportation of hazardous chemicals also make its logistics costs quite high. Utility Model Content

[0004] In order to solve the problems existing in the prior art, the purpose of the utility model is to provide a negative pressure container for storing electronic gas. The negative pressure container filled with a carrier material can contain electronic gases such as phosphine, arsine and boron trifluoride, expanding the product types of negative pressure containers that can contain electronic gases and ensuring the healthy development of the negative pressure container market.

[0005] Unless otherwise specified, the pressure in the present invention refers to absolute pressure.

[0006] In order to achieve the above purpose, the utility model adopts the following technical solutions:

[0007] The utility model provides a negative pressure container for storing electronic gas, the negative pressure container comprising a bottle body and a valve, the bottle body is filled with a carrier material, the carrier material comprises graphene; one or more air guide tubes are also arranged in the bottle body, the air guide tubes are at least partially surrounded by the carrier material, the top of the air guide tubes is connected to the valve of the negative pressure container, and a plurality of air guide ports are arranged on the side wall of the air guide tubes for loading and unloading gas.

[0008] The carrier material selected by the utility model has a high specific surface area and a large pore volume, and can load electronic gas by physical adsorption and gas liquefaction, so that the pressure in the negative pressure container is less than 1 atmosphere at room temperature, and no leakage occurs, which is safer during storage, transportation and use.

[0009] Furthermore, the stacking volume of the carrier material in the container is greater than 90% of the container volume.

[0010] Furthermore, when a plurality of air guide tubes are arranged in the bottle body, the plurality of air guide tubes are evenly arranged in radial direction in the bottle body.

[0011] Furthermore, the air guide ports are evenly distributed on the air guide pipe.

[0012] Furthermore, the pressure resistance range of the negative pressure container is 50-100 atmospheres.

[0013] On the side wall of the air guide tube, multiple air guide ports are arranged along the extension direction of the air guide tube, which shortens the diffusion path of the electronic gas in the carrier material and ensures that the electronic gas can be loaded or unloaded in multiple areas simultaneously in the negative pressure container, thereby facilitating the improvement of the loading efficiency of the carrier material for the electronic gas when the electronic gas is filled into the negative pressure container, and also facilitating the improvement of the unloading rate when the electronic gas is discharged.

[0014] In terms of compound type, the graphene is selected from one or more of modified or unmodified graphene (such as graphene, graphene oxide, fluorinated graphene, hydrogenated graphene, silanized graphene, etc.), modified or unmodified graphene derivatives (such as graphene derivatives, graphene oxide derivatives, fluorinated graphene derivatives, hydrogenated graphene derivatives, silanized graphene derivatives, etc.).

[0015] The graphene can be single-layer, double-layer or multi-layer, and the graphene surface is rich in wrinkles. The sheets can be stacked in an orderly or disordered manner, and the arrangement between the layers is also conducive to loading more electron gas. By modifying the graphene, the adsorption and loading capacity of the electron gas can be further improved, and more micro-nano pores can be constructed to improve the condensation loading capacity.

[0016] The graphene can also be doped (or hybridized) with different elements. The doped (or hybridized) graphene can significantly reduce the adsorption activation energy and increase the loading speed and capacity. Appropriate doping can significantly increase the loading amount while ensuring that the electronic gas will not decompose. The doped (or hybridized) elements are selected from metal elements and / or non-metal elements and their compounds. The metal elements are preferably transition metal elements, rare earth metal elements or alkaline earth metals of the second group.

[0017] The graphene can also be bonded with metal or non-metal elements to form a skeleton structure. The electron gas can condense in the gaps in the skeleton structure, thereby achieving a high loading capacity.

[0018] In terms of shape, the graphene is selected from one or more of graphene sheets, graphene spheres (fullerenes), graphene tubes (carbon nanotubes), graphene rolls and graphene ribbons.

[0019] Further, the graphene consists of graphene having 15 layers or less or a graphene aggregate including graphene particles consisting of graphene having 15 layers or less.

[0020] Furthermore, the carrier material also includes activated carbon, and the graphene is uniformly dispersed in the activated carbon.

[0021] Further, the mass ratio of the graphene to the activated carbon is 1:100-100:1, preferably 1:100-60:100. Exemplarily, the mass ratio of the graphene to the activated carbon can be 1:100, 2:100, 3:100, 4:100, 5:100, 6:100, 7:100, 8:100, 9:100, 10:100, 20:100, 30:100, 40:100, 50:100, 60:100, etc.

[0022] Furthermore, the activated carbon is selected from one or more of sawdust activated carbon, fruit shell activated carbon, biomass activated carbon, and asphalt-based microsphere activated carbon.

[0023] Furthermore, the carrier material may also contain a certain amount of molecular sieves, porous silicon materials, metal-organic frameworks (MOF), covalent organic frameworks (COF), halloysite, attapulgite, alumina, pseudo-boehmite, silicon oxide, desolate, rectorite, sepiolite, etc.

[0024] Furthermore, the bottle body is made of carbon steel or stainless steel, and the air guide tube is made of stainless steel.

[0025] Furthermore, the negative pressure container also includes a nozzle for releasing gas and a safety device for monitoring and controlling the gas pressure in the negative pressure container.

[0026] Furthermore, in order to ensure the purity of the electronic gas coming out of the negative pressure container, the gas guide port is equipped with a filter screen or a filter membrane to prevent the carrier material from mixing into the electronic gas.

[0027] Furthermore, a bottle cap is provided on the top of the bottle body.

[0028] Furthermore, the electronic gas includes but is not limited to one of arsine, phosphine, silane, diborane, boron trifluoride, phosgene, and hydrogen sulfide.

[0029] Furthermore, the gas pressure in the negative pressure container is less than 1 atmosphere at room temperature.

[0030] The beneficial effects of the utility model are as follows:

[0031] The utility model provides a negative pressure container for storing electronic gas, which is filled with graphene, a carrier material with high specific surface area and large pore volume, and can load electronic gas, such as arsine, phosphine, boron trifluoride, etc., by physical adsorption and gas liquefaction, showing excellent loading capacity. When the gas loading pressure of the negative pressure container of the utility model is less than 1 atmosphere at room temperature, the gas loading capacity is greater than the loading capacity of electronic gas in existing containers, which can effectively reduce the storage and transportation costs of electronic gas; the gas in the negative pressure container loaded with electronic gas will not leak out due to the negative pressure state, which ensures the safety of use and storage, expands the product types of negative pressure containers that can accommodate electronic gas, and ensures the healthy development of the negative pressure container market. The negative pressure container developed by the utility model is reusable, which improves the utilization rate of the negative pressure container and reduces the storage and transportation costs of electronic gas.

[0032] The utility model arranges a plurality of air guide ports on the side wall of the air guide tube in the extension direction of the air guide tube, thereby shortening the diffusion path of the electronic gas in the carrier material, ensuring that the electronic gas can be loaded or unloaded in multiple areas simultaneously in the negative pressure container, thereby facilitating the improvement of the loading efficiency of the carrier material for the electronic gas when the electronic gas is filled into the negative pressure container, and also facilitating the improvement of the export rate when the electronic gas is exported. BRIEF DESCRIPTION OF THE DRAWINGS

[0033] The specific implementation of the utility model is further described in detail below with reference to the accompanying drawings.

[0034] Figure 1 One of the schematic diagrams of the negative pressure container for storing electronic gas provided by the utility model is shown.

[0035] Figure 2 A second schematic diagram showing a negative pressure container for storing electronic gas provided by the utility model.

[0036] Figure 3 A third schematic diagram showing a negative pressure container for storing electronic gas provided by the utility model.

[0037] Description of the accompanying drawings: 1 bottle body, 2 valve, 3 carrier material, 4 air guide tube, 5 nozzle, 6 pressure gauge or pressure sensor. DETAILED DESCRIPTION

[0038] In order to more clearly illustrate the utility model, the utility model is further described below in conjunction with preferred embodiments and drawings. Those skilled in the art should understand that the content described below is illustrative rather than restrictive, and should not be used to limit the scope of protection of the utility model.

[0039] Considering that the carrier material used in the negative pressure container must have the following two functions: 1. It can load electronic gas when loading gas. To ensure the safety of use, the gas pressure after loading is lower than one atmosphere; 2. It can also unload gas when unloading gas, and the purity of the unloaded gas remains the original high purity (electronic gas needs to be more than 99.99% when used, for example, the purity of phosphine and arsine is not less than 99.9999%, and the purity of boron trifluoride is not less than 99.995%). Therefore, the actual role of this carrier material is the function of a carrier, which can safely carry the target gas from one time and space to another time and space. If the material used can only achieve the first function, that is, it can only load gas (such as adsorbed gas), but the loaded gas cannot be unloaded (such as desorption), or even if the gas can be unloaded, but the unloaded gas has lost its original high purity, then it cannot be used as a carrier material for negative pressure containers.

[0040] The loading of electronic gas can be achieved by physical adsorption, which is referred to as adsorption loading in the present invention. Adsorbent materials usually have a large surface area. Because the atoms, molecules or active centers on the surface of the adsorbent material have high surface energy, the gas molecules have a large interaction force with them and are adsorbed.

[0041] According to different mechanisms, the adsorption process can be divided into two categories: one is irreversible chemical adsorption, in which the adsorbed substance undergoes a chemical reaction with the adsorbent material during the adsorption process and is converted into other substances, so that the adsorbed substance is apparently adsorbed by the adsorbent material. The characteristic of this type of adsorption is that the adsorbed substance cannot be desorbed from the adsorbent material in the subsequent process because the adsorbed substance has reacted during the adsorption process. This type of adsorption is generally used in the process of removing harmful substances, including environmental protection, production safety, etc. Obviously, this type of adsorption must never be used in negative pressure containers for storing electronic gases. Electronic gases require very high purity when used. Even if a trace amount of other substances is newly generated during the adsorption process or some impurities are discharged together during the desorption process, the original high purity will be destroyed. The other type is physical adsorption. The characteristic of this type of adsorption is that the molecular structure of the adsorbate is kept intact during the adsorption and desorption process, and the apparent result is that the adsorbate only undergoes a physical process with the adsorbent material during the adsorption process. The adsorption loading mechanism of the carrier material used for electronic gases must be physical adsorption.

[0042] Another important physical process is to liquefy the electron gas in the carrier material. This loading is called condensation loading in the present invention. According to the Kelvin equation:

[0043]

[0044] Where R is the universal gas constant, T is the temperature of the negative pressure container; the parameters determined by the gas type include: saturated vapor pressure p * , corresponding to the surface tension γ of the liquid and the molar volume V of the liquid m ; The remaining two variables that can be manipulated are the radius r of the droplet and the actual vapor pressure p. In order to make the actual vapor pressure lower than one atmosphere, a negative liquid radius is required, which can be achieved by constructing micro-nano holes (i.e., the size of the holes is in the nanometer or micrometer range, less than 1 mm) in the carrier material. Once the holes in the carrier material are too large, the actual vapor pressure will be close to the saturated vapor pressure. Then, under the working conditions of the negative pressure container, these large holes will lose the condensation loading function because they cannot liquefy the electron gas.

[0045] Graphene has high physical stability and is the thinnest two-dimensional material in the material world. It has a large specific surface area and good adsorption capacity. Such thin two-dimensional graphene naturally brings such characteristics: it can be bent, wrinkled, folded, etc. at will to form graphene materials with different structural morphologies. Therefore, graphene is an ideal material for constructing micro-nano holes. For example, carbon nanotubes are a kind of graphene with a special shape that is bent into a ring-shaped hole. Therefore, the graphene in the utility model covers carbon nanotubes.

[0046] Activated carbon is an ideal basic material. It is cheap, rich in pores, low in bulk density, and large in specific surface area. It can fully contact with the electronic gas and load the electronic gas. The carrier material of the utility model also includes activated carbon. The graphene is used together with the activated carbon to further increase the loading amount of the electronic gas.

[0047] The utility model provides a negative pressure container for storing electronic gas, see Figure 1-Figure 3 The negative pressure container includes a bottle body 1 and a valve 2, the bottle body is filled with a carrier material 3, and the carrier material contains graphene; one or more air guide tubes 4 are also arranged in the bottle body, the air guide tubes are at least partially surrounded by the carrier material, and the top of the air guide tubes is connected to the valve of the negative pressure container, and multiple air guide ports are arranged on the side wall of the air guide tubes for loading and unloading gas.

[0048] The utility model can load a variety of electronic gases (such as arsine, phosphine, boron trifluoride, etc.) by means of adsorption loading and condensation loading by filling a carrier material with a high specific surface area and a large pore volume in a negative pressure container, showing excellent loading capacity, and the pressure in the negative pressure container is less than 1 atmosphere at room temperature, and the gas in the negative pressure container will not leak out, so it is safe to use and store, and expands the product types of negative pressure containers that can accommodate electronic gases. In addition, multiple air guide ports are arranged on the side wall of the air guide tube along the extension direction of the air guide tube, shortening the diffusion path of the electronic gas in the carrier material, ensuring that the electronic gas can be loaded or unloaded in multiple areas in the negative pressure container at the same time, thereby facilitating the improvement of the loading efficiency of the carrier material on the electronic gas when filling the negative pressure container with electronic gas, and also facilitating the improvement of the export rate when the electronic gas is exported.

[0049] In one embodiment, the bulk volume of the support material in the container is greater than 90% of the volume of the container.

[0050] In a specific embodiment, when a plurality of air guide tubes are disposed in the bottle body, the plurality of air guide tubes are radially uniformly disposed in the bottle body.

[0051] In a specific embodiment, the air guide ports are evenly distributed on the air guide tube.

[0052] In a specific embodiment, the pressure resistance value of the negative pressure container is 50-100 atmospheres.

[0053] In a specific embodiment, the graphene is selected from one or more of modified or unmodified graphene (e.g., graphene, graphene oxide, fluorinated graphene, hydrogenated graphene, silanized graphene, etc.), modified or unmodified graphene derivatives (e.g., graphene derivatives, graphene oxide derivatives, fluorinated graphene derivatives, hydrogenated graphene derivatives, silanized graphene derivatives, etc.).

[0054] In a specific embodiment, the graphene can be a single layer, a double layer, or a multilayer, the graphene surface is rich in wrinkles, the sheets can be stacked in an orderly or disordered manner, and the arrangement between the layers is also conducive to loading more electron gas. By modifying the graphene, the loading capacity of the electron gas is further improved and more micro-nano holes are constructed to improve the condensation loading capacity.

[0055] In a specific embodiment, the graphene can also be doped (or hybridized) with different elements. The doped (or hybridized) graphene can significantly reduce the adsorption activation energy and increase the loading speed and capacity. Appropriate doping can greatly increase the loading amount while ensuring that the electronic gas will not decompose. The doped (or hybridized) elements are selected from metal elements and / or non-metal elements and their compounds, and the metal elements are preferably transition metal elements, rare earth metal elements or alkaline earth metals of the second group.

[0056] The graphene is bonded with a metal or non-metal element to have a skeleton structure, and the electron gas can be condensed in the gaps in the skeleton structure, thereby achieving a high loading capacity.

[0057] In a specific embodiment, the graphene is selected from one or more of graphene sheets, graphene spheres (fullerenes), graphene tubes (carbon nanotubes), graphene rolls and graphene ribbons.

[0058] In a specific embodiment, the support material further comprises activated carbon, and the graphene is uniformly dispersed in the activated carbon.

[0059] The activated carbon is derived from one or more of sawdust activated carbon, fruit shell activated carbon, biomass activated carbon, and asphalt-based microsphere activated carbon; the activated carbon is rich in pores, has a low bulk density, and a large specific surface area, and can be fully contacted with the electronic gas for loading. The pores and large surface area of ​​the activated carbon provide space for holding graphene, and the use of it in combination with graphene can save the amount of graphene and reduce the cost of the negative pressure container.

[0060] In a specific embodiment, the carrier material may also contain a certain amount of molecular sieves, porous silicon materials, metal organic framework compounds, covalent organic frameworks, halloysite, attapulgite, alumina, pseudo-boehmite, silicon oxide, desolate, rectorite, sepiolite, etc.

[0061] In a specific embodiment, the bottle body is made of carbon steel or stainless steel, and the air guide tube is made of stainless steel.

[0062] In a specific embodiment, the negative pressure container further includes a nozzle 5 for releasing gas and a safety device for monitoring and controlling the gas pressure in the negative pressure container.

[0063] In a specific embodiment, the safety device includes a pressure gauge or a pressure sensor 6 .

[0064] In a specific embodiment, in order to ensure the purity of the electronic gas unloaded from the negative pressure container, the gas guide port is equipped with a filter screen or a filter membrane to prevent the carrier material from mixing into the electronic gas.

[0065] In a specific embodiment, a bottle cap is further provided on the top of the bottle body.

[0066] In a specific embodiment, the electronic gas includes but is not limited to one of arsine, phosphine, silane, diborane, boron trifluoride, phosgene, and hydrogen sulfide.

[0067] In a specific embodiment, the gas pressure in the negative pressure container is less than 1 atmosphere at room temperature.

[0068] Obviously, the above embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not limitations on the implementation methods of the present invention. For ordinary technicians in the relevant field, other different forms of changes or modifications can be made based on the above description. It is impossible to list all the implementation methods here. All obvious changes or modifications derived from the technical solution of the present invention are still within the scope of protection of the present invention.

Claims

1. A negative pressure container for storing electronic gas, characterized in that: The negative pressure container includes a bottle body and a valve, the bottle body is filled with a carrier material, and the carrier material contains graphene; one or more air guide tubes are also arranged in the bottle body, the air guide tubes are at least partially surrounded by the carrier material, the top of the air guide tubes is connected to the valve of the negative pressure container, and a plurality of air guide ports are arranged on the side wall of the air guide tubes for loading and unloading gas.

2. The negative pressure container according to claim 1, characterized in that: The bulk volume of the support material in the container is greater than 90% of the volume of the container.

3. The negative pressure container according to claim 1, characterized in that: The air guide ports are evenly distributed on the air guide pipe.

4. The negative pressure container according to claim 1, characterized in that: The pressure resistance value of the negative pressure container is 50-100 atmospheres.

5. The negative pressure container according to claim 1, characterized in that: The graphene is selected from one or more of graphene sheets, graphene spheres, graphene tubes, graphene rolls and graphene ribbons.

6. The negative pressure container according to claim 1, characterized in that: The support material also comprises activated carbon.

7. The negative pressure container according to claim 6, characterized in that: The mass ratio of the graphene to the activated carbon is 1:100-100:

1.

8. The negative pressure container according to claim 6, characterized in that: The activated carbon is selected from one or more of sawdust activated carbon, fruit shell activated carbon, biomass activated carbon, and asphalt-based microsphere activated carbon.

9. The negative pressure container according to claim 1, characterized in that: The negative pressure container stores electronic gas, and the electronic gas is selected from one of arsine, phosphine, silane, diborane, boron trifluoride, phosgene, and hydrogen sulfide.

10. The negative pressure container according to claim 9, characterized in that: The gas pressure in the negative pressure container is less than 1 atmosphere at room temperature.

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