Acetylene fluid supply package, system comprising the same and method of fabricating semiconductor device using the same

Abstract

To provide an acetylene fluid supply package that results in improved storage, handling and delivery capabilities, a system including the same, and a method for producing a semiconductor device utilizing the same.SOLUTION: There is provided a composition comprising acetylene fluid at least partially solubilized in an improved solvent. The improved solvents exhibit non-toxicity and are further characterized by low vapor pressures to minimize solvent carryover during delivery of the acetylene fluid, while retaining suitable acetylene solubilizing capacity. In one aspect, there is provided an acetylene fluid supply package, comprising a pressure vessel; a porous filler in the pressure vessel; and an improved solvent within the porous filler, the solvent solubilizing with acetylene absorbed within the improved solvent; the improved solvent comprising triethyl phosphate (TEP), the TEP loaded into the pressure vessel in an amount no greater than about 0.64 kg of TEP per liter of volume of the pressure vessel.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The inventive concept relates to novel compositions of improved solvents that solubilize acetylene fluids. In particular, the improved solvents are non-toxic for storage, distribution, and handling of acetylene fluids, and further feature low vapor pressures that minimize solvent carryover during delivery of acetylene fluids while maintaining adequate solubilization capacity for acetylene. [Background technology]

[0002] Acetylene is widely used in industry for a variety of applications, such as welding and chemical synthesis. Of particular importance is its increasing use in the electronics industry as a feedstock for depositing carbon and carbon-containing films. Applications include the deposition of amorphous carbon hardmask films.

[0003] However, due to its thermal instability, storing acetylene poses numerous difficulties: acetylene can explosively decompose into carbon and hydrogen under storage conditions of high pressure and temperature, even in the absence of air or oxygen.

[0004] To address thermal instability, acetylene cylinders are uniquely constructed. Each cylinder contains a porous filler (e.g., silica) along with a solvent, typically containing acetone, dimethylformamide (DMF), or N-methyl-2-pyrrolidone (NMP), dispersed throughout the porous filler medium. Traditionally, these solvents have been chosen for their ability to solubilize acetylene. The porous filler medium is generally a porous mass with a porosity of approximately 90% by volume. The function of the porous filler medium is to separate acetylene into small units within the pores, which helps inhibit acetylene decomposition. The function of the solvent is to absorb large amounts of acetylene at relatively low pressures, allowing for high cylinder loadings in low-pressure cylinders. The solvent is dispersed throughout the voids and surrounding the porous filler medium.

[0005] Notwithstanding the improved thermal stability of such cylinder systems, applicants have discovered that certain modifications to existing acetylene cylinder fluid supply packages, as described herein, result in improved storage, handling and delivery capabilities. Summary of the Invention

[0006] In a first aspect, an acetylene fluid supply package includes a pressure vessel; a porous filler within the pressure vessel; and an improved solvent within the porous filler, the improved solvent solubilizing acetylene absorbed within the improved solvent, the improved solvent comprising triethyl phosphate (TEP), the TEP being filled into the pressure vessel in an amount of about 0.64 kg or less of TEP per liter of pressure vessel volume.

[0007] In a second aspect, a system is provided comprising at least one acetylene fluid supply package and an acetylene-utilizing process tool in fluid communication with the at least one acetylene fluid supply package, the at least one acetylene fluid supply package comprising: a pressure vessel; a porous filler within the pressure vessel; and an improved solvent within the porous filler, the improved solvent solubilizing acetylene absorbed within the improved solvent, the improved solvent comprising triethyl phosphate (TEP), the TEP being filled into the pressure vessel in an amount of about 0.64 kg or less of TEP per liter of pressure vessel volume, the at least one acetylene fluid supply package being configured to allow release of acetylene fluid under dispensing conditions, and the acetylene-utilizing process tool being configured to receive acetylene fluid from the at least one acetylene fluid supply package.

[0008] In a third aspect, a method of manufacturing a semiconductor device includes providing a semiconductor substrate and forming a carbon-containing layer on the semiconductor substrate using an acetylene fluid delivery package, the acetylene fluid delivery package including a pressure vessel, a porous filler within the pressure vessel, and a solvent within the porous filler, the solvent solubilizing acetylene absorbed within the solvent, the solvent having a vapor pressure of 6 Torr or less at 20° C. and a Hansen solubility factor (δh) of 5 MPa. 0.5 and the reproductive toxicity of the solvent is lower than that of dimethylformamide (DMF). [Brief explanation of the drawings]

[0009] These and other aspects and features of the inventive concept will become more apparent from a full detailed description of illustrative embodiments thereof, taken in conjunction with the accompanying drawings. [Figure 1] 1A-1C are schematic diagrams illustrating various acetylene fluid supply packages according to some embodiments. [Figure 2] 1A-1C are schematic diagrams illustrating various acetylene fluid supply packages according to some embodiments. [Figure 3] 1A-1C are schematic diagrams illustrating various acetylene fluid supply packages according to some embodiments. [Figure 4] FIG. 1 is a schematic diagram illustrating a deposition system including an acetylene fluid supply package according to some embodiments. [Figure 5] 10 is a graph illustrating the effect of an acetylene fluid supply package according to some embodiments. [Figure 6] 10 is a graph illustrating the effect of an acetylene fluid supply package according to some embodiments. [Figure 7] 10 is a graph illustrating the effect of an acetylene fluid supply package according to some embodiments. [Figure 8] 1A-1D illustrate intermediate steps in a method for manufacturing a semiconductor device according to some embodiments. [Figure 9] 1A-1D illustrate intermediate steps in a method for manufacturing a semiconductor device according to some embodiments. [Figure 10] 1A-1D illustrate intermediate steps in a method for manufacturing a semiconductor device according to some embodiments. [Figure 11] 1A-1D illustrate intermediate steps in a method for manufacturing a semiconductor device according to some embodiments. [Figure 12] 1A-1D illustrate intermediate steps in a method for manufacturing a semiconductor device according to some embodiments. [Figure 13] 1A-1D illustrate intermediate steps in a method for manufacturing a semiconductor device according to some embodiments. [Figure 14] 1A-1D illustrate intermediate steps in a method for manufacturing a semiconductor device according to some embodiments. [Figure 15] 1A-1D illustrate intermediate steps in a method for manufacturing a semiconductor device according to some embodiments. [Figure 16] 1A-1D illustrate intermediate steps in a method for manufacturing a semiconductor device according to some embodiments. [Figure 17] 1A-1D illustrate intermediate steps in a method for manufacturing a semiconductor device according to some embodiments. [Figure 18] 1A-1D illustrate intermediate steps in a method for manufacturing a semiconductor device according to some embodiments. [Figure 19] 1A-1D illustrate intermediate steps in a method for manufacturing a semiconductor device according to some embodiments. [Figure 20] 1A-1D illustrate intermediate steps in a method for manufacturing a semiconductor device according to some embodiments. [Figure 21] 1A-1D illustrate intermediate steps in a method for manufacturing a semiconductor device according to some embodiments. [Figure 22] 1A-1D illustrate intermediate steps in a method for manufacturing a semiconductor device according to some embodiments. [Figure 23] 1A-1D illustrate intermediate steps in a method for manufacturing a semiconductor device according to some embodiments. [Figure 24] 1A-1D are intermediate views illustrating a method for manufacturing a semiconductor device according to some embodiments. DETAILED DESCRIPTION OF THE INVENTION

[0010] The compositions, fluid supply packages, and systems disclosed herein can comprise, consist of, or consist essentially of any of the specific components and structures illustratively described herein. The present disclosure further contemplates narrowly defined compositions, fluid supply packages, and systems, where, for example, one or more of the specifically described parts, components, and structures can be specifically omitted when defining an operating embodiment of the present disclosure.

[0011] It should also be understood that the embodiments as described below are merely examples, and that the inventive concept is not limited to the embodiments illustrated in the drawings, which are for purposes of illustrating the embodiments, are not intended to be drawn to scale, and in certain instances, omit details that are not necessary for an understanding of the embodiments.

[0012] As used herein and throughout, the term "fluid" is intended to include gases, vapors, liquids, and mixtures of the foregoing. "Acetylene fluid," as described herein and throughout, is intended to mean that substantially all of the acetylene is stored under pressure in the vapor phase during storage in the container, although the acetylene fluid may pick up small amounts of solvent carryover when removed from the container. The term "solvent" or "solvent fluid" is intended to refer substantially to a solvent in a liquid phase that is in substantial equilibrium with a corresponding vapor phase of relatively low vapor pressure.

[0013] Any of the terms "container" or "cylinder," or "package" or "delivery package" or "fluid supply package," may be used interchangeably herein and refer to a container that can be stored, filled, delivered, or transported.

[0014] As used herein and throughout with respect to vapor pressure, "about" means ±3 Torr.

[0015] The inventive concept recognizes the shortcomings of existing acetylene fluid supply packages. For example, applicants have observed that acetone, when used as a solvent, has an unacceptably high vapor pressure, and thus acetone vapor can be drawn from the storage container and unnecessarily transported with the dispensed acetylene. Acetone solvent is a contaminant in acetylene in several applications, such as deposition of carbon and carbon-containing films, including amorphous carbon hardmask films in the electronics industry. Ultimately, therefore, acetone can reduce the deposition rate of the film, affecting process uniformity and consistency.

[0016] To reduce contamination in applications where solvent impurities are unacceptable in acetylene-derived carbon-containing films, alternative solvents with lower vapor pressures than acetone have been utilized for acetylene storage and distribution. For example, DMF and N-methyl-2-pyrrolidone (NMP) are utilized as solvents as part of acetylene fluid supply packages. However, both DMF and NMP are toxic. In particular, DMF and NMP pose a risk of reproductive toxicity (i.e., teratogenicity). Due to these health risks, the commercial use of DMF and NMP is restricted in some countries. Substances that pose a risk of reproductive toxicity are classified as having the H360 hazard presentation code under the Globally Harmonized System of Classification and Labeling of Chemicals (GHS). As used herein, toxic refers to substances classified as having the H360 hazard presentation code.

[0017] Therefore, in view of such drawbacks associated with the use of conventional solvents in acetylene storage and delivery systems, Applicant has identified an improved solvent that is a safer alternative to conventional solvents for the storage and delivery of acetylene. The inventive concept requires a combination of specific attributes. The attributes of the improved solvent include: (i) a vapor pressure at 20°C of about 6 Torr or less; (ii) a higher degree of non-toxicity compared to dimethylformamide (DMF) and N-methyl-2-pyrrolidone (NMP); (iii) a chemical structure comprising at least one O, N, or F atom, wherein the at least one O, N, or F atom is not bonded to a hydrogen atom, and wherein the chemical structure is further characterized by an absence of boron, calcium, and nickel; and (iv) a vapor pressure at 20°C of about 5 MPa. 0.5 The improved solvent, possessing the aforementioned attributes, can be used as part of an acetylene storage and delivery system that does not exhibit a reduction in acetylene solubilization performance compared to conventional solvents.

[0018] On the other hand, conventional solvents such as DMF and NMP are generally classified as H360 under the Globally Harmonized System of Classification and Labelling of Chemicals (see Table 2 below). In other words, they pose a risk of reproductive toxicity and teratogenicity. The solvents of the present invention do not pose a risk of reproductive toxicity and are therefore characterized by the absence of an H360 hazard presentation code as classified by the GHS. The solvents of the present invention are generally more benign as a result of the absence of the H360 classification.

[0019] In addition to being more non-toxic, the solvents of the present invention maintain sufficient solubility and interaction with acetylene. Applicant has identified a combination of attributes necessary to provide effective solubility of the solvent within the acetylene fluid. The solvent molecules and acetylene molecules are attracted to each other so that at least a portion of the acetylene molecules can exist with the solvent in a thermodynamically stable state. On the other hand, if the solvent molecules and acetylene molecules repel each other, acetylene's solubility in the solvent is expected to be insufficient (i.e., its solubility in acetylene will be lower than that of traditionally used solvents such as DMF, acetone, and NMP). Acetylene has a chemical structure of C2H2, with triple bonds between the carbon atoms. Each carbon atom is covalently bonded to a hydrogen atom, which represents an available center for interacting with the solvent molecules. This hydrogen atom preferably hydrogen bonds with the negative polarity site of the solvent molecule, enabling sufficient solubility. Such negative polarity sites can be made available by selecting a polar solvent with electronegative sites provided by N, O, or F atoms. The solubility of acetylene in a solvent increases with the solvent's ability to hydrogen bond with the acetylene molecule. Applicant has discovered that the effectiveness of hydrogen bonding can be reliably assessed by the Hansen Solubility Interaction Parameter, designated as δh, which is defined in the art as the energy from hydrogen bonding between molecules. This parameter indicates the strength with which a solvent can form either intramolecular or intermolecular hydrogen bonds. The higher the value of δh, the greater the effectiveness of the solvent in forming hydrogen bonds with it. In accordance with the concepts of the present invention, a higher δh for a particular solvent indicates greater solubility of the acetylene fluid within the solvent molecule. In a preferred embodiment, δh is about 5 MPa. 0.5 Exceeds.

[0020] Another attribute required for the inventive concept is the avoidance, reduction, or minimization of OH, FH, or NH bonds in the solvent molecule, so that the molecular structure of the solvent contains at least one O, N, or F atom that is not bonded to an H atom in the solvent molecule. Applicant has discovered that the presence of an excess of OH, FH, or NH bonds in the solvent molecule can potentially limit the availability of electronegative sites at which hydrogen bonding with acetylene molecules can occur, thereby creating intermolecular hydrogen bonds, since the solvent molecule has a tendency to self-hydrogen bond with itself. By way of example, and not by way of limitation, if the solvent molecule contains two oxygen atoms, the tendency for self-hydrogen bonding in the solvent molecule cannot be reduced by bonding at least one of the two oxygen atoms to a hydrogen atom in the molecule.

[0021] The combination of (i) a sufficiently high δh and (ii) a solvent molecular structure that includes at least one O, N, or F atom that is not internally bonded to an H atom promotes the ability of the solvent molecules to more effectively interact with and solubilize the acetylene molecule. In other words, a solvent structure that avoids or minimizes intramolecular H-bonding within the solvent molecule can provide a pressure of approximately 5 MPa. 0.5 The combination of δh above can promote hydrogen bonding between the solvent and the acetylene molecule.

[0022] While providing a solvent with non-toxicity and effective solubility in the acetylene fluid is important, the present invention further seeks to reduce carryover during acetylene distribution by providing solvent molecules with a relatively low vapor pressure. In this regard, the solvents of the present invention have a vapor pressure at 20° C. of about 6 Torr or less. Utilizing solvent molecules with lower vapor pressures minimizes contaminants in the acetylene dispensed to downstream applications. The relatively low vapor pressure of the solvents of the present invention allows for minimal solvent carryover during acetylene dispense, thereby enabling delivery of high-purity acetylene. In contrast, conventional solvents such as acetone have a vapor pressure of 187 Torr at 20° C., which poses the risk of introducing large amounts of contaminants, as large amounts of acetone tend to be removed from the container with the acetylene (see Table 2 below).

[0023] Having described all the necessary attributes of the solvents of the present invention, Table 1 shows representative, non-limiting examples of solvents according to the principles of the inventive concept. As can be seen, triethyl phosphate (TEP), dihydrolevoglucosenone (Cyrene), tetraethylene glycol dimethyl ether, acetic anhydride, cyclohexanone, pentoxone, and mesityl oxide are solvents that are expected to be safer to handle and exhibit sufficient solubility with the acetylene fluid in the container. All of the solvents of the present invention do not have an H360 classification and exhibit relatively low vapor pressures of about 6 Torr or less, designated as δh, of about 5 MPa. 0.5 The solvent is characterized by a Hansen Solubility Interaction Parameter (δh) greater than 0.05 and a molecular structure that eliminates, reduces, or minimizes OH, FH, or NH bonds in the solvent molecule, such that the molecular structure of the solvent contains at least one O, N, or F atom that is not bonded to an H atom in the solvent molecule. Furthermore, the solvent's chemical structure does not contain P, B, Ca, or Ni atoms. This combination of attributes represents a significant improvement and departure from conventional solvents used in acetylene storage and delivery. Table 2 lists DMF, acetone, and NMP under the heading "Prior Art" as representative conventional solvents used in acetylene storage. As can be seen, conventional solvents have one or more drawbacks, such as H360 toxicity and / or unacceptably high vapor pressure. Hansen Solubility Parameters (δh) values ​​were generated using commercially available software known as HSPiP software, available at the official website https: / / www.hansen-solubility.com / contact.php.

[0024] [Table 1]

[0025] [Table 2]

[0026] It should be understood that other solvents not listed in Table 1 are also contemplated by the concepts of the present invention. For example, solvents of the present invention may include, but are not limited to, the following compounds: (1) N,N,N',N'-Tetramethylmethyl-phosphondiamide

[0027] [ka] (2) Tetramethylene sulfoxide

[0028] [ka] (3) Tetramethylurea

[0029] [ka] (4) N-acetylpyrrolidine

[0030] [ka] (5) Tris(N,N-tetramethylene)phosphoramide

[0031] [ka] (6) Methylnaphthodioxane

[0032] [ka] (7) Trimethyl phosphite

[0033] [ka] (8) Tetramethyldiamidophosphoryl fluoride

[0034] [ka]

[0035] 1-3 are schematic diagrams illustrating various acetylene fluid supply packages in accordance with certain embodiments of the inventive concept.

[0036] Referring to FIG. 1, an acetylene fluid supply package according to certain embodiments includes a storage vessel (or pressure vessel) 12 having an interior volume occupied by a porous medium (or porous filler) 20 (e.g., silica) pre-packed within the vessel 12. One or more of the inventive solvents 30 are dispersed or packed within and around the porous medium 20. C2H2 is stored by solubilizing C2H2 (32) in the solvent 30 to a desired pressure. Typical packing pressures range from 200 to 300 psig at 21°C. A pressure regulation device (52) is attached to the outlet 14 of the cylinder 12 to reduce the outlet pressure to a desired pressure (approximately 15 to 30 psig) before connecting to a flow control device for ease of operation. A shut-off valve 16 is shown along the top of the vessel 12. The acetylene fluid is at least partially solubilized in the improved solvent 30.

[0037] Outlet 14 may function as a gate through which acetylene fluid may be discharged from or introduced into vessel 12. For example, acetylene fluid may be discharged from or introduced into vessel 12 through a gas line 50 connected to outlet 14. A shut-off valve 16 may be installed at outlet 14 to selectively open and close outlet 14, thereby controlling the acetylene fluid. In certain embodiments, gas line 50 may further be provided with a first valve 52. First valve 52 may control the amount of acetylene fluid flowing through gas line 50 and may also function as a pressure regulating device so that cylinder pressure is reduced to a desired level.

[0038] Referring to FIG. 2, an acetylene fluid supply package according to some embodiments includes the vessel 12 of FIG. 1, where at least a portion of the acetylene fluid is solubilized in one or more of the solvents 30 of the present invention and dispersed within and around a porous media 20 in combination with a solvent trap 60. A cylinder or storage vessel (12) packed with a porous filler material (20) is filled with the desired solvent (30). The solvent is dispersed in the voids within and around the porous filler material. C2H2 is stored by solubilizing the C2H2 in the solvent to a desired pressure. Typical packing pressures are in the range of 200-300 psig at 21°C. The solvent trap 60 is a canister containing an adsorbent mounted upstream of the outlet of the cylinder and a pressure regulation device 52. It should be understood that the canister can be filled with any suitable desired adsorbent medium, such as activated carbon, zeolite, or metal-organic framework, capable of capturing the solvent of the present invention that may pass through the canister as a result of being withdrawn from the interior volume of the vessel 12. In this manner, removal of any carryover solvent can be achieved, thereby improving the purity of the delivered acetylene, which is desirable for important applications such as the deposition of carbon films for electronic device manufacturing.

[0039] Referring to FIG. 3, an acetylene fluid supply package according to some embodiments includes a solvent trap 60 located downstream of the pressure regulation device 52 .

[0040] It should be understood that Figures 1-3 represent non-limiting examples of storage and delivery packages having improved solvent 30, porous media 20, and acetylene. Other configurations for the storage and delivery packages are contemplated without departing from the scope of the inventive concepts. For example, the acetylene fluid supply package of the present disclosure may be of any configuration suitable for containing acetylene fluid during storage and transport conditions and for evacuating the acetylene fluid from the fluid supply package during dispensing conditions. It should be understood that a single solvent 30 may be utilized, or a mixture of two or more solvents 30 may be utilized, with the resulting mixture characterized by each of the attributes sought by the inventive concepts as described above. Dispensing conditions may be provided by actuating a fluid dispensing assembly to effect dispensing, for example, by opening a valve in a valve head of the fluid dispensing assembly of the package.

[0041] The inventive concepts contemplate various areas of use for the compositions described herein. For example, some processes include, but are not limited to, chemical vapor deposition, plasma-enhanced chemical vapor deposition, beam-line ion implantation, and plasma immersion ion implantation. An example of the use of the acetylene delivery package (i.e., acetylene fluid supply package) of the inventive concepts is shown in FIG. 4. FIG. 4 is a schematic diagram illustrating a deposition system including an acetylene fluid supply package according to some embodiments. FIG. 4 illustrates the use of the acetylene delivery package operably connected to specific process equipment in a process for depositing carbon films for electronic device manufacturing applications.

[0042] Referring to FIG. 4, one or more acetylene delivery packages GP are configured within a gas cabinet 10. Acetylene is drawn from any of the acetylene delivery packages of FIGS. 1, 2, or 3, and then the acetylene is dispensed into a process chamber 80 via a flow control device 70, which can be configured to establish an acetylene flow rate ranging from 0.1 slpm to 10 slpm. The process chamber 80 is preferably maintained at a pressure ranging from 0.1 to 10 Torr. To support the deposition of high-purity carbon films, the target substrate W is heated to an elevated temperature ranging from 100°C to 800°C. The process chamber 80 can include a plasma source to support the carbon deposition process. It should be understood that the acetylene delivery package can be operated at other flow rates, temperatures, and pressures.

[0043] It should further be understood that multiple acetylene delivery packages, such as those shown in Figure 1, can be loaded into the gas cabinet 10. The outlet of each acetylene delivery package is connected to a dedicated flow control device 70, with each device running to the inlet of a process chamber 80. Acetylene can be stored within each delivery package at a pressure of up to about 300 psig at 21°C. Upon actuation of the shut-off valve to the open position, a controlled flow of acetylene is dispensed from its dedicated container.

[0044] It should further be appreciated that multiple acetylene delivery packages GP may be bundled together to form a package bundle, and then the combined flow line is split into different flow lines, each connected to a dedicated flow control device 70.

[0045] In some embodiments, a platen 92 may be disposed within the process chamber 80. For example, the platen 92 may be disposed in a lower portion of the interior space of the process chamber 80. The platen 92 may be loaded with a target substrate W and support the loaded target substrate W. The platen 92 may be an electrostatic chuck that holds the target substrate W by electrostatic force, although the present disclosure is not limited thereto.

[0046] In some embodiments, a showerhead 94 may be disposed within the process chamber 80 and face the platen 92. For example, the showerhead 94 may be disposed at an upper portion of the interior space of the process chamber 80. The showerhead 94 may provide acetylene onto the filled target substrate W. For example, the showerhead 94 may be connected to an acetylene delivery package GP within the gas cabinet 10 by a gas pipe 50. Acetylene discharged from the acetylene delivery package GP may travel along the gas pipe 50 and be supplied into the process chamber 80 via the showerhead 94.

[0047] In some embodiments, the gas pipe 50 may further include a second valve 54. The second valve 54 may control the amount of acetylene fluid flowing into the flow control device 70. For example, the second valve 54 may be provided in the gas pipe 50 connecting the first valve 52 and the flow control device 70.

[0048] In some embodiments, the gas pipe 50 may further be provided with a third valve 56. The third valve 56 can control the amount of acetylene fluid flowing into the showerhead 94. For example, the third valve 56 may be provided in the gas pipe 50 connecting the flow control device 70 and the showerhead 94.

[0049] As-deposited carbon films can be used in a variety of applications, including, but not limited to, protective layers for underlying films during subsequent etching process steps, or conductive carbon films for electron transport. Many applications are sensitive to impurities or unwanted contaminants, which can adversely affect film properties, such as optical properties, electrical properties, or robustness in other subsequent processes. In such a scenario, a supply of acetylene stabilized in a solvent containing reactive elements can form non-volatile reaction products under deposition conditions, which is undesirable. Even solvents with relatively low vapor pressures can be transported into the process chamber in various trace amounts and adversely affect film properties. Therefore, solvents for acetylene containing metallic or inorganic impurities, such as boron, calcium, or nickel, are undesirable for this application. In this regard, one of the attributes of the inventive concept is that the chemical structure is characterized by the absence of boron, calcium, and nickel.

[0050] The ability of the inventive concept to produce high purity films is advantageous over conventional solvents such as acetone, which acts as a contaminant in some of the applications described above where high purity acetylene is required, and which can adversely affect the properties of carbon films utilized during the fabrication of electronic devices.

[0051] As explained, the inventive concept provides a novel solvent that exhibits a higher degree of non-toxicity, characterized by the absence of an H360 hazard presentation code, while maintaining acetylene solubilization capabilities in a manner that allows high purity acetylene product to be removed from storage and distribution containers.

[0052] Each of the improved solvents 30 has a different solubilizing capacity for acetylene, which translates into a specific volumetric expansion of the solvent 30 within the cylinder 12. The loading of each solvent 30 into the cylinder 12 must be determined for each solvent, taking into account the volumetric expansion of the particular solvent 30 as a result of gaseous acetylene dissolving therein, so that the cylinder 12 maintains sufficient free space of at least about 10% of the cylinder's free volume. Furthermore, the loading of each improved solvent 30 must allow sufficient acetylene to dissolve therein without overpressurizing the cylinder 12. Therefore, the loading parameter of each improved solvent 30 into the cylinder 12 of the inventive concept, which is important, is a specific value, as determined experimentally by the applicant. For example, the amount of triethyl phosphate (TEP) that can be loaded into the cylinder 12 is about 0.64 kg or less of TEP per liter of cylinder volume, preferably about 0.61 kg or less of TEP per liter of cylinder volume, and more preferably about 0.58 kg or less of TEP per liter of cylinder volume.

[0053] 5-7 are graphs illustrating the effectiveness of acetylene fluid delivery packages according to some embodiments. For ease of explanation, portions that overlap with those described above with reference to FIGS. 1-4 will be briefly described or omitted.

[0054] [Experimental Example 1] The pressure vessel filled with porous silica particles was filled with triethyl phosphate as a solvent and acetylene was dissolved in it under a filling pressure of 250 psig at 21° C., thereby producing an acetylene fluid supply package.

[0055] [Comparative Example 1] An acetylene fluid supply package was prepared in the same manner as in Experimental Example 1, except that acetone was used as the solvent.

[0056] [Carryover evaluation] The solvent carryover of the fluid discharged from the acetylene fluid supply package manufactured according to Experimental Example 1 was measured and is shown in Figure 5. In addition, the solvent carryover of the fluid discharged from the acetylene fluid supply packages manufactured according to Experimental Example 1 and Comparative Example 1 was measured and is shown in Figure 6.

[0057] 5 and 6, it can be seen that the acetylene fluid supply package manufactured according to Experimental Example 1 had significantly reduced solvent carryover compared to the acetylene fluid supply package manufactured according to Comparative Example 1.

[0058] For example, when the vessel pressure is about 70 psig, it can be seen that the solvent carryover (i.e., acetone carryover) of the fluid discharged from the acetylene fluid supply package according to Comparative Example 1 is about 42,000 ppm, while the solvent carryover (i.e., triethyl phosphate carryover) of the fluid discharged from the acetylene fluid supply package according to Experimental Example 1 is significantly reduced to about 66 ppm. This can be understood as being because the vapor pressure of triethyl phosphate (about 0.3 Torr at 20° C.) is significantly lower than the vapor pressure of acetone (about 187 Torr at 20° C.).

[0059] [Evaluation of carbon films] Carbon films were deposited on wafers using the acetylene fluid supply packages manufactured in Experimental Example 1 and Comparative Example 1, and the physical properties (thickness, reflectivity, and density) of the deposited carbon films were measured and shown in Figure 7. The carbon films were deposited on wafers using the deposition system described with reference to Figure 4. In addition, as a reference for the carbon films deposited in Experimental Example 1 and Comparative Example 1, carbon films were deposited on wafers using pure acetylene gas without solvent carryover.

[0060] Referring to FIG. 7, it can be seen that the physical properties of the carbon film deposited using the acetylene fluid supply package of Experimental Example 1 were significantly improved compared to the carbon film deposited using the acetylene fluid supply package of Comparative Example 1.

[0061] In particular, it can be seen that the carbon film deposited by the acetylene fluid supply package according to Comparative Example 1 exhibits physical properties significantly different from the reference carbon film, whereas the carbon film deposited by the acetylene fluid supply package according to Experimental Example 1 exhibits physical properties similar to those of the reference carbon film. This can be understood as being because, as described above, the solvent carryover (i.e., triethyl phosphate carryover) of the fluid discharged from the acetylene fluid supply package according to Experimental Example 1 is significantly lower than the solvent carryover (acetone carryover) of the fluid discharged from the acetylene fluid supply package according to Comparative Example 1.

[0062] As mentioned above, the solvent has high solubility in acetylene (for example, about 5 MPa 0.5 The solvent has a low vapor pressure (e.g., about 6 Torr or less), which significantly reduces the carryover of solvents mixed with acetylene and discharged. Furthermore, the solvent has low reproductive toxicity and is easy to apply. Therefore, an acetylene fluid supply package capable of supplying acetylene stably can be provided.

[0063] Hereinafter, a method for manufacturing a semiconductor device according to an exemplary embodiment will be described with reference to Figures 8 to 24. Note that the following embodiments are merely examples, and the present disclosure is not limited to the embodiments.

[0064] 8-12 illustrate intermediate steps in a method for manufacturing a semiconductor device according to some embodiments. For ease of explanation, portions that overlap with those described above with reference to FIGS. 1-7 are briefly described or omitted.

[0065] Referring to FIG. 8, an etch target layer 110, a hard mask layer 112, and a photoresist layer 114 are sequentially formed on a semiconductor substrate 100.

[0066] The semiconductor substrate 100 may be bulk silicon or silicon-on-insulator (SOI). Alternatively, the semiconductor substrate 100 may be a silicon substrate, or may be formed of other materials, such as silicon germanium, silicon germanium-on-insulator (SGOI), indium antimony, lead telluride, indium arsenide, indium phosphide, gallium arsenide, or gallium antimony, but the present disclosure is not limited thereto. For convenience of explanation, the semiconductor substrate 100 will be described below as a silicon substrate.

[0067] An etch target film 110 may be deposited on the semiconductor substrate 100. The etch target film 110 may include an insulating material, such as at least one of silicon oxide, silicon nitride, silicon oxynitride, and combinations thereof, although the present disclosure is not limited thereto.

[0068] The hard mask film 112 may be deposited on the etch target film 110. The hard mask film 112 may be formed by a deposition process using acetylene as a raw material. The deposition process may include, for example, a chemical vapor deposition (CVD) process, but the present disclosure is not limited thereto. For example, acetylene may be provided on the etch target film 110 from the acetylene fluid supply package described with reference to FIGS. 1-3, and the hard mask film 112 may be a carbon-containing layer formed from the provided acetylene. The hard mask film 112 may also be an amorphous carbon layer (ACL) formed from acetylene, but the present disclosure is not limited thereto.

[0069] The photoresist film 114 may be laminated on the hard mask film 112. The photoresist film 114 may be formed on the hard mask film 112 by a coating process such as spin coating, dip coating, or spray coating.

[0070] Referring to FIG. 9, the photoresist film 114 is patterned to form a photoresist pattern 114p.

[0071] For example, an exposure process may be performed on the photoresist film 114. The exposure process may divide the photoresist film 114 into exposed and unexposed portions. Subsequently, a development process may be performed on the photoresist film 114. If the development process is a positive tone development (PTD) process, the exposed portions may be removed and the unexposed portions may remain, forming a photoresist pattern 114p. If the development process is a negative tone development (NTD) process, the unexposed portions may be removed and the exposed portions may remain, forming a photoresist pattern 114p.

[0072] Referring to FIG. 10, the hard mask layer 112 is patterned to form a hard mask pattern 112p.

[0073] For example, an etching process may be performed using the photoresist pattern 114p as an etch mask. The etching process may include, for example, a dry etching process, but the present disclosure is not limited thereto. As a result, a hard mask pattern 112p, to which the photoresist pattern 114p is transferred, may be formed on the etch target film 110.

[0074] Referring to FIG. 11, an etching process is performed on the etch target layer 110 using the hard mask pattern 112p as an etch mask.

[0075] The etching process may include, for example, a dry etching process, although the present disclosure is not limited thereto. As the etching process progresses, a recess 110r may be formed in the etch target film 110. In some embodiments, the depth of the recess 110r may be less than the thickness of the etch target film 110. After the etch process is performed on the etch target film 110, the hard mask pattern 112p may be removed.

[0076] Referring to FIG. 12, a conductive pattern 116 is formed in the recess 110r.

[0077] For example, a conductive film filling the recess 110r can be formed on the etch target film 110. Subsequently, the conductive film can be subjected to a planarization process. The planarization process can include, for example, a CMP (chemical mechanical polishing) process, but the present disclosure is not limited thereto. This can form a plurality of conductive patterns 116 that are insulated from each other by the etch target film 110.

[0078] In some embodiments, the conductive pattern 116 may be used as a conductive line in a semiconductor device. As an example, the conductive pattern 116 may be used as a word line in a volatile memory device such as a DRAM (Dynamic Random Access Memory), although the present disclosure is not limited in this respect.

[0079] As semiconductor devices become more highly integrated, there is a demand for hard mask films with improved etch selectivity. Some embodiments of the semiconductor device fabrication method can provide a hard mask film 112 with improved etch selectivity by utilizing the acetylene fluid supply package described above. Specifically, as described above, some embodiments of the acetylene fluid supply package can significantly reduce solvent carryover during the deposition process by using a solvent. This allows a high-quality carbon-containing layer (e.g., an amorphous carbon layer) to be provided as the hard mask film 112.

[0080] 13-19 illustrate intermediate steps in a method for manufacturing a semiconductor device according to some embodiments. For ease of explanation, portions that overlap with those described above with reference to FIGS. 1-12 are briefly described or omitted.

[0081] Referring to FIG. 13, a first mold layer MS1 is formed on a semiconductor substrate 100. As shown in FIG.

[0082] The first mold layer MS1 may include a first mold insulating film 121 and a first mold sacrificial film 122 alternately stacked on the semiconductor substrate 100.

[0083] The first mold insulating layer 121 and the first mold sacrificial layer 122 may include an insulating material, such as at least one of silicon oxide, silicon nitride, and silicon oxynitride, but the present disclosure is not limited thereto. In some embodiments, the first mold sacrificial layer 122 may include a material having an etch selectivity with respect to the first mold insulating layer 121. For example, the first mold insulating layer 121 may include a silicon oxide layer, and the first mold sacrificial layer 122 may include a silicon nitride layer.

[0084] Referring to FIG. 14, a first hole CHa is formed in the first mold layer MS1.

[0085] The first holes CHa may extend in a direction intersecting (e.g., vertically) the top surface of the semiconductor substrate 100 and penetrate the first mold layer MS1. Thus, the first holes Cha may cross the plurality of first mold insulating layers 121 and the plurality of first mold sacrificial layers 122. In some embodiments, the first holes Cha may penetrate the first mold layer MS1 to expose a portion of the top surface of the semiconductor substrate 100.

[0086] Referring to FIG. 15, a sacrificial pattern 123 is formed in the first hole CHa.

[0087] The sacrificial pattern 123 may fill the first hole CHa. The sacrificial pattern 123 may be formed by a deposition process using acetylene as a raw material. The deposition process may include, for example, a CVD (chemical vapor deposition) process, but the present disclosure is not limited thereto. For example, acetylene may be provided on the first mold layer MS1 from the acetylene fluid supply package described above with reference to FIGS. 1 to 3, and the sacrificial pattern 123 may be a carbon-containing layer formed from the provided acetylene. Such a sacrificial pattern 123 may have an etch selectivity with respect to the first mold layer MS1.

[0088] Referring to FIG. 16, a second mold layer MS2 is formed on the first mold layer MS1 and the sacrificial pattern 123.

[0089] The second mold layer MS2 may include a second mold insulating film 124 and a second mold sacrificial film 125 alternately stacked on the semiconductor substrate 100.

[0090] The second mold insulating layer 124 and the second mold sacrificial layer 125 may include an insulating material, such as at least one of silicon oxide, silicon nitride, and silicon oxynitride, although the present disclosure is not limited thereto. In some embodiments, the second mold sacrificial layer 125 may include a material having an etch selectivity with respect to the second mold insulating layer 124. In some embodiments, the second mold insulating layer 124 may include the same material as the first mold insulating layer 121, and the second mold sacrificial layer 125 may include the same material as the first mold sacrificial layer 122. As an example, the second mold insulating layer 124 may include a silicon oxide layer, and the second mold sacrificial layer 125 may include a silicon nitride layer.

[0091] Referring to FIG. 17, second holes CHb are formed in the second mold layer MS2.

[0092] The second holes CHb extend in a direction intersecting (e.g., vertically) the top surface of the semiconductor substrate 100 and penetrate the second mold layer MS2. Therefore, the second holes CHb may cross the plurality of second mold insulating layers 124 and the plurality of second mold sacrificial layers 125. In some embodiments, the second holes CHb may penetrate the second mold layer MS2 to expose at least a portion of the top surface of the sacrificial pattern 123.

[0093] Referring to FIG. 18, the sacrificial pattern 123 is selectively removed.

[0094] For example, an etching process can be performed to remove the sacrificial pattern 123 using the second holes CHb. The etching process can include, for example, a wet etching process, but the present disclosure is not limited thereto. The sacrificial pattern 123 can be selectively removed because it has etch selectivity with respect to the first mold layer MS1 and the second mold layer MS2. By removing the sacrificial pattern 123, through holes CH including the first holes Cha and the second holes CHb that are connected to each other can be formed in the first mold layer MS1 and the second mold layer MS2.

[0095] Referring to FIG. 19, a data storage layer 126 and a semiconductor layer 127 are formed in the through-hole CH.

[0096] The data storage layer 126 and the semiconductor layer 127 may be sequentially stacked in the through-hole CH.

[0097] The data storage layer 126 may conformally extend along the side profile of the through-hole CH. The data storage layer 126 may include at least one of silicon oxide, silicon nitride, silicon oxynitride, and a high-k material having a higher dielectric constant than silicon oxide, for example.

[0098] The semiconductor film 127 may extend along the top surface of the semiconductor substrate 100 and the sidewalls of the data storage film 126. In some embodiments, the semiconductor film 127 may conformally extend along the top surface of the semiconductor substrate 100 and the sidewalls of the data storage film 126. The semiconductor film 127 may include, for example, a semiconductor material such as monocrystalline silicon, polycrystalline silicon, an organic semiconductor material, or a carbon nanostructure, although the present disclosure is not limited thereto.

[0099] In some embodiments, the semiconductor film 127 may be used as a channel of a semiconductor device. By way of example, the semiconductor film 127 may be used as a channel of a non-volatile memory device such as a NAND flash, although the present disclosure is not limited thereto.

[0100] In some embodiments, a fill pattern 128 may be further formed in the through hole CH. The fill pattern 128 may be formed to fill the remaining through hole CH after the data storage layer 126 and the semiconductor layer 127 are filled. The fill pattern 128 may include an insulating material, such as silicon oxide, although the present disclosure is not limited thereto.

[0101] As semiconductor devices become more highly integrated, carbon-containing layers have been proposed as sacrificial patterns with improved performance. Some embodiments of the semiconductor device manufacturing method can utilize the acetylene fluid supply package described above to provide a high-quality carbon-containing layer as the sacrificial pattern 123.

[0102] 20-23 illustrate intermediate steps in a method for manufacturing a semiconductor device according to some embodiments. For ease of explanation, portions that overlap with those described above with reference to FIGS. 1-12 are briefly described or omitted.

[0103] Referring to FIG. 20, a first active pattern 131 and a second active pattern 132 spaced apart from each other are formed on a semiconductor substrate 100 .

[0104] The first and second active patterns 131 and 132 may protrude from the top surface of the semiconductor substrate 100. The first and second active patterns 131 and 132 may be formed by etching a portion of the semiconductor substrate 100, or may be epitaxial layers grown on the semiconductor substrate 100.

[0105] In some embodiments, the first active pattern 131 may include a first fin pattern 131a and a second fin pattern 131b that protrude from the top surface of the semiconductor substrate 100 and extend parallel to one another, and the second active pattern 132 may include a third fin pattern 132a and a fourth fin pattern 132b that protrude from the top surface of the semiconductor substrate 100 and extend parallel to one another. Here, the distance by which the first fin pattern 131a and the third fin pattern 132a are spaced apart may be longer than the distance between the first fin pattern 131a and the second fin pattern 131b and the distance between the third fin pattern 132a and the fourth fin pattern 132b.

[0106] In some embodiments, the first active pattern 131 and the second active pattern 132 may be used as channels of a semiconductor device. As an example, the first active pattern 131 and the second active pattern 132 may be used as channels of a field effect transistor (FET) formed in a logic device, although the present disclosure is not limited thereto.

[0107] Referring to FIG. 21, a first gap fill layer 133a is formed on the semiconductor substrate 100, the first active patterns 131 and the second active patterns 132. As shown in FIG.

[0108] The first gap fill film 133a may fill the region between the first fin pattern 131a and the second fin pattern 131b and the region between the third fin pattern 132a and the fourth fin pattern 132b. The first gap fill film 133a may be formed by a deposition process using acetylene as a raw material. The deposition process may include, for example, a chemical vapor deposition (CVD) process, but the present disclosure is not limited thereto. For example, acetylene may be provided on the semiconductor substrate 100, the first active pattern 131, and the second active pattern 132 from the acetylene fluid supply package described above with reference to FIGS. 1 to 3, and the first gap fill film 133a may be a carbon-containing layer formed from the provided acetylene. Such a first gap fill film 133a may fill a portion of the region 133G between the first active pattern 131 and the second active pattern 132.

[0109] Referring to FIG. 22, a second gap fill layer 133b is formed on the first gap fill layer 133a.

[0110] The second gap-fill film 133b may fill the remaining region 133G between the first active pattern 131 and the second active pattern 132 after the first gap-fill film 133a is filled. The second gap-fill film 133b may be formed by a deposition process using acetylene as a raw material. The deposition process may include, for example, a CVD (chemical vapor deposition) process, but the present disclosure is not limited thereto. For example, acetylene may be supplied onto the first gap-fill film 133a from the acetylene fluid supply package described above with reference to FIGS. 1 to 3, and the second gap-fill film 133b may be a carbon-containing layer formed from the supplied acetylene. The first gap-fill film 133a and the second gap-fill film 133b may form a gap-fill insulating film 133 that fills the region 133G between the first active pattern 131 and the second active pattern 132.

[0111] Referring to FIG. 23, an etch-back process is performed on the gap-fill insulating film 133.

[0112] By performing an etch-back process, the gap-fill insulating film 133 can be adjusted to have a predetermined thickness. Unlike the drawing, the thickness of the gap-fill insulating film 133 may be adjusted to expose at least a portion of the first active pattern 131 and at least a portion of the second active pattern 132.

[0113] As semiconductor devices become more highly integrated, carbon-containing layers have been proposed as gap-fill films with improved gap-fill performance. The semiconductor device manufacturing method according to some embodiments can provide a high-quality carbon-containing layer as the gap-fill insulating film 133 using the acetylene fluid supply package described above.

[0114] 24 is an intermediate view illustrating a method for manufacturing a semiconductor device according to some embodiments. For convenience of explanation, parts that overlap with those described above with reference to FIGS. 1 to 12 will be briefly described or omitted.

[0115] Referring to FIG. 24, a graphene layer 140 is formed on a semiconductor substrate 100 .

[0116] The graphene layer 140 may include graphene formed by a deposition process using acetylene as a raw material. The deposition process may include, for example, a chemical vapor deposition (CVD) process, but the present disclosure is not limited thereto. For example, acetylene may be provided on the semiconductor substrate 100 from the acetylene fluid supply package described above with reference to FIGS. 1-3, and the graphene layer 140 may include graphene formed from the provided acetylene.

[0117] Although the graphene layer 140 is illustrated as a single layer, this is merely an example, and the graphene layer 140 may also be a multi-layer structure in which multiple graphene layers are stacked. Furthermore, although the graphene layer 140 is illustrated as being in contact with only the top surface of the semiconductor substrate 100, this is merely an example, and other material films may be interposed between the semiconductor substrate 100 and the graphene layer 140.

[0118] Graphene has been attracting attention as a next-generation material in many fields due to its excellent electrical, mechanical, and chemical properties. Some embodiments of the method for manufacturing a semiconductor device can provide a high-quality graphene layer 140 by utilizing the acetylene fluid supply package described above.

[0119] While what are considered to be particular embodiments of the inventive concepts have been shown and described, it will of course be understood that various modifications and changes in form or detail can be readily made without departing from the spirit and scope of the inventive concepts. It is therefore intended that the inventive concepts not be limited to the exact forms and details shown and described herein, nor is it intended to be limited to anything less than the full scope of the inventive concepts disclosed herein and claimed below.

Claims

1. 1. An acetylene fluid supply package comprising: A pressure vessel; a porous filler in the pressure vessel; an improved solvent within the porous filler, the solvent solubilizing acetylene absorbed within the improved solvent; 1. An acetylene fluid supply package, wherein the improved solvent comprises triethyl phosphate (TEP), and the TEP is charged to the pressure vessel in an amount of about 0.64 kg or less of TEP per liter of pressure vessel volume.

2. 2. The acetylene fluid supply package of claim 1, wherein the TEP is charged to the pressure vessel in an amount of about 0.61 kg or less of TEP per liter of pressure vessel volume.

3. 2. The acetylene fluid supply package of claim 1, wherein the TEP is charged to the pressure vessel in an amount of about 0.58 kg or less of TEP per liter of pressure vessel volume.

4. 10. The acetylene fluid supply package of claim 1, further comprising said acetylene stabilized at 21°C and a pressure of up to 300 psig.

5. 1. A system comprising: at least one acetylene fluid supply package; and an acetylene-utilizing process tool in fluid communication with the at least one acetylene fluid supply package, the at least one acetylene fluid supply package comprising: A pressure vessel; a porous filler in the pressure vessel; an improved solvent within the porous filler, the solvent solubilizing acetylene absorbed within the improved solvent; the improved solvent comprises triethyl phosphate (TEP), and the TEP is charged to the pressure vessel in an amount of about 0.64 kg or less of TEP per liter of pressure vessel volume; the at least one acetylene fluid supply package is configured to allow discharge of the acetylene fluid under dispensing conditions; The system further comprises the acetylene-utilizing process tool configured to receive the acetylene fluid from the at least one acetylene fluid supply package.

6. The system of claim 5 , wherein the process tool comprises a chemical vapor deposition tool.

7. The system of claim 5 , wherein the at least one acetylene fluid supply package is contained in a gas cabinet.

8. 6. The system of claim 5, wherein the TEP is loaded into the pressure vessel in an amount of about 0.61 kg or less of TEP per liter of pressure vessel volume.

9. 6. The system of claim 5, wherein the TEP is loaded into the pressure vessel in an amount of about 0.58 kg or less of TEP per liter of pressure vessel volume.

10. 1. A method for manufacturing a semiconductor device, comprising: Providing a semiconductor substrate; forming a carbon-containing layer on the semiconductor substrate using an acetylene fluid supply package; the acetylene fluid supply package comprising a pressure vessel, a porous filler within the pressure vessel, and a solvent within the porous filler, the solvent solubilizing acetylene absorbed within the solvent; the vapor pressure of the solvent is 6 Torr or less at 20°C; The Hansen solubility factor (δh) of the solvent is 5 MPa ０．５ That's all, The reproductive toxicity of the solvent is less than that of dimethylformamide (DMF).

11. 11. The method of claim 10, wherein the solvent comprises triethyl phosphate (TEP), and the TEP is charged to the pressure vessel in an amount of about 0.64 kg or less of TEP per liter of pressure vessel volume.

12. 11. The method of claim 10, wherein the solvent comprises at least one of N,N,N',N'-tetramethylmethyl-phosphondiamide, tetramethylene sulfoxide, tetramethylurea, N-acetylpyrrolidine, tris(N,N-tetramethylene)phosphoramide, methylnaphthodioxane, trimethyl phosphite, and tetramethyldiamidophosphoryl fluoride.

13. forming an etch target film on the semiconductor substrate; 11. The method of claim 10, further comprising: etching the etch target film using the carbon-containing layer as an etch mask.

14. forming a mold layer over the semiconductor substrate, the carbon-containing layer being formed in the mold layer; The method of claim 10 , further comprising removing the carbon-containing layer in the mold layer.

15. forming a first active pattern and a second active pattern spaced apart from each other on the semiconductor substrate; The method of claim 10 , wherein the carbon-containing layer fills at least a portion between the first active pattern and the second active pattern.

16. The method of claim 10 , wherein the carbon-containing layer comprises graphene.

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