Chemical dispensing device and method for dispensing chemicals into a reaction chamber

Abstract

A chemical dispensing apparatus for providing chlorine vapor to a reaction chamber and a method for dispensing chlorine vapor to a reaction chamber are provided. A chemical dispensing apparatus (100) includes a chemical storage container (102) for storing a chlorine-containing species, a reservoir (104) in fluid communication with the chemical storage container (102) for converting the chlorine-containing species (103) to chlorine vapor, and a reaction chamber (106) in fluid communication with the reservoir (104). A method for dispensing chlorine vapor into the reaction chamber includes providing a chemical storage container (102) containing the chlorine-containing species, flowing the chlorine-containing species from the chemical storage container to the reservoir, converting the chlorine-containing species to chlorine vapor within the reservoir, and controllably flowing the chlorine vapor into the reaction chamber.

Description

[Technical Field]

[0001] FIELD OF THE DISCLOSURE The present disclosure relates generally to chemical dispensing devices and methods for dispensing chemicals into reaction chambers, and more particularly to the storage and conversion of chlorine-containing species into chlorine vapor for use in reaction chambers. [Background technology]

[0002] Some semiconductor fabrication processes utilized in the manufacture of semiconductor device structures may utilize highly corrosive and toxic chemical species that may require complex safety protocols involving proper procedures for safe storage, handling, and disposal.

[0003] A non-limiting example of a toxic chemical species commonly used in semiconductor fabrication processes is chlorine (Cl2) vapor. Chlorine vapor is a gaseous chemical species. For example, chlorine vapor may be utilized in cleaning, etching, and deposition processes, and each semiconductor process requires specialized storage, handling, and disposal of chlorine vapor and any chlorine-based reaction by-products. It is well known that chlorine vapor is highly corrosive, and therefore storage, especially long-term stable storage, may require specialized corrosion-resistant storage containers and purity monitoring procedures. In addition, chlorine vapor is a highly toxic gas that attacks both the eyes and skin as well as the respiratory system. Therefore, an apparatus and method that can utilize alternative chemical species to replace chlorine vapor in the fabrication of semiconductor device structures is desirable. Summary of the Invention

[0004] This Summary is provided to introduce a selection of concepts in a simplified form. These concepts are described in more detail below in the Detailed Description of the Disclosure. This Summary is not intended to identify key features or essential features of the claimed subject matter, nor is it intended to be used to limit the scope of the claimed subject matter.

[0005] In some embodiments, a chemical dispensing apparatus for providing chlorine vapor to a reaction chamber is provided, the apparatus may include a chemical storage container configured to store a chlorine-containing species, a reservoir container in fluid communication with the chemical storage container, the reservoir container configured to convert the chlorine-containing species to chlorine vapor, and a reaction chamber in fluid communication with the reservoir container.

[0006] Embodiments of the present disclosure may also provide a method of supplying chlorine vapor to a reaction chamber. The method may include providing a chemical storage vessel containing a chlorine-containing species, flowing the chlorine-containing species from the chemical storage vessel to a reservoir vessel, converting the chlorine-containing species to chlorine vapor within the reservoir vessel, and controllably flowing the chlorine vapor into the reaction chamber.

[0007] Certain objects and advantages of the present invention have been described hereinabove for purposes of summarizing the invention and the advantages achieved over the prior art. Of course, it is to be understood that not necessarily all such objects or advantages may be achieved in accordance with any particular embodiment of the invention. Thus, for example, those skilled in the art will recognize that the invention may be embodied or performed in a manner that achieves or optimizes one advantage or group of advantages as taught or suggested herein, without necessarily achieving other objects or advantages that may be taught or suggested herein.

[0008] All of these embodiments are intended to be within the scope of the invention disclosed herein. These and other embodiments will be readily apparent to those skilled in the art from the following detailed description of certain embodiments, taken in conjunction with the accompanying drawings, and the invention is not limited to any particular embodiments disclosed. [Brief explanation of the drawings]

[0009] While the specification concludes with claims particularly pointing out and distinctly claiming what are regarded as embodiments of the present disclosure, the advantages of the presently disclosed embodiments may be more readily apparent from the following description of certain examples of the presently disclosed embodiments when read in conjunction with the accompanying drawings.

[0010] [Figure 1] FIG. 1 is a schematic diagram of a chemical delivery device providing chlorine vapor to a reaction chamber according to an embodiment of the present disclosure.

[0011] [Figure 2] FIG. 2 is a process flow diagram of an exemplary method for dispensing chlorine vapor into a reaction chamber according to an embodiment of the present disclosure. DETAILED DESCRIPTION OF THE INVENTION

[0012] Although certain embodiments and examples are disclosed below, it will be understood by those skilled in the art that the invention extends beyond the specifically disclosed embodiments and / or uses of the invention, and obvious variations and equivalents thereof. Accordingly, it is not intended that the scope of the disclosed invention should be limited by the specifically disclosed embodiments described below.

[0013] The figures shown herein are not meant to be actual illustrations of any particular materials, structures or devices, but merely idealized representations used to describe embodiments of the present disclosure.

[0014] As used herein, the term "substrate" may refer to any underlying material or materials that may be used or upon which a device, circuit or film may be formed.

[0015] As used herein, the term "chlorine-containing species" may refer to any species that contains a chlorine (Cl) moiety, excluding chlorine vapor itself.

[0016] Embodiments of the present disclosure may include apparatus and methods for dispensing chlorine vapor into a reaction chamber of a semiconductor processing apparatus. According to embodiments of the present disclosure, pure chlorine vapor is replaced with one or more chlorine-containing species that can be less corrosive and less toxic than pure chlorine vapor. Therefore, the chemical dispensing apparatus and methods of embodiments of the present disclosure do not require stringent corrosion and safety protocols, increasing the efficiency and safety of semiconductor device fabrication.

[0017] 1, which illustrates a semiconductor device including a chemical dispensing apparatus for a reaction chamber. In some embodiments of the present disclosure, apparatus 100 includes a chemical storage container 102, which may be configured to store a chlorine-containing species 103, a reservoir 104 in fluid communication with chemical storage container 102, which is configured to convert the chlorine-containing species into chlorine vapor, and a reaction chamber 106 in fluid communication with reservoir 104.

[0018] It should be noted that chemical dispensing apparatus 100 as shown in FIG. 1 is a simplified schematic version of a chemical dispensing apparatus of the present disclosure and does not include each and every element, i.e., each and every valve, particle filter, seal, gas line, etc., that may be utilized in the construction of a chemical dispensing apparatus of the present disclosure. Chemical dispensing apparatus 100 as shown in FIG. 1 is a simplified schematic version of a chemical dispensing apparatus that provides sufficient disclosure to those skilled in the art to understand embodiments of the present disclosure. Note: This provides an important feature of the device.

[0019] More specifically, the apparatus 100 may include a chemical storage container 102 that may be configured to store a chlorine-containing species 103. In some embodiments of the present disclosure, the chlorine-containing species 103 to be stored in the chemical storage container 102 may be in the form of a solid, liquid, or gas. In some embodiments, the chlorine-containing species 103 to be stored in the chemical storage container 102 may be less harmful, corrosive, and / or toxic than pure chlorine vapor. However, even if the chlorine-containing species 103 is less harmful than pure chlorine vapor, it may still need to be handled and stored carefully.

[0020] In some embodiments of the present disclosure, the chemical storage container 102 may include a quartz material, i.e., the chemical storage container may be substantially made of a quartz material that is substantially chemically inert to the chlorine-containing species 103 stored in the chemical storage container 102. In alternative embodiments of the present disclosure, the chemical storage container 102 may be made of a corrosion-resistant metal or metal alloy, such as, for example, Hastelloy, Monel, or a combination thereof.

[0021] In some embodiments of the present disclosure, the chemical storage vessel 102 may comprise an interior surface 105 that contacts the chlorine-containing species 103. Due to the direct contact between the interior surface 105 of the chemical storage vessel 102 and the chlorine-containing species 103, the interior surface 105 of the vessel may comprise a corrosion-resistant coating that provides a corrosion-resistant surface for the chemical storage vessel, i.e., the corrosion-resistant coating is provided on the interior surface of the chemical storage vessel 102 such that the chlorine-containing species directly contacts the corrosion-resistant coating and not the quartz / metal surface of the chemical storage vessel.

[0022] In some embodiments of the present disclosure, the corrosion-resistant coating on the inner surface 105 may include a fluorine-based corrosion-resistant coating. For example, the fluorine-based corrosion-resistant coating may include one or more of polytetrafluoroethylene (PTFE), fluorinated ethylene propylene copolymer (FEP), perfluoroalkoxy (PFA), polyethylene terephthalate copolymer (PETG), or a polyamide-based copolymer.

[0023] In addition to the interior surfaces of the chemical storage vessels being coated with a corrosion-resistant coating, in some embodiments of the present disclosure, all vapor passages, i.e., gas lines, between the various components of the apparatus 100 may be configured to be corrosion-resistant to the chlorine-containing species stored in the chemical storage vessels 102 and to any reaction by-products that may be produced during the conversion of the chlorine-containing species to chlorine vapor. For example, the vapor passages, valves, connectors, seals, mass flow sections, and certain areas of the apparatus 100 that may come into contact with one or more corrosive species may all be fabricated from corrosion-resistant materials, including Hastelloy, Monel, nickel-based alloys, tantalum, tantalum-based alloys, silicon carbide, boron nitride, aluminum nitride, fused silica, bonded amorphous silicon, and other known chlorine-resistant materials. Additionally, portions of the chemical dispensing apparatus 100 that may be wetted by chlorine-containing species or reaction by-products may be covered with a fluorine-based corrosion-resistant liner, including but not limited to polytetrafluoroethylene (PTFE), fluorinated ethylene propylene copolymer (FEP), or perfluoroalkoxy (PFA).

[0024] In some embodiments of the present disclosure, the chemical storage vessel 102 may further comprise one or more heating units 112 configured to heat the chlorine-containing species 103 stored in the chemical storage vessel 102. In some embodiments of the present disclosure, the one or more heating units 112 may be configured to heat the chlorine-containing species 103 stored in the chemical storage vessel 102. In some embodiments of the present disclosure, the one or more heating units 112 may be configured to heat the chlorine-containing species 103 stored in the chemical storage vessel 102 at a temperature greater than about 0° C., or greater than about 20° C., or greater than about 100° C., or greater than about 150° C., or greater than about 200° C., or greater than about 200° C., or greater than about 300° C., or greater than about 150° C., or greater than about 200° C., or greater than about 300° C., or greater than about 150° C., or greater than about 200° C., or greater than about 300° C., or greater than about 150° C., or greater than about 200° C., or greater than about 300° C., or greater than about 150° C., or greater than about 150° C., or greater than about 200° C., or greater than about 15 ... The chlorine-containing species 103 may be heated to temperatures approximately greater than 400°C.

[0025] In some embodiments, one or more heating elements 112 associated with the chemical storage vessel 102 are configured to convert the chlorine-containing species from a solid to a liquid or gas. In some embodiments, the one or more heating elements 112 associated with the chemical storage vessel 102 may be utilized to control the viscosity of the chlorine-containing species stored in the chemical storage vessel 102.

[0026] More specifically, the vapor path 108 may be connected to the chemical storage vessel 102 such that one or more carrier gases may be transported from a carrier gas storage vessel (not shown) into the chemical storage vessel 102 via the vapor path 108. A mass flow controller 107 may be located on the vapor path 108 and proximate to the chemical storage vessel 102. For example, the mass flow controller 107 may be calibrated to control the mass flux of the carrier gas entering the chemical storage vessel 102, thereby allowing for greater control over the subsequent flow of the chlorine-containing species 103.

[0027] A carrier gas (e.g., hydrogen, nitrogen, helium, argon, and mixtures thereof) may flow over the exposed surfaces of the chlorine-containing species 103, thereby picking up a portion of the chlorine-containing species 103 and transporting the chlorine-containing species, along with the carrier gas, to a desired location within the apparatus 100. In alternative embodiments of the present disclosure, the carrier gas may be "bubbled" through the chlorine-containing species 103, for example, by optional vapor passages 108, thereby agitating and picking up a portion of the chlorine-containing species and transporting the chlorine-containing species, along with the carrier gas, to a desired location within the apparatus 100. For example, in some embodiments, the chlorine-containing species 103 may comprise a highly viscous liquid that is not suitable for vapor transport by bubbling a carrier gas through the chlorine-containing species. Therefore, in some embodiments of the present disclosure, one or more heating elements 112 associated with the chemical storage vessel 102 are utilized to reduce the viscosity of the chlorine-containing species 103, making it more suitable for bubbling a carrier gas through the chlorine-containing species 103 to transport the species to further portions of the apparatus 100.

[0028] In some embodiments of the present disclosure, the chlorine-containing species 103 may comprise a solid, a liquid, or a gas. In some embodiments, the chlorine-containing species 103 may comprise a solid. In some embodiments, the chlorine-containing species 103 may comprise a liquid. In some embodiments, the chlorine-containing species 103 stored in the chemical storage vessel 102 may comprise a non-metal or metalloid chloride, such as at least one of S2Cl2, Se2Cl2, SCl2, SCl, PCl5, SeCl4, SeCl2, SiCl4, SbCl3, SbCl5, BCl3, SOCl2, SeO2Cl2, SO2Cl2, or SeOCl2. In some embodiments, the chlorine-containing species may include carbon and chlorine atoms, such as, for example, CCl4 or C2Cl6. In some embodiments, the chlorine-containing species may include substituted or unsubstituted alkyl and aryl poly-acyl halides, such as succinyl chloride, malonyl chloride, fumaryl chloride, methylene succinyl chloride, glutaryl chloride, or oxalyl chloride. In some embodiments, the chloride-containing species may include metal oxyhalides, such as TiOCl, NbOCl, MoOCl, WOCl, or ReOCl. In some embodiments, the chlorine-containing species may include metal oxyhalides, such as TiOCl, NbOCl, MoOCl, WOCl, or ReOCl. In some embodiments, the chlorine-containing species may include metal oxyhalides, such as ClF, BrCl, ClF, ClF, ICl, or ICl. a Y b In some embodiments, the chlorine-containing species may include interhalogen compounds having the general formula O, such as, for example, FClO, FClO, or perchlorates (e.g., ClO). b X a and O b X a Y c In some embodiments, the chlorine-containing species may include an oxyhalide having the formula: In some embodiments, the chlorine-containing species may include fumaryl chloride (C2H2C2O2Cl2). In some embodiments, the chlorine-containing species may include a chloronitrate. In some embodiments, the chlorine-containing species is metal-free. In some embodiments, the chlorine-containing species 103 stored in the chemical storage container 102 may include a substituted or unsubstituted alkylsulfenyl chloride, including but not limited to trichloromethanesulfenyl chloride or chlorocarbonylsulfenyl chloride. In some embodiments, the chlorine-containing species 103 stored in the chemical storage container 102 may include a substituted or unsubstituted alkylsulfonyl chloride, such as but not limited to trichloromethanesulfonyl chloride.

[0029] In some embodiments of the present disclosure, at least a portion of the chlorine-containing species is transported directly from the chemical storage vessel 102 to the reaction chamber 106 via the vapor passage 110. In such embodiments, the chlorine-containing species bypasses the reservoir 104 and is transported directly to the reaction chamber 106 via the vapor passage 110. In such embodiments, the valve 109A on the vapor passage 110 may be at least partially open to allow the chlorine-containing species to flow directly into the reaction chamber 106.

[0030] In embodiments in which the chlorine-containing species is dispensed directly from the chemical storage container 102 to the reaction chamber 106, the chlorine-containing species may be in a gaseous state or may be converted to a gaseous state by utilizing one or more heaters 112 associated with the chemical storage container 102. In some embodiments, the vapor path 110 may include a mass flow controller 114 disposed along the vapor path 110 before entering the reaction chamber 106. In some embodiments, the mass flow controller 114 may be calibrated to the particular chlorine-containing species present in the chemical storage container 102 such that the mass flow controller 114 may control the mass flux of the chlorine-containing species into the reaction chamber 106.

[0031] In some embodiments of the present disclosure, at least a portion of the chlorine-containing species is transported along with any carrier gas to reservoir 104 via vapor passage 114. For example, valve 109B may be at least partially open to allow vapor to flow from chemical storage vessel 102 to reservoir 104. In such embodiments, the chlorine-containing species may undergo a conversion process within reservoir 104, which converts the chlorine-containing species to chlorine (Cl) vapor.

[0032] In some embodiments of the present disclosure, the reservoir 104 may include, i.e., may be made substantially of, a quartz material. In alternative embodiments, the reservoir 104 may be made of a corrosion-resistant metal or metal alloy, such as, for example, Hastelloy, Monel, or a combination thereof.

[0033] In some embodiments of the present disclosure, the chlorine-containing species may undergo a decomposition process within reservoir 104. In other embodiments of the present disclosure, the chlorine-containing species may undergo a chemical reaction with a suitable chemical reagent within reservoir 104. In some embodiments, the reaction between the chlorine-containing species and the suitable chemical reagent may be activated by irradiation and / or electrical means.

[0034] In some embodiments of the present disclosure, the chlorine-containing species may decompose within the reservoir 104, thereby forming chlorine (Cl) vapor and one or more decomposition by-products. In some embodiments, one or more heating units 116 may be associated with the reservoir 104. In some embodiments, one or more energy units, such as, for example, a power source or an irradiation source, may be associated with the reservoir 104. For example, the one or more heating units 116 associated with the reservoir 104 may be located external to the reservoir 104 (as shown in FIG. 1 ), or in alternative embodiments, the one or more heating units may be located within the reservoir 104 (not shown). The one or more heating units 116 (or alternative energy units, such as, for example, an irradiation unit or an electrical unit) associated with the reservoir 104 may be utilized to decompose the chlorine-containing species into chlorine vapor and one or more decomposition by-products. For example, in some embodiments of the present disclosure, one or more heaters 116 associated with the reservoir 104 may be utilized to heat the chlorine-containing species within the reservoir 104. In some embodiments of the present disclosure, the one or more heaters 116 associated with the reservoir 104 may be configured to heat the chlorine-containing species to a temperature greater than approximately 0° C., or greater than approximately 20° C., or greater than approximately 100° C., or greater than approximately 150° C., or greater than approximately 200° C., or greater than approximately 300° C., or even greater than approximately 400° C. In some embodiments, the one or more heaters 116 associated with the reservoir 104 may heat the chlorine-containing species to a temperature at which the chlorine-containing species thermally decomposes into chlorine (Cl) vapor and one or more decomposition by-products.

[0035] In some embodiments of the present disclosure, decomposition of the chlorine-containing species may result in the formation of chlorine (Cl) vapor and one or more decomposition by-products. In some embodiments of the present disclosure, the reservoir 104 may include a means for separating the chlorine (Cl) vapor from the one or more decomposition products, such that only the chlorine vapor is transported to the reaction chamber 106. For example, in some embodiments, the chlorine-containing species may include SOCl, and upon heating to a temperature greater than 80° C. using one or more heating elements 116, the chlorine-containing species may decompose to form chlorine vapor and decomposition products including SO. In some embodiments of the present disclosure, the decomposition by-products may be selectively separated from the chlorine vapor using nickel (Ni) powder or other catalytically activated surfaces, such that only the chlorine vapor is dispensed into the reaction chamber 106.

[0036] As previously mentioned, in some embodiments of the present disclosure, decomposition of the chlorine species may result in the formation of chlorine vapor and one or more decomposition by-products. In some embodiments, the decomposition by-products may be utilized in the reaction chamber 106, i.e., the one or more decomposition by-products may be utilized by a process operating in the reaction chamber 106. Thus, in some embodiments of the present disclosure, the one or more decomposition by-products produced during the decomposition of the chlorine-containing species are transported to the reaction chamber 106.

[0037] In some embodiments of the present disclosure, the reservoir 104 may include a receptacle 118 that holds a chemical reagent 120. In some embodiments, the reservoir 104 may be fluidly connected via an additional vapor passage (not shown) to allow an additional chemical reagent, such as, for example, an oxygen-containing reagent (e.g., O, O, or HO), to enter the reservoir 104 for reaction with the chlorine-containing species. In some embodiments of the present disclosure, the chemical reagent 120 may be selected to react with the chlorine-containing species to produce chlorine (Cl) vapor and one or more reaction byproducts. For example, a chlorine-containing species may flow from the chemical storage container 102 into the reservoir 104 via the vapor passage 114, whereupon the chlorine-containing species may react with the chemical reagent 120 held in the receptacle 118. The reaction between the chlorine-containing species and the chemical reagent 120 may result in the formation of chlorine (Cl) vapor, which may be transported to the reaction chamber 106, and one or more reaction byproducts. In some embodiments of the present disclosure, one or more reaction byproducts remain retained in receptacle 118, while in other embodiments, one or more reaction byproducts may be transferred to reaction chamber 106 for use in the semiconductor fabrication process.

[0038] In some embodiments of the present disclosure, reservoir 104 may include a means for separating chlorine vapor from one or more reaction products produced by the reaction between the chlorine-containing species and chemical reagent 120. As a non-limiting example embodiment, chemical reagent 120 may include manganese oxide (MnO), and the chlorine-containing species may include hydrochloric acid (HCl). As the HCl passes through the MnO, chlorine vapor may be produced, along with reaction by-products including non-volatile MnCl hydrate powder, which may be kept in receptacle 118. In some embodiments of the present disclosure, chemical reagent 120 may include a solid or vapor, such as an oxygen-containing reagent (e.g., O, HO, or O), a transition metal (e.g., nickel (Ni) or manganese (Mn)), The electrode may include at least one of lithium (Li), aluminum (Al), or a metal oxide (e.g., Al2O3 or MnO2).

[0039] In some embodiments of the present disclosure, the reaction between the chlorine-containing species and the chemical reagent 120 may occur at an elevated temperature. For example, one or more heating elements 116 associated with the reservoir 104 may be utilized to heat the chemical reagent 120 prior to reaction with the chlorine-containing species. As non-limiting example embodiments, the chemical reagent 120 may be heated within the reservoir 104 to a temperature greater than approximately 0° C., greater than approximately 20° C., or even greater than approximately 100° C. In some embodiments of the present disclosure, an alternative energy element may be associated with the reservoir 104 such that the reaction between the chlorine-containing species and the chemical reagent may be facilitated via an alternative energy element, such as, for example, an electrical energy element or a radiation energy element.

[0040] In some embodiments of the present disclosure, the chlorine vapor generated in the reservoir 104 may be transported directly to the reaction chamber 106 for use in the semiconductor fabrication process; in other words, the chlorine vapor generated in the reservoir 104 may be immediately utilized in the reaction chamber 106. In such embodiments, the chlorine vapor may flow through an at least partially open valve 124 and then through a mass flow controller 126 located prior to the entrance to the reaction chamber 106. In some embodiments, the mass flow controller 126 is calibrated for the chlorine vapor and any reaction by-products so that the mass flux of the chlorine vapor entering the reaction chamber can be carefully controlled.

[0041] In other embodiments of the present disclosure, chlorine vapor generated in the reservoir may be accumulated in a vapor reservoir prior to entering the reaction chamber. More specifically, an optional vapor reservoir 122 may be disposed between the reservoir 104 and the reaction chamber 106, and such vapor reservoir 122 may collect and accumulate chlorine vapor generated by the reservoir 104. In some embodiments of the present disclosure, the vapor reservoir 122 may be integral to and disposed within the reservoir 104, while in other embodiments, the vapor reservoir 122 may be disposed external to the reservoir but fluidly connected to the reservoir 104 (as shown in FIG. 1 ). In some embodiments of the present disclosure, the vapor reservoir 122 may accumulate sufficient chlorine vapor to supply the reaction chamber for one or more fabrication processes. As a non-limiting example embodiment, the vapor reservoir 122 may have a chlorine vapor content of 0.01 g / cm 3 Higher or 1g / cm 3 Higher, or 10g / cm 3 In some embodiments of the present disclosure, the vapor reservoir 122 may be configured to dispense, store, and / or extract chlorine vapor at a chlorine fraction pressure of greater than 0.01 Torr, or greater than 0.10 Torr, or greater than 1 Torr, or greater than 10 Torr, or even greater than 50 Torr. In some embodiments of the present disclosure, the vapor reservoir 122 may dispense, store, and / or extract chlorine vapor such that the vapor reservoir 122 may provide a chlorine flow with a flow rate of greater than 0.1 sccm, or greater than 1 sccm, or greater than 10 sccm, or greater than 100 sccm, or greater than 500 sccm, or even greater than 1000 sccm.

[0042] In some embodiments of the present disclosure, chlorine vapor and / or chlorine-containing species are dispensed into a reaction chamber 106. The reaction chamber 106 and associated semiconductor processing equipment (not shown) can take many forms depending on the semiconductor fabrication process being performed in the reaction chamber 106. In some embodiments of the present disclosure, the reaction chamber may comprise a reaction chamber that is at least one of an atomic layer etcher, an atomic layer deposition equipment, a plasma etcher, a chemical vapor deposition equipment, or a pre-treatment equipment. In some embodiments, the equipment does not include a plasma.

[0043] In some embodiments, the reaction chamber 106 may further comprise a substrate support 128. , on which at least one substrate 130 may be positioned for processing. In some embodiments, chlorine vapor may be dispensed from reservoir 104 and enter reaction chamber 106, where the chlorine vapor may contact substrate 130.

[0044] As a non-limiting example embodiment, the reaction chamber 106 may comprise the reaction chamber of an atomic layer etching apparatus, and the substrate may be contacted with chlorine vapor to chlorinate the exposed surface of the substrate 130, i.e., a monolayer of chlorine may be present on the surface of the substrate 130. After chlorinating the surface of the substrate 130, a subsequent process step may include ion bombardment of the chlorinated surface using the optional plasma surface 132; for example, the ions impinging on the substrate surface may include argon ions. Chlorinating the substrate surface and subsequently bombarding the chlorinated surface with argon ions may result in partial removal of the substrate 130 in an atomic layer etching process. The steps of chlorinating the substrate surface and bombarding the chlorinated surface with argon ions may be repeated multiple times until the desired amount of the substrate 130 is removed.

[0045]

[0023] Embodiments of the present disclosure may also include a method of dispensing chlorine vapor into a reaction chamber. The method of the present disclosure can be illustrated with reference to Figure 2, which shows a process flow diagram for an exemplary method 200 according to an embodiment of the present disclosure.

[0046] The exemplary method 200 may include process block 210, which includes providing a chemical storage container containing a chlorine-containing species. More specifically, the method may include fabricating the chemical storage container from a quartz material or a corrosion-resistant metal or metal alloy, such as, for example, Hastelloy or Monel. Additionally, fabricating the chemical storage container may include fabricating the chemical storage container with an inner surface covered with a fluorine-based film, such as, for example, polytetrafluoroethylene (PTFE), fluorinated ethylene propylene copolymer (FEP), or perfluoroalkoxy (PFA). The method of providing a chemical storage container may also further include providing one or more heating units configured to heat the chemical storage container and the chlorine-containing species stored therein. For example, in some embodiments, the method of the present disclosure may include heating the chlorine-containing species in the chemical storage container to a temperature greater than 0° C., greater than 20° C., greater than 100° C., greater than 200° C., greater than 300° C., or even greater than 400° C.

[0047] The method for providing a chemical storage container containing chlorine-containing species further comprises: 2、 The method may include selecting the chlorine-containing species to include a chemical that is liquid or solid at room temperature and ambient pressure, such as at least one of SCl, PCl5, SeCl4, SeCl2, SiCl4, SbCl3, SbCl5, BCl3, SeO2Cl2, SO2Cl2, SeOCl2, SbCl5, or SnCl4. Alternatively, the chlorine-containing species may be selected from a substituted (or unsubstituted) alkylsulfenyl chloride or a substituted (or unsubstituted) alkylsulfonyl chloride.

[0048] The method 200 may continue at process block 220, which includes flowing the chlorine-containing species into a reservoir. More specifically, flowing the chlorine-containing species into the reservoir may include providing a carrier gas into the chemical reservoir. For example, the carrier gas may include at least one of hydrogen, nitrogen, helium, argon, and mixtures thereof. The carrier gas may be utilized to carry the chlorine-containing species into the reservoir. For example, in some embodiments of the method, the carrier gas may be passed over the surface of the chlorine-containing species, while in other embodiments, the carrier gas may be "bubbled" through the chlorine-containing species to assist in picking up the vapor. To further control the flow of the chlorine-containing species into the reservoir, the mass flux of the carrier gas into the chemical reservoir may be controlled by utilizing a mass flow controller.

[0049] Method 200 may continue at process block 230, which includes converting the chlorine-containing species to chlorine vapor in the reservoir. More specifically, methods of the present disclosure may include converting the chlorine-containing species to chlorine vapor by decomposing the chlorine-containing species in the reservoir. For example, the method may include decomposing the chlorine-containing species by heating the chlorine-containing species to a temperature greater than 0° C., greater than 20° C., greater than 100° C., greater than 200° C., greater than 300° C., or even greater than 400° C. Decomposing the chlorine-containing species to form chlorine vapor may also produce one or more decomposition byproducts that may be separated from the chlorine vapor or, alternatively, dispensed into a reaction chamber for use in a fabrication process.

[0050] The methods of the present disclosure may also include converting the chlorine-containing species to chlorine vapor by reacting the chlorine-containing species with a chemical reagent disposed in a reservoir. For example, the chemical reagent utilized to react with the chlorine-containing species may include at least one of an oxygen-containing reagent (e.g., O2, HO, or O3), a transition metal (e.g., nickel (Ni) or manganese (Mn)), lithium (Li), aluminum (Al)), or a metal oxide (e.g., Al2O3 or MnO2). The reaction between the chlorine-containing species and the chemical reagent may produce chlorine vapor and one or more reaction byproducts. In some embodiments of the present disclosure, the methods may include separating the one or more reaction byproducts from the chlorine vapor, or alternatively, the one or more reaction byproducts may be dispensed into a reaction chamber for use in a fabrication process.

[0051] The method 200 may continue at process block 240, which includes controllably flowing chlorine vapor into the reaction chamber. More specifically, the chlorine vapor generated in the reservoir may be dispensed into the reaction chamber using a mass flow controller to adjust the mass flux of the chlorine vapor entering the reaction chamber. For example, a mass flow controller may be disposed between the reservoir and the reaction chamber to control the mass flux of the chlorine vapor before entering the reaction chamber. In some embodiments of the present disclosure, the method may include converting a chlorine-containing species to chlorine vapor before operating the process in the reaction chamber.

[0052] In some embodiments of the present disclosure, the method for controllably flowing chlorine vapor into a reaction chamber may further include accumulating and storing the chlorine vapor in a vapor reservoir before entering the reaction chamber. For example, the vapor reservoir may be disposed between the reservoir and the reaction chamber, and may accumulate and store the chlorine vapor generated in the reservoir. In some embodiments, the method of the present disclosure may include converting chlorine-containing species into chlorine vapor while simultaneously operating a process in the reaction chamber.

[0053] In some embodiments of the present disclosure, the method of controllably flowing chlorine vapor into a reaction chamber may further include exposing a substrate in the reaction chamber to the chlorine vapor. For example, exposing the substrate to the chlorine vapor may comprise a portion of a semiconductor fabrication process performed in the reaction chamber, the semiconductor fabrication process comprising at least one of a deposition process, an etching process, or a cleaning process. As a non-limiting example, exposing the substrate in the reaction chamber to the chlorine vapor may comprise a portion of an atomic layer etching process, where exposing the substrate to the chlorine vapor results in chlorination of the exposed surface of the substrate. The atomic layer etching process may be performed by bombarding the chlorinated surface of the substrate with ions, such as argon ions. Bombarding the chlorinated substrate surface with ions may be achieved by providing a plasma source to the reaction chamber, such as a remote plasma source or a direct current plasma source. Exposing the substrate to the chlorine vapor and subsequent ion bombardment may etch a portion of the substrate in an atomic layer etching process. In some embodiments of the present disclosure, the method may include exposing the substrate to the chlorine vapor in a manner that allows for controlled atomic etching of the substrate until a desired amount of the substrate is removed by the etching process. This may include repeated exposure and subsequent bombardment of the ions with the chlorinated surface. In some embodiments of the present disclosure, the apparatus 100 may not include a plasma source.

[0054] The exemplary embodiments of the present disclosure described above are merely examples of embodiments of the present invention, as defined by the appended claims and their legal equivalents, and therefore do not limit the scope of the present invention. Any equivalent embodiments are intended to be within the scope of the present invention. Indeed, various modifications of the present disclosure in addition to those shown and described herein may become apparent to those skilled in the art from the description, including alternative useful combinations of the described elements. Such modifications and embodiments are also intended to fall within the scope of the appended claims. [Mode of the invention] [1] 1. A chemical dispensing apparatus for providing chlorine vapor to a reaction chamber, comprising: a chemical storage vessel configured to store a chlorine-containing species; a reservoir vessel in fluid communication with the chemical storage vessel, the reservoir vessel configured to convert the chlorine-containing species to the chlorine vapor; a reaction chamber in fluid communication with the reservoir. [2] 2. The apparatus of claim 1, wherein the reaction chamber comprises the reaction chamber of an atomic layer etching apparatus. [3] 2. The apparatus of claim 1, wherein the chemical storage vessel comprises a quartz material. [4] 10. The apparatus of claim 1, wherein the chemical storage container has an interior surface covered with a fluororesin-based film, the fluororesin-based film comprising at least one of polytetrafluoroethylene (PTFE), fluorinated ethylene propylene copolymer (FEP), perfluoroalkoxy (PFA), polyethylene terephthalate copolymer (PETG), or polyamide-based copolymer. [5] 11. The apparatus of claim 1, wherein the reservoir further comprises one or more heating elements configured to thermally decompose the chlorine-containing species. [6] 2. The apparatus of claim 1, further comprising a vapor storage unit for storing the chlorine vapor, the vapor storage unit being disposed between the reservoir and the reaction chamber. [7] 2. The apparatus of claim 1, wherein the reservoir further comprises a chemical reagent configured to react with the chlorine-containing species to produce the chlorine vapor. [8] 10. The apparatus of claim 1, further comprising one or more heating units configured to heat the chlorine-containing species stored in the chemical storage vessel. [9] 2. The apparatus of claim 1, wherein the chlorine vapor comprises chlorine (Cl2).

[10] 1. A method for dispensing chlorine vapor into a reaction chamber, comprising: providing a chemical storage vessel, the chemical storage vessel containing a chlorine-containing species; flowing the chlorine-containing species from the chemical storage vessel to a reservoir; converting the chlorine-containing species into chlorine vapor within the reservoir; and controllably flowing the chlorine vapor into the reaction chamber.

[11] The chemical storage container has an inner surface covered with a fluorine-based film, 11. The method of claim 10, wherein the film comprises at least one of polytetrafluoroethylene (PTFE), fluorinated ethylene propylene copolymer (FEP), perfluoroalkoxy (PFA), polyethylene terephthalate copolymer (PETG), or polyamide-based copolymer.

[12] 11. The method of claim 10, wherein the chemical storage vessel comprises a quartz material.

[13] 11. The method of claim 10, further comprising providing one or more heating units configured to heat the chlorine-containing species stored in the chemical storage vessel.

[14] The chlorine-containing species include S2Cl2, Se2Cl2, SCl 2、 11. The method of claim 10, comprising at least one of SCl, PCl5, SeCl4, SeCl2, SiCl4, SbCl3, ICl3, Icl, SbCl5, BCl3, SeO2Cl2, SO2Cl2, SeOCl2, or SnCl4.

[15] 11. The method of claim 10, wherein the chlorine-containing species comprises at least one of CCl4, C2Cl6, succinyl chloride, malonyl chloride, fumaryl chloride, methylene succinic acid chloride, glutaryl chloride, oxalyl chloride, TiOCl2, NbOCl3, MoOCl4, WOCl4, ReO2Cl3, ClF, BrCl, ClF3, ClF5, ICl3, ICl, FClO2, FClO3, or Cl2O.

[16] 11. The method of claim 10, wherein the chlorine-containing species comprises a substituted or unsubstituted alkylsulfenyl chloride or a substituted or unsubstituted alkylsulfonyl chloride.

[17] 11. The method of claim 10, wherein converting the chlorine-containing species to chlorine vapor further comprises decomposing the chlorine-containing species.

[18] 11. The method of claim 10, wherein converting the chlorine-containing species to chlorine vapor further comprises reacting the chlorine-containing species with a chemical reagent.

[19] 19. The method of claim 18, wherein the chemical reagent comprises at least one of oxygen (O2), water (H2O), ozone (O3), a transition metal, or a metal oxide.

[20] 11. The method of claim 10, wherein the reaction chamber comprises the reaction chamber of an atomic layer etching system. [twenty one] 11. The method of claim 10, further comprising providing a vapor reservoir for accumulating and storing the chlorine vapor, the vapor reservoir being disposed between the reservoir and the reaction chamber. [twenty two] 11. The method of claim 10, wherein controllably flowing the chlorine vapor into the reaction chamber further comprises exposing a substrate disposed within the reaction chamber to the chlorine vapor. [twenty three] 23. The method of claim 22, wherein exposing the substrate in the reaction chamber to the chlorine vapor further comprises etching a portion of the substrate.

Claims

1. 1. A chemical dispensing apparatus for providing chlorine vapor to a reaction chamber, comprising: a chemical storage vessel configured to store a chlorine-containing species; a reservoir vessel in fluid communication with the chemical storage vessel, the reservoir vessel configured to thermally decompose the chlorine-containing species into the chlorine vapor and decomposition by-products; a vapor storage unit for storing chlorine vapor, the vapor storage unit being disposed downstream of the storage vessel; a mass flow controller that controls the mass flux of the chlorine vapor before it enters the reaction chamber; Equipped with The chlorine-containing species include S2Cl2, Se2Cl2, SCl2, SCl, PCl5, SeCl4, SeCl2, SiCl4, SbCl3, ICl3, ICl, SbCl5, BCl3, SeO2Cl2, SO2Cl2, SeOCl2, SnCl4, CCl4, C2Cl6, succinyl chloride, malonyl chloride, fumaryl chloride, methylene succinic acid chloride, glutaryl chloride, oxalyl chloride, TiOCl2, NbOCl3, MoOCl4, WOCl4, ReO2Cl3, ClF, BrCl, ClF3, ClF5, FClO2, FClO. 3, Cl 2 O, a substituted or unsubstituted alkylsulfenyl chloride, or a substituted or unsubstituted alkylsulfonyl chloride.

2. The apparatus of claim 1 , wherein the chemical storage vessel comprises a quartz material.

3. 10. The apparatus of claim 1, wherein the chemical storage vessel comprises an interior surface covered with a fluororesin-based film, the fluororesin-based film comprising at least one of polytetrafluoroethylene (PTFE), fluorinated ethylene propylene copolymer (FEP), perfluoroalkoxy (PFA), polyethylene terephthalate copolymer (PETG), or a polyamide-based copolymer.

4. 10. The apparatus of claim 1, wherein the reservoir further comprises one or more heating elements configured to thermally decompose the chlorine-containing species.

5. 1. A chemical dispensing apparatus for providing chlorine vapor to a reaction chamber, comprising: a chemical storage vessel configured to store a chlorine-containing species; a reservoir vessel in fluid communication with the chemical storage vessel, the reservoir vessel configured to decompose the chlorine-containing species into the chlorine vapor and decomposition by-products; a mass flow controller that controls the mass flux of the chlorine vapor before it enters the reaction chamber; Equipped with the reservoir further comprises a chemical reagent configured to react with the chlorine-containing species to produce the chlorine vapor; The apparatus, wherein the chemical reagent comprises at least one of oxygen (O 2 ), water (H 2 O), ozone (O 3 ), a transition metal, or a metal oxide.

6. 10. The apparatus of claim 1, further comprising one or more heating units configured to heat the chlorine-containing species stored in the chemical storage vessel.

7. The chlorine vapor is chlorine (Cl ２ 10. The apparatus of claim 1, comprising:

8. 1. A method for dispensing chlorine vapor into a reaction chamber, comprising: providing a chemical storage vessel, the chemical storage vessel containing a chlorine-containing species; flowing the chlorine-containing species from the chemical storage vessel to a reservoir; thermally decomposing the chlorine-containing species within the reservoir into chlorine vapor and decomposition by-products; controllably flowing the chlorine vapor into the reaction chamber; Including, The chlorine-containing species include S2Cl2, Se2Cl2, SCl2, SCl, PCl5, SeCl4, SeCl2, SiCl4, SbCl3, ICl3, ICl, SbCl5, BCl3, SeO2Cl2, SO2Cl2, SeOCl2, SnCl4, CCl4, C2Cl6, succinyl chloride, malonyl chloride, fumaryl chloride, methylene succinic acid chloride, glutaryl chloride, oxalyl chloride, TiOCl2, NbOCl3, MoOCl4, WOCl4, ReO2Cl3, ClF, BrCl, ClF3, ClF5, FClO2, FClO. 3, Cl 2 O, a substituted or unsubstituted alkylsulfenyl chloride, or a substituted or unsubstituted alkylsulfonyl chloride.

9. 10. The method of claim 8, wherein the chemical storage vessel comprises an interior surface covered with a fluororesin-based film, the fluororesin-based film comprising at least one of polytetrafluoroethylene (PTFE), fluorinated ethylene propylene copolymer (FEP), perfluoroalkoxy (PFA), polyethylene terephthalate copolymer (PETG), or a polyamide-based copolymer.

10. The method of claim 8 , wherein the chemical storage vessel comprises a quartz material.

11. 10. The method of claim 8, further comprising providing one or more heating sections configured to heat the chlorine-containing species stored in the chemical storage vessel.

12. 1. A method for dispensing chlorine vapor into a reaction chamber, comprising: providing a chemical storage vessel, the chemical storage vessel containing a chlorine-containing species; flowing the chlorine-containing species from the chemical storage vessel to a reservoir; decomposing the chlorine-containing species into chlorine vapor and decomposition by-products within the reservoir; and controllably flowing the chlorine vapor into the reaction chamber; decomposing the chlorine-containing species into chlorine vapor and decomposition by-products further comprises reacting the chlorine-containing species with a chemical reagent; The method, wherein the chemical reagent comprises at least one of oxygen (O 2 ), water (H 2 O), ozone (O 3 ), a transition metal, or a metal oxide.

13. 1. A method for dispensing chlorine vapor into a reaction chamber, comprising: providing a chemical storage vessel, the chemical storage vessel containing a chlorine-containing species; flowing the chlorine-containing species from the chemical storage vessel to a reservoir; thermally decomposing the chlorine-containing species into chlorine vapor and decomposition by-products within the reservoir or using a chemical reagent to decompose the chlorine-containing species into chlorine vapor and decomposition by-products; providing a vapor reservoir between the reservoir and the reaction chamber for accumulating and storing the chlorine vapor; controllably flowing the chlorine vapor into the reaction chamber; Including, In the case of thermal decomposition, the chlorine-containing species are S2Cl2, Se2Cl2, SCl2, SCl, PCl5, SeCl4, SeCl2, SiCl4, SbCl3, ICl3, ICl, SbCl5, BCl3, SeO2Cl2, SO2Cl2, SeOCl2, SnCl4, CCl4, C2Cl6, succinyl chloride, malonyl chloride, fumaryl chloride, methylene succinic acid chloride, glutaryl chloride, oxalyl chloride, TiOCl2, NbOCl3, MoOCl4, WOCl4, ReO2Cl3, ClF, BrCl, ClF3, ClF5, FClO2. , FClO 3 , Cl 2 O, substituted or unsubstituted alkylsulfenyl chloride, or substituted or unsubstituted alkylsulfonyl chloride; In the case of decomposition using a chemical reagent, the chemical reagent comprises at least one of oxygen (O 2 ), water (H 2 O), ozone (O 3 ), a transition metal, or a metal oxide.

14. 9. The method of claim 8, wherein said controllably flowing chlorine vapor comprises exposing a substrate to said chlorine vapor.

15. The method of claim 14 , wherein exposing the substrate to the chlorine vapor comprises etching a portion of the substrate.

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