Method for manufacturing semiconductor device

Abstract

The present invention provides a method for manufacturing a semiconductor device, comprising the steps of: introducing, into a reaction chamber, a semiconductor substrate including a structure on which a trench or a via hole is formed; introducing a metal precursor including molybdenum fluoride into the reaction chamber so as to deposit a thin film on the structure; and repeatedly performing the deposition step so as to fill the structure with the thin film, wherein at least a portion of the thin film is etched in situ with the deposition step by the molybdenum fluoride, and, as the deposition step is repeatedly performed, the flow rate of the metal precursor introduced into the reaction chamber decreases.

Description

Method for manufacturing semiconductor devices

[0001] The present invention relates to a method for manufacturing a semiconductor device.

[0002]

[0003] Typically, semiconductor device manufacturing methods require state-of-the-art deposition methods to form metal films, such as tungsten metal films and copper metal films.

[0004] However, tungsten and copper metal films typically require a thick barrier layer between the metal film and the dielectric material. This thick barrier layer can be used to improve device reliability and yield by preventing metal species from diffusion into the underlying dielectric material. However, this thick barrier layer typically exhibits high electrical resistivity and can increase the overall electrical resistivity of the semiconductor device.

[0005] In contrast, molybdenum can have a low coefficient of thermal expansion, low resistivity, and high thermal conductivity, and is widely used in the manufacture of semiconductor devices, including use in diffusion barriers, electrodes, photomasks, power electronic device substrates, and low-resistivity gate and interconnect materials.

[0006] However, when forming a molybdenum metal film in a high aspect ratio trench or via hole, the metal film may first be filled on the upper part of the trench or via hole, and the upper gap of the trench or via hole may be closed, resulting in the formation of a void in the middle part of the trench or via hole. This problem has caused a problem of deterioration in the overall electrical characteristics of the semiconductor device.

[0007]

[0008] The present invention provides a method for manufacturing a semiconductor device having improved processability and electrical characteristics.

[0009]

[0010] A method for manufacturing a semiconductor device according to the present invention comprises the steps of introducing a semiconductor substrate including a structure having a trench or via hole formed therein into a reaction chamber, introducing a metal precursor including molybdenum fluoride into the reaction chamber to deposit a thin film on the structure, and repeatedly performing the deposition step to fill the structure with the thin film, wherein at least a portion of the thin film is etched in-situ by the molybdenum fluoride during the deposition step, and as the deposition step is repeatedly performed, a flow rate of the metal precursor introduced into the reaction chamber is reduced.

[0011] In one embodiment of the present invention, the structure may have an aspect ratio of 2:1 or more and 20:1 or less.

[0012] In one embodiment of the present invention, the flow rate of the metal precursor can be reduced when the filling ratio of the thin film is 30 vol% or more to 90 vol% or less based on the total volume of the structure.

[0013] In one embodiment of the present invention, the reduced flow rate of the metal precursor may be 10% or more and 90% or less compared to the initial flow rate of the metal precursor introduced into the reaction chamber.

[0014] In one embodiment of the present invention, the flow rate of the metal precursor can be reduced stepwise when the filling ratio of the thin film is 30 vol% or more to 90 vol% or less based on the total volume of the structure.

[0015] In one embodiment of the present invention, when the filling ratio of the thin film is 30 vol% or more and less than 50 vol% based on the total volume of the structure, the reduced first flow rate of the metal precursor may be 50% or more and less than 90% of the initial flow rate of the metal precursor introduced into the reaction chamber, and when the filling ratio of the thin film is 50 vol% or more and less than 90 vol%, the reduced second flow rate of the metal precursor may be 10% or more and less than 50% of the initial flow rate of the metal precursor introduced into the reaction chamber.

[0016] In one embodiment of the present invention, the structure may have an aspect ratio of greater than 20:1 and less than or equal to 100:1.

[0017] In one embodiment of the present invention, the flow rate of the metal precursor can be reduced when the filling ratio of the thin film is 10 vol% or more to 90 vol% or less based on the total volume of the structure.

[0018] In one embodiment of the present invention, the reduced flow rate of the metal precursor may be 5% or more and 90% or less compared to the initial flow rate of the metal precursor introduced into the reaction chamber.

[0019] In one embodiment of the present invention, the flow rate of the metal precursor can be reduced stepwise when the filling ratio of the thin film is 10 vol% or more to 90 vol% or less based on the total volume of the structure.

[0020] In one embodiment of the present invention, when the filling ratio of the thin film is 10 vol% or more and less than 40 vol% based on the total volume of the structure, the reduced first flow rate of the metal precursor may be 50% or more and less than 90% of the initial flow rate of the metal precursor introduced into the reaction chamber, and when the filling ratio of the thin film is 40 vol% or more and less than 90 vol%, the reduced second flow rate of the metal precursor may be 5% or more and less than 50% of the initial flow rate of the metal precursor introduced into the reaction chamber.

[0021] In one embodiment of the present invention, the step of introducing a reducing precursor into the reaction chamber before or after introducing the metal precursor may be included.

[0022] In one embodiment of the present invention, as the deposition step is repeatedly performed, the flow rate of the reducing precursor introduced into the reaction chamber can be reduced.

[0023] In one embodiment of the present invention, the semiconductor device manufacturing method may be by atomic layer deposition (ALD).

[0024]

[0025] The method for manufacturing a semiconductor device according to the present invention includes molybdenum fluoride as a metal precursor. The molybdenum fluoride has a relatively low melting point and boiling point, can be easily vaporized, and can be efficiently introduced into a reaction chamber for manufacturing a semiconductor device.

[0026] In addition, the method for manufacturing a semiconductor device according to the present invention can suppress the formation of an overhang or protrusion on the upper part of a trench or via hole due to the etching action of fluorine contained in the metal precursor. As a result, the formation of a void or seam inside the trench or via hole can be suppressed, so that the electrical characteristics required in the semiconductor device can be smoothly expressed. In addition, since a separate etching process is not required to etch the overhang or protrusion formed on the upper part of the trench or via hole, the efficiency of the manufacturing process can be improved, and impurities that may be generated in the etching process are not caused.

[0027] The method for manufacturing a semiconductor device according to the present invention is controlled to reduce the flow rate of a metal precursor introduced into a reaction chamber. Consequently, during the initial thin film deposition step, the deposition action of the metal precursor is greater within the trench or via hole, allowing for smooth deposition of a molybdenum thin film within the trench or via hole without clogging the trench or via hole entrance.

[0028] In addition, after a certain amount of molybdenum thin film deposition is formed inside the trench or via hole, the flow rate of the metal precursor is controlled to decrease, so that the etching action of fluorine on the molybdenum thin film formed inside the trench or via hole can be relatively reduced. As a result, a molybdenum gapfill layer can be efficiently formed inside the trench or via hole.

[0029]

[0030] FIG. 1 illustrates a cross-sectional view of a semiconductor substrate including a structure in which a trench or via hole is formed.

[0031] Figure 2 illustrates the deposition of a metal precursor onto a structure.

[0032] Figure 3 illustrates that a first thin film is formed on the structure by a reducing precursor.

[0033] FIG. 4 illustrates that at least a portion of the first thin film is etched by the metal precursor at the same time as the metal precursor is deposited.

[0034] Figure 5 illustrates that a second thin film is formed by a reducing precursor.

[0035] Figure 6 illustrates a cross-sectional view to show changes in the flow rate of a metal precursor.

[0036] Figure 7 illustrates a cross-sectional view of a gap fill layer formed as a thin film after a CMP process.

[0037]

[0038] The structural or functional descriptions of the embodiments disclosed in this specification or application are merely illustrative for the purpose of explaining embodiments according to the technical idea of ​​the present invention, and the embodiments according to the technical idea of ​​the present invention can be implemented in various forms other than the embodiments disclosed in this specification or application, and the technical idea of ​​the present invention is not construed as being limited to the embodiments described in this specification or application.

[0039] Additionally, when a component is referred to as "including" in this specification or application, unless otherwise specifically stated, this does not exclude other components, but rather implies the inclusion of additional components. Furthermore, all numerical ranges indicating physical property values, dimensions, etc. of the components described in this specification or application should be understood to be modified by the term "about" in all cases, unless otherwise specified.

[0040]

[0041] Hereinafter, a method for manufacturing a semiconductor device according to the present invention will be described.

[0042]

[0043] A method for manufacturing a semiconductor device according to the present invention comprises the steps of introducing a semiconductor substrate including a structure having a trench or via hole formed therein into a reaction chamber, introducing a metal precursor including molybdenum fluoride into the reaction chamber to deposit a thin film on the structure, and repeatedly performing the deposition step to fill the structure with the thin film, wherein at least a portion of the thin film is etched in-situ by the molybdenum fluoride during the deposition step, and as the deposition step is repeatedly performed, a flow rate of the metal precursor introduced into the reaction chamber is reduced.

[0044]

[0045] A method according to the present invention comprises the step of introducing a semiconductor substrate including a structure having a trench or via hole formed therein into a reaction chamber.

[0046] FIG. 1 illustrates a cross-sectional view of a semiconductor substrate including a structure in which a trench or via hole is formed.

[0047] Referring to FIG. 1, a semiconductor substrate (100) includes a structure (130) in which a trench or via hole is formed. The semiconductor substrate (100) may include a silicon wafer (110). The silicon wafer (110) may include single crystal silicon.

[0048] The semiconductor substrate (100) may include an insulating layer (120) disposed on the silicon wafer (110). The insulating layer (120) may include at least one of silicon dioxide (SiO2), silicon suboxide, silicon nitride (Si3N4), silicon oxynitride (SiON), silicon oxycarbide (SiOC), silicon oxycarbide nitride (SiOCN), and silicon carbon nitride (SiCN). The insulating layer (120) may include a dielectric surface.

[0049] The above semiconductor substrate (100) is made of aluminum oxide (Al2O3), hafnium oxide (HfO2), tantalum oxide (Ta2O5), zirconium oxide (ZrO2), titanium oxide (TiO2), and hafnium silicate (HfSiO x ), and lanthanum oxide (La2O3).

[0050] The above structure (130) may be formed by etching a portion of the insulating layer (120) to form a trench or via hole. The inner bottom portion of the structure (130) may be formed so that the silicon wafer (110) is exposed.

[0051] The above structure (130) can be formed through a photo process and an etching process. The above structure (130) can be formed by a known method.

[0052] After the semiconductor substrate (100) including the structure (130) is introduced into the reaction chamber, the interior of the reaction chamber can be purged.

[0053] The above purging can be performed by reducing the pressure in the reaction chamber by flowing an inert gas at a predetermined pressure, and then re-pressurizing the reaction chamber before initiating another gas exposure. The inert gas can include nitrogen, argon, helium, and mixtures thereof. The purging can be performed for 0.1 to 30 seconds, 0.2 to 20 seconds, 0.5 to 10 seconds, or 0.5 to 5 seconds.

[0054] The method according to the present invention comprises the step of introducing a metal precursor comprising molybdenum fluoride into the reaction chamber and depositing a thin film on the structure.

[0055] The above molybdenum fluoride may include at least one of molybdenum hexafluoride (MoF6) and molybdenum fluorideoxide (MoF4O).

[0056] The melting point of the above molybdenum fluoride may be from about -30°C to about 100°C, from about -20°C to about 80°C, or from about 0°C to about 60°C.

[0057] The boiling point of the above molybdenum fluoride may be from about -20°C to about 200°C, from about -10°C to about 150°C, or from about 0°C to about 100°C at atmospheric pressure.

[0058] The weight average molecular weight of the above molybdenum fluoride may be from about 100 g / mol to about 400 g / mol, from about 150 g / mol to about 350 g / mol, or from about 200 g / mol to about 350 g / mol.

[0059] The vapor pressure of the above molybdenum fluoride may be from about 500 Torr to about 1000 Torr, or from about 550 Torr to about 800 Torr at room temperature.

[0060] The density of the above molybdenum fluoride may be about 2 g / cm3 to about 5 g / cm3, about 2.5 g / cm3 to about 4.5 g / cm3, or about 3 g / cm3 to about 4 g / cm3.

[0061] Since the above molybdenum fluoride has a melting point and boiling point within the above range, it can have improved ease of handling. Furthermore, since the above molybdenum fluoride has a melting point and boiling point within the above range, it can be easily deposited even when the temperature of the reaction chamber is relatively low. Furthermore, since the process temperature is relatively low, the temperature uniformity within the reaction chamber can be easily controlled, and the metal precursor can be deposited with a uniform thickness throughout.

[0062] The above metal precursor can be manufactured by the following method.

[0063] First, the fluorine gas can be purified. The fluorine gas can be passed through a cooling tower at a temperature of about -90°C to about -70°C. Accordingly, the amount of hydrogen fluoride gas contained in the fluorine gas can be appropriately reduced. In addition, the fluorine gas can be passed through an adsorption tower, so that the content of hydrogen fluoride gas contained in the fluorine gas can be appropriately reduced.

[0064] Thereafter, a molybdenum metal may be placed in the reactor. The molybdenum metal may include a metal other than molybdenum in an appropriate amount. The amount of the metal other than molybdenum may be appropriately controlled. The metal other than molybdenum may be added to the molybdenum metal in an appropriate amount. The molybdenum metal may be purified to appropriately remove the metal other than molybdenum. The metal other than molybdenum may be iron, chromium, cobalt, manganese, lead, zinc, nickel, copper, cadmium, titanium, aluminum, sodium, potassium, magnesium, or calcium.

[0065] The metal other than the above molybdenum may be included in the molybdenum metal in an amount of 0.5 ppm to 20 ppm, based on the total weight of the molybdenum metal.

[0066] Thereafter, the fluorine gas may be introduced into the reactor. Before the fluorine gas is introduced, the reactor may be heated to a temperature of about 150°C to about 250°C. Thereafter, the fluorine gas may be introduced into the heated reactor. Thereafter, the fluorine gas and the molybdenum metal may react at a temperature of about 200°C to about 350°C for about 2 hours to about 4 hours. The pressure inside the reactor may be about 0.001 MPa to about 0.05 MPa. Accordingly, molybdenum fluoride may be produced.

[0067] Thereafter, the generated molybdenum fluoride can be condensed and cooled to a temperature of about -50°C to about 0°C. Thereafter, gaseous impurities generated in the process can be removed by a vacuum device.

[0068] Thereafter, the cooled molybdenum fluoride can be purified through a distillation purification process at a temperature of about 40°C to about 60°C.

[0069] Accordingly, a metal precursor containing the above molybdenum fluoride as a main component can be manufactured.

[0070] The metal precursor may include a transition metal. The metal precursor may include the transition metal in the form of a compound. The metal precursor may include the transition metal in the form of a fluoride.

[0071] The above transition metal may be selected from the group consisting of iron (Fe), chromium (Cr), cobalt (Co), manganese (Mn), lead (Pb), zinc (Zn), nickel (Ni), copper (Cu), cadmium (Cd), and titanium (Ti). The above transition metal may include at least one or more from the group consisting of iron, chromium, cobalt, manganese, lead, zinc, nickel, copper, cadmium, and titanium.

[0072] Figure 2 illustrates the deposition of a metal precursor onto a structure.

[0073] Referring to FIG. 2, the metal precursor can be deposited on the silicon wafer (110), the insulating layer (120), and the structure (130).

[0074] The metal precursor may be vaporized at a temperature of about 50° C. to about 200° C. The temperature within the reaction chamber may be about 100° C. to about 250° C. The temperature of the silicon wafer (110) may be about 50° C. to about 200° C. The pressure within the reaction chamber may be about 0.01 Torr to about 100 Torr.

[0075] The metal precursor may be introduced into the reaction chamber at a flow rate of about 50 sccm to about 500 sccm, about 50 sccm to about 400 sccm, about 50 sccm to about 300 sccm, or about 50 sccm to about 200 sccm. The metal precursor may be supplied into the reaction chamber for about 1 second to about 10 seconds, about 1 second to about 9 seconds, about 1 second to about 8 seconds, or about 2 seconds to about 8 seconds.

[0076] The above metal precursor can be deposited on the structure (130) to form the first metal precursor layer (140a).

[0077] In order to prevent the metal precursor from diffusing into the insulating layer (120), a metal layer (not shown) may be formed on the silicon wafer (110), the insulating layer (120), and the structure (130) before forming the first metal precursor layer (140a).

[0078] The above metal layer may include at least one material selected from materials including titanium series including Ti, TiN, and TiSiN, tantalum series including Ta, TaN, and TaSiN, and tungsten series including W and WN.

[0079] After the first metal precursor layer (140a) is formed, a purge process may be performed. The interior of the reaction chamber may be purged through the purge process. The purge process may introduce an inert gas, such as argon, into the reaction chamber, thereby removing process residues within the reaction chamber.

[0080] In the above purge process, the inert gas can be supplied to the reaction chamber at a flow rate of about 100 sccm to about 300 sccm, or about 150 sccm to about 250 sccm.

[0081] In the above purge process, the inert gas can be supplied into the reaction chamber for about 15 seconds to about 45 seconds, or about 20 seconds to about 40 seconds.

[0082] The method according to the present invention may comprise a step of introducing a reducing precursor into the reaction chamber before or after introducing the metal precursor.

[0083] The above reducing precursor can be introduced into the reaction chamber after the first metal precursor layer (140a) is formed by introducing the metal precursor and the interior of the reaction chamber is purged.

[0084] The above reducing precursors are forming gas (H2+ N2), ammonia (NH3), hydrazine (N2H4), alkylhydrazine (tertiary butylhydrazine, C4H 12 At least one may be selected from the group consisting of N2), hydrogen gas (H2), hydrogen atoms (H), hydrogen plasma, hydrogen radicals, alcohols, aldehydes, carboxylic acids, amines, silane (SiH4), disilane (Si2H6), trisilane (Si3H8), germane (GeH4), digermain (Ge2H6), borane (BH3), and diborane (B2H6).

[0085] The reducing precursor may comprise a mixture of the diborane and hydrogen gas. The volume ratio of the diborane and the hydrogen gas may be from about 1:7 to about 1:15, or from about 1:8 to about 1:14.

[0086] Since the reducing precursor simultaneously contains the diborane and the hydrogen gas in appropriate amounts, it can have improved reducing properties. In addition, since the reducing precursor simultaneously contains the diborane and the hydrogen gas in appropriate amounts, the content of boron included in the thin film formed by the metal precursor can be significantly reduced.

[0087] Figure 3 illustrates that a first thin film is formed on the structure by a reducing precursor.

[0088] Referring to FIG. 3, the molybdenum fluoride included in the first metal precursor layer (140a) is reduced by the reducing precursor, so that a first thin film (150a) including molybdenum can be formed.

[0089] The reducing precursor may be introduced into the reaction chamber at a flow rate of about 50 sccm to about 500 sccm, about 50 sccm to about 400 sccm, about 50 sccm to about 300 sccm, or about 50 sccm to about 200 sccm. The reducing precursor may be supplied into the reaction chamber for about 1 second to about 10 seconds, about 1 second to about 9 seconds, about 1 second to about 8 seconds, or about 2 seconds to about 8 seconds.

[0090] While the reducing precursor is supplied, the temperature of the reaction chamber may be from about 300° C. to about 650° C. The temperature of the silicon wafer (110) may be from about 350° C. to about 600° C. The pressure within the chamber may be from about 0.01 Torr to about 100 Torr.

[0091] After the first thin film (150a) containing the above molybdenum is formed, a purge process may be performed. The interior of the reaction chamber may be purged through the purge process. The purge process may cause an inert gas, such as argon, to be introduced into the reaction chamber, thereby removing process residues within the reaction chamber.

[0092] The above purge process can be performed by a process substantially identical to the above-described purge process.

[0093] The method according to the present invention comprises a step of filling the structure with the thin film by repeatedly performing the deposition step, wherein at least a portion of the thin film is etched in-situ by the molybdenum fluoride during the deposition step.

[0094] FIG. 4 illustrates that at least a portion of the first thin film is etched by the metal precursor at the same time as the metal precursor is deposited.

[0095] Referring to FIG. 4, when a metal precursor including molybdenum fluoride is introduced into the first thin film (150a) including molybdenum, a second metal precursor layer (140b) is formed on the first thin film (150a), and at least a portion of the first thin film (150a) is etched in-situ by the molybdenum fluoride.

[0096] In the past, there was a problem in which an overhang or protrusion was formed at the entrance or top of a trench or via hole by a metal precursor deposition process.

[0097] This resulted in the formation of voids or seams within the internal areas of the trenches or via holes, significantly increasing electrical resistance. To address this issue, a separate etching process was required to etch away the overhangs or protrusions formed within the trenches or via holes. However, this process reduced the efficiency of the manufacturing process and resulted in problems caused by impurities used in the separate etching process.

[0098] The method according to the present invention can suppress the formation of an overhang or protrusion on the upper portion of the structure (130) due to the etching action of fluorine contained in the molybdenum fluoride.

[0099] Due to this, the formation of a void or seam in the internal area of ​​the structure (130) is suppressed, so that the electrical characteristics required in the semiconductor device can be smoothly expressed.

[0100] In addition, since a separate etching process is not required to etch an overhang or protrusion formed at the top or entrance of the structure (130), the efficiency of the manufacturing process can be improved and impurities that may be generated in a separate etching process are not caused.

[0101] Figure 5 illustrates that a second thin film is formed by a reducing precursor.

[0102] Referring to FIG. 5, the molybdenum fluoride included in the second metal precursor layer (140b) is reduced by the reducing precursor, so that a second thin film (150b) including molybdenum can be formed.

[0103] As described above, when a metal precursor including molybdenum fluoride is introduced into the second thin film (150b) including molybdenum, a metal precursor layer is formed again on the second thin film (150b), and at least a portion of the second thin film (150b) can be etched in-situ by the molybdenum fluoride.

[0104] The above process is performed repeatedly so that the inside of the structure (130) can be filled with a thin film.

[0105] The above thin film may be a laminate of multiple thin films, such as a first thin film (150a) and a second thin film (150b) containing molybdenum.

[0106] The above thin film may be formed by repeating the process of forming a thin film including molybdenum about 20 to about 100 times.

[0107] The method according to the present invention is such that as the deposition step is repeatedly performed, the flow rate of the metal precursor introduced into the reaction chamber is reduced.

[0108] In the initial stage of forming a thin film, the deposition action of the metal precursor within the structure (130) is relatively dominant, so that the thin film can be smoothly deposited within the structure (130). However, after a certain amount of the thin film is deposited within the structure (130), the etching action of the thin film formed within the structure (130) may increase due to the etching action of fluorine contained in the metal precursor.

[0109] To solve this problem, in the present invention, the flow rate of the metal precursor introduced into the reaction chamber is controlled to be reduced so that a thin film containing molybdenum is smoothly deposited inside the structure (130).

[0110] The flow rate of the metal precursor can be adjusted differently depending on the aspect ratio of the structure (130). The larger the aspect ratio of the structure (130), the easier it is to form an overhang or protrusion.

[0111] Figure 6 illustrates a cross-sectional view to show changes in the flow rate of a metal precursor.

[0112] Referring to FIG. 6, the structure (130) may have a width (W) and a height (H). The structure (130) may have an aspect ratio, which is a ratio of height (H):width (W). The structure (130) may have an aspect ratio, which is a ratio of height (H):width (W), of 2:1 or more to 20:1 or less, 3:1 or more to 20:1 or less, 4:1 or more to 20:1 or less, 5:1 or more to 15:1 or less, or 8:1 or more to 15:1 or less.

[0113] When the structure (130) has the above aspect ratio range, the flow rate of the metal precursor may be reduced when the filling ratio of the thin film (150) based on the total volume of the structure (130) is 30 vol% or more to 90 vol% or less, 35 vol% or more to 90 vol% or less, 40 vol% or more to 90 vol% or less, 40 vol% or more to 80 vol% or less, or 40 vol% or more to 70 vol% or less. The filling ratio may be measured by a known method.

[0114] The reduced flow rate of the metal precursor may be 10% to 90%, 20% to 90%, 30% to 90%, or 40% to 90% of the initial flow rate of the metal precursor introduced into the reaction chamber.

[0115] When the above structure (130) has the above aspect ratio range, the flow rate of the metal precursor can be reduced stepwise when the filling ratio of the thin film (150) is 30 vol% or more to 90 vol% or less based on the total volume of the structure (130).

[0116] When the filling ratio of the thin film (150) is 30 vol% or more and less than 50 vol% based on the total volume of the structure (130), the reduced first flow rate of the metal precursor may be 50% or more and less than 90% of the initial flow rate of the metal precursor introduced into the reaction chamber, and when the filling ratio of the thin film (150) is 50 vol% or more and less than 90 vol%, the reduced second flow rate of the metal precursor may be 10% or more and less than 50% of the initial flow rate of the metal precursor introduced into the reaction chamber.

[0117] When the filling ratio of the thin film (150) is 30 vol% or more and less than 50 vol% based on the total volume of the structure (130), the reduced first flow rate of the metal precursor may be 50% or more and less than 80% of the initial flow rate of the metal precursor introduced into the reaction chamber, and when the filling ratio of the thin film (150) is 50 vol% or more and less than 90 vol%, the reduced second flow rate of the metal precursor may be 10% or more and less than 40% of the initial flow rate of the metal precursor introduced into the reaction chamber.

[0118] When the filling ratio of the thin film (150) is 30 vol% or more and less than 50 vol% based on the total volume of the structure (130), the reduced first flow rate of the metal precursor may be 55% or more and less than 75% of the initial flow rate of the metal precursor introduced into the reaction chamber, and when the filling ratio of the thin film (150) is 50 vol% or more and less than 90 vol%, the reduced second flow rate of the metal precursor may be 15% or more and less than 30% of the initial flow rate of the metal precursor introduced into the reaction chamber.

[0119] The above structure (130) may have an aspect ratio of more than 20:1 and less than or equal to 100:1, more than or equal to 25:1 and less than or equal to 100:1, more than or equal to 30:1 and less than or equal to 100:1, more than or equal to 30:1 and less than or equal to 90:1, or more than or equal to 30:1 and less than or equal to 80:1.

[0120] When the structure (130) has the above aspect ratio range, the flow rate of the metal precursor can be reduced when the filling ratio of the thin film (150) based on the total volume of the structure (130) is 10 vol% or more to 90 vol% or less, 15 vol% or more to 90 vol% or less, 20 vol% or more to 90 vol% or less, 25 vol% or more to 80 vol% or less, or 25 vol% or more to 70 vol% or less.

[0121] The reduced flow rate of the metal precursor may be 5% to 90%, 8% to 90%, 10% to 90%, or 20% to 90% of the initial flow rate of the metal precursor introduced into the reaction chamber.

[0122] When the structure (130) has the above aspect ratio range, the flow rate of the metal precursor can be reduced stepwise when the filling ratio of the thin film (150) is 10 vol% or more to 90 vol% or less based on the total volume of the structure (130).

[0123] When the filling ratio of the thin film (150) based on the total volume of the structure (130) is 10 vol% or more and less than 40 vol%, the reduced first flow rate of the metal precursor may be 50% or more and less than 90% of the initial flow rate of the metal precursor introduced into the reaction chamber, and when the filling ratio of the thin film (150) is 40 vol% or more and less than 90 vol%, the reduced second flow rate of the metal precursor may be 5% or more and less than 50% of the initial flow rate of the metal precursor introduced into the reaction chamber.

[0124] When the filling ratio of the thin film (150) based on the total volume of the structure (130) is 10 vol% or more and less than 40 vol%, the reduced first flow rate of the metal precursor may be 60% or more and less than 80% of the initial flow rate of the metal precursor introduced into the reaction chamber, and when the filling ratio of the thin film (150) is 40 vol% or more and less than 90 vol%, the reduced second flow rate of the metal precursor may be 10% or more and less than 40% of the initial flow rate of the metal precursor introduced into the reaction chamber.

[0125] When the filling ratio of the thin film (150) based on the total volume of the structure (130) is 10 vol% or more and less than 40 vol%, the reduced first flow rate of the metal precursor may be 55% or more and less than 75% of the initial flow rate of the metal precursor introduced into the reaction chamber, and when the filling ratio of the thin film (150) is 40 vol% or more and less than 90 vol%, the reduced second flow rate of the metal precursor may be 15% or more and less than 30% of the initial flow rate of the metal precursor introduced into the reaction chamber.

[0126] As the above deposition step is repeatedly performed, the flow rate of the reducing precursor introduced into the reaction chamber may be reduced. The reduction rate of the reducing precursor may be reduced at the same rate as the reduction rate of the flow rate of the metal precursor.

[0127] The method for manufacturing a semiconductor device according to the present invention may be performed using atomic layer deposition (ALD). The atomic layer deposition may refer to a vapor deposition process in which multiple continuous deposition cycles are performed in the reaction chamber.

[0128] During each cycle, the metal precursor can be chemically adsorbed onto the deposition surface, forming a monolayer or sub-monolayer that does not readily react with additional metal precursors. The atomic layer deposition method can include processes such as chemical vapor atomic layer deposition, atomic layer epitaxy, molecular beam epitaxy, and chemical beam epitaxy when performed with alternating pulses of a reducing precursor and a purge gas.

[0129] According to the method of the present invention, after the structure is filled with the thin film, a chemical mechanical polishing process can be performed.

[0130] Figure 7 illustrates a cross-sectional view of a gap fill layer formed as a thin film after a CMP process.

[0131] Referring to FIG. 7, a thin film (151) can be formed on the insulator (120), and the structure (130) can be filled with the thin film (150).

[0132] The above thin film (150, 151) may include molybdenum.

[0133] The upper part of the above insulating layer (120) may be covered by the above thin film (151).

[0134]

[0135] When applied to a semiconductor device, a metal wiring may be formed within the structure (130). Accordingly, a process of removing the thin film (151) formed on the upper portion of the insulating layer (120) may be performed. The removal process may be performed by a chemical mechanical polishing (CMP) process, and may be performed until the upper surface of the insulating layer (120) is exposed.

[0136] After the above CMP process, the thin film can be formed only within the structure (130).

[0137] The gap fill layer (150) formed with the above thin film can be applied as a metal wiring.

[0138] A semiconductor device manufactured according to the above semiconductor device manufacturing method may include a semiconductor substrate (100) including a structure (130) in which a trench or via hole is formed, and a gap-fill layer (150) that can fill the structure (130) and includes molybdenum, and the porosity of the gap-fill layer (150) based on the total volume of the structure (130) may be less than 0.01 vol%.

[0139] The above semiconductor device can be manufactured using the above-described semiconductor device manufacturing method. The structure (130) and the semiconductor substrate (100) may be the same as the structure (130) and the semiconductor substrate (100) described above.

[0140] The above gap fill layer (150) may include molybdenum as a main component.

[0141] The above gap fill layer (150) may contain molybdenum in an amount of 80 wt% or more, 85 wt% or more, 90 wt% or more, 95 wt% or more, 99 wt% or more, or 99.99 wt% or more.

[0142] The above gap fill layer (150) may include a transition metal other than molybdenum.

[0143] The above transition metal may be present in a content of about 1 ppm to about 100 ppm, about 3 ppm to about 100 ppm, about 5 ppm to about 100 ppm, or about 10 ppm to about 90 ppm based on the total weight of the gap fill layer (150).

[0144] The gap fill layer (150) may contain iron in an amount of about 0.5 ppm to about 10 ppm. The gap fill layer (150) may contain iron in an amount of about 1 ppm to about 7 ppm. The gap fill layer (150) may contain iron in an amount of about 1.5 ppm to about 5 ppm.

[0145] The gap fill layer (150) may contain chromium in an amount of about 0.5 ppm to about 10 ppm. The gap fill layer (150) may contain chromium in an amount of about 0.7 ppm to about 7 ppm. The gap fill layer (150) may contain chromium in an amount of about 1 ppm to about 5 ppm.

[0146] The gap fill layer (150) may contain cobalt in an amount of about 0.5 ppm to about 10 ppm. The gap fill layer (150) may contain cobalt in an amount of about 0.7 ppm to about 7 ppm. The gap fill layer (150) may contain cobalt in an amount of about 1.5 ppm to about 5 ppm.

[0147] The gap fill layer (150) may contain manganese in an amount of about 0.5 ppm to about 10 ppm. The gap fill layer (150) may contain manganese in an amount of about 1 ppm to about 7 ppm. The gap fill layer (150) may contain manganese in an amount of about 1.5 ppm to about 5 ppm.

[0148] The gap fill layer (150) may contain lead in an amount of about 0.5 ppm to about 10 ppm. The gap fill layer (150) may contain lead in an amount of about 1 ppm to about 7 ppm. The gap fill layer (150) may contain lead in an amount of about 1.5 ppm to about 5 ppm.

[0149] The gap fill layer (150) may contain zinc in an amount of about 0.5 ppm to about 10 ppm. The gap fill layer (150) may contain zinc in an amount of about 1 ppm to about 7 ppm. The gap fill layer (150) may contain zinc in an amount of about 1.5 ppm to about 5 ppm.

[0150] The gap fill layer (150) may contain nickel in an amount of about 1 ppm to about 20 ppm. The gap fill layer (150) may contain nickel in an amount of about 1.5 ppm to about 7 ppm. The gap fill layer (150) may contain nickel in an amount of about 2 ppm to about 5 ppm.

[0151] The gap fill layer (150) may contain copper in an amount of about 0.5 ppm to about 10 ppm. The gap fill layer (150) may contain copper in an amount of about 0.7 ppm to about 7 ppm. The gap fill layer (150) may contain copper in an amount of about 1 ppm to about 5 ppm.

[0152] The gap fill layer (150) may contain cadmium in an amount of about 0.3 ppm to about 10 ppm. The gap fill layer (150) may contain cadmium in an amount of about 0.5 ppm to about 7 ppm. The gap fill layer (150) may contain cadmium in an amount of about 0.7 ppm to about 5 ppm.

[0153] The gap fill layer (150) may contain titanium in an amount of about 0.5 ppm to about 10 ppm. The gap fill layer (150) may contain titanium in an amount of about 0.7 ppm to about 7 ppm. The gap fill layer (150) may contain titanium in an amount of about 1 ppm to about 5 ppm.

[0154] In addition, the gap fill layer (150) may contain aluminum in an amount of about 0.5 ppm to about 10 ppm. The gap fill layer (150) may contain aluminum in an amount of about 1 ppm to about 7 ppm. The gap fill layer (150) may contain aluminum in an amount of about 1.5 ppm to about 5 ppm. The gap fill layer (150) may contain aluminum in the form of fluoride.

[0155] The above gap fill layer (150) may include an alkali metal.

[0156] The content of the alkali metal may be about 1 ppm to about 30 ppm based on the total weight of the gap fill layer (150). The content of the alkali metal may be about 2 ppm to about 25 ppm based on the total weight of the gap fill layer (150). The content of the alkali metal may be about 2 ppm to about 20 ppm based on the total weight of the gap fill layer (150). The content of the alkali metal may be about 2 ppm to about 10 ppm based on the total weight of the gap fill layer (150).

[0157] The alkali metal may be selected from at least one group consisting of sodium (Na) or potassium (K). The alkali metal may include sodium and potassium.

[0158] The gap fill layer (150) may contain sodium in an amount of about 0.5 ppm to about 10 ppm. The gap fill layer (150) may contain sodium in an amount of about 1 ppm to about 7 ppm. The gap fill layer (150) may contain sodium in an amount of about 1.5 ppm to about 5 ppm.

[0159] The gap fill layer (150) may contain potassium in an amount of about 0.5 ppm to about 10 ppm. The gap fill layer (150) may contain potassium in an amount of about 1 ppm to about 7 ppm. The gap fill layer (150) may contain potassium in an amount of about 1.5 ppm to about 5 ppm.

[0160] The above gap fill layer (150) may include the alkaline earth metal.

[0161] The content of the alkaline earth metal may be about 1 ppm to about 30 ppm based on the total weight of the gap fill layer (150). The content of the alkaline earth metal may be about 2 ppm to about 25 ppm based on the total weight of the gap fill layer (150). The content of the alkaline earth metal may be about 2 ppm to about 20 ppm based on the total weight of the gap fill layer (150). The content of the alkaline earth metal may be about 2 ppm to about 10 ppm based on the total weight of the gap fill layer (150).

[0162] The alkaline earth metal may be selected from at least one group consisting of magnesium (Mg) and calcium (Ca). The alkali metal may include magnesium and calcium.

[0163] The gap fill layer (150) may contain magnesium in an amount of about 0.5 ppm to about 10 ppm. The gap fill layer (150) may contain magnesium in an amount of about 1 ppm to about 7 ppm. The gap fill layer (150) may contain magnesium in an amount of about 1.5 ppm to about 5 ppm.

[0164] The gap fill layer (150) may contain calcium in an amount of about 0.5 ppm to about 10 ppm. The gap fill layer (150) may contain calcium in an amount of about 1 ppm to about 7 ppm. The gap fill layer (150) may contain calcium in an amount of about 1.5 ppm to about 5 ppm.

[0165] The sheet resistance of the gap fill layer (150) may be less than about 100Ω / □. The sheet resistance of the gap fill layer (150) may be less than about 90Ω / □. The sheet resistance of the gap fill layer (150) may be less than about 80Ω / □. The sheet resistance of the gap fill layer (150) may be less than about 70Ω / □. The sheet resistance of the gap fill layer (150) may be less than about 60Ω / □. The sheet resistance of the gap fill layer (150) may be less than about 50Ω / □. The minimum value of the sheet resistance of the gap fill layer (150) may be 0.01Ω / □.

[0166] The resistivity of the gap fill layer (150) may be less than about 200 μΩ·cm. In addition, the resistivity of the gap fill layer (150) may be less than about 180 μΩ·cm. In addition, the resistivity of the gap fill layer (150) may be less than about 160 μΩ·cm. In addition, the resistivity of the gap fill layer (150) may be less than about 140 μΩ·cm. In addition, the resistivity of the gap fill layer (150) may be less than about 120 μΩ·cm. In addition, the resistivity of the gap fill layer (150) may be less than about 100 μΩ·cm. The minimum value of the resistivity of the gap fill layer (150) may be about 0.1 μΩ·cm.

[0167] The thickness of the gap fill layer (150) may be about 10 nm to about 200 nm. The thickness of the gap fill layer (150) may be about 15 nm to about 150 nm. The thickness of the gap fill layer (150) may be about 10 nm to about 150 nm. The thickness of the gap fill layer (150) may be about 10 nm to about 100 nm. The thickness of the gap fill layer (150) may be about 5 nm to about 200 nm. The thickness of the gap fill layer (150) may be about 5 nm to about 50 nm.

[0168] Since the above gap fill layer (150) has the surface resistance and resistivity as described above, the semiconductor device according to the present invention can have improved performance.

[0169] The porosity of the gap fill layer (150) based on the total volume of the structure (130) may be less than 0.01 vol%, less than 0.008 vol%, less than 0.006 vol%, or less than 0.003 vol%. The porosity may be calculated using a transmission electron microscope (TEM). When the above range is satisfied, the semiconductor device may have improved resistance characteristics.

[0170] The above gap fill layer (150) may have a first peak, a second peak, and a third peak. The first peak, the second peak, and the third peak may be measured by X-ray diffraction.

[0171] The first peak may be a peak of the crystal diffraction plane (110) of Mo, the second peak may be a peak of the crystal diffraction plane (200) of Mo, and the third peak may be a peak of the crystal diffraction plane (211) of Mo.

[0172] The 2θ of the first peak may be about 40° to about 43°. The 2θ of the first peak may be about 58° to about 62°. The 2θ of the first peak may be about 73° to about 77°.

[0173] The ratio of the intensity of the first peak to the intensity of the second peak may be from 2:1 to 50:1. The ratio of the intensity of the first peak to the intensity of the second peak may be from 3:1 to 40:1. The ratio of the intensity of the first peak to the intensity of the second peak may be from 4:1 to 30:1.

[0174] Additionally, the ratio of the intensity of the first peak to the intensity of the third peak may be 2:1 to 50:1. The ratio of the intensity of the first peak to the intensity of the third peak may be 3:1 to 40:1. The ratio of the intensity of the first peak to the intensity of the third peak may be 4:1 to 30:1.

[0175] Since the gap fill layer (150) has the above crystal characteristics, the gap fill layer (150) can have improved electrical characteristics.

[0176] The gap fill layer (150) may be applied to 3D NAND metal wiring. The lower portion of the semiconductor substrate may include transistors, word lines, bit lines, etc., including sources, drains, and gates. In addition, it may include wiring or contacts connected to the transistors, the word lines, or the bit lines. The metal wiring formed by the gap fill layer (150) may be electrically connected to at least one lower wiring or contact included in the lower structure of the semiconductor substrate. In addition, the metal wiring formed by the gap fill layer (150) may not be electrically connected to the lower structure of the semiconductor substrate, but may be connected to other parts, etc.

[0177]

[0178] Hereinafter, the present invention will be described in more detail based on examples and comparative examples. However, the following examples and comparative examples are merely illustrative examples for further explaining the present invention, and the present invention is not limited to the following examples and comparative examples.

[0179]

[0180] Manufacturing example

[0181] Manufacturing Example 1

[0182] After placing about 50 g of molybdenum metal powder (AMEICAN ELEMENT, MO-M-05) in a reactor, the reactor was preheated to a temperature of about 200°C, and the inside of the reactor was depressurized.

[0183] Thereafter, purified fluorine gas was introduced into the reactor, and the fluorine gas and the molybdenum metal powder were reacted at a temperature of about 280°C for about 2 hours. The product from the reactor was captured in a collector at about -50°C.

[0184] Thereafter, the collector was heated to a temperature of approximately 40°C, and the produced molybdenum fluoride was distilled. The distilled molybdenum fluoride was purified in a reflux column at approximately 35°C and condensed in a cylinder at 0°C. After repeating the purification process five times, approximately 90 g of purified molybdenum fluoride was produced.

[0185] Manufacturing Example 2

[0186] Molybdenum fluoride was manufactured by the same process as Manufacturing Example 1, except that molybdenum metal powder (Luoyang Combat Tungsten&Molybdenum Material, MOLYBDENUM POWDER) was used instead of the molybdenum metal powder (AMEICAN ELEMENT, MO-M-05) of Manufacturing Example 1.

[0187]

[0188] Example

[0189] Example 1

[0190] A 30-inch single-crystal silicon wafer containing a silicon oxide layer was placed in a reaction chamber. At least a portion of the silicon oxide layer had a trench formed therein, and the aspect ratio, which is the ratio of the depth to the width of the trench, was 10:1.

[0191] After the temperature inside the reaction chamber was preheated to about 180°C, molybdenum fluoride of Preparation Example 1 as a metal precursor was introduced into the reaction chamber in a gaseous state at a flow rate of 100 sccm for about 2 seconds. Thereafter, the inside of the reaction chamber was purged with argon for about 30 seconds, and the temperature inside the reaction chamber was raised to about 200°C.

[0192] Thereafter, a mixed gas of diborane and hydrogen gas (diborane content 5 vol%) as a reducing precursor was introduced into the reaction chamber at a flow rate of 200 sccm for about 10 seconds. Thereafter, the inside of the reaction chamber was purged with argon for about 30 seconds, and the above process was repeated 10 times.

[0193] Thereafter, the filling rate of the trench was 50 vol%, and at this time, the flow rate of the molybdenum fluoride of Manufacturing Example 1 introduced into the reaction chamber was reduced from 100 sccm to 50 sccm. In addition, the flow rate of the reducing precursor was reduced from 200 sccm to 100 sccm, and the above process was repeated 20 times, and a molybdenum gapfill layer was formed inside the trench.

[0194]

[0195] Example 2

[0196] A 30-inch single-crystal silicon wafer containing a silicon oxide layer was placed in a reaction chamber. At least a portion of the silicon oxide layer had a trench formed therein, and the aspect ratio, which is the ratio of the depth to the width of the trench, was 10:1.

[0197] The temperature inside the reaction chamber was preheated to approximately 180°C, and then molybdenum fluoride of Preparation Example 1 as a metal precursor was introduced into the reaction chamber in a gaseous state at a flow rate of 100 sccm for approximately 2 seconds. Thereafter, the inside of the reaction chamber was purged with argon for approximately 30 seconds, and the temperature inside the reaction chamber was raised to approximately 200°C.

[0198] Thereafter, a mixed gas of diborane and hydrogen gas (diborane content 5 vol%) as a reducing precursor was introduced into the reaction chamber at a flow rate of 200 sccm for about 10 seconds. Thereafter, the inside of the reaction chamber was purged with argon for about 30 seconds, and the above process was repeated five times.

[0199] Thereafter, the filling rate of the trench was 40 vol%, and at this time, the flow rate of the molybdenum fluoride of Manufacturing Example 1 introduced into the reaction chamber was reduced from 100 sccm to 60 sccm. In addition, the flow rate of the reducing precursor was reduced from 200 sccm to 120 sccm, and the above process was repeated 10 times.

[0200] Thereafter, the filling rate of the trench was 70 vol%, and at this time, the flow rate of the molybdenum fluoride of Manufacturing Example 1 introduced into the reaction chamber was reduced from 60 sccm to 20 sccm. In addition, the flow rate of the reducing precursor was reduced from 120 sccm to 50 sccm, and the above deposition process was repeated 15 times, and a molybdenum gapfill layer was formed inside the trench.

[0201]

[0202] Examples 3 to 8 and Comparative Examples 1 to 4

[0203] The same process as in Example 1 was followed, except that the metal precursor type, trench aspect ratio, metal precursor flow rate, and reducing agent flow rate conditions were changed as shown in Table 1 below.

[0204]

[0205] Metal precursor trench aspect ratio 1) Metal precursor initial flow rateChanged metal precursor flow rateMetal precursor flow rate change pointReducing agent initial flow rateChanged reducing agent flow rate1st2nd1st2nd1st2ndUnit-sccmvol% 2)sccm Example 1 Manufacturing Example 110:110050-50-200100-Example 2 Manufacturing Example 110:11006020407020012050 Example 3 Manufacturing Example 210:110050-60-200100-Example 4 Manufacturing Example 210:11007030308020012050 Example 5 Manufacturing Example 140:110040-50-200100-Example 6 Manufacturing Example 140:11006020407020012050 Example 7 Manufacturing Example 240:110050-60-200100-Example 8 Manufacturing Example 240:11007030308020012050Comparative Example 1Manufacturing Example 110:1100No change--200No changeComparative Example 2MoO2Cl2 3) 10:110040-50-200100-Comparative Example 3 Manufacturing Example 240:1100 No Change--200 No Change Comparative Example 4 MoO2Cl2 3) 40:1100 No change--200 No change1) Trench aspect ratio: The ratio of trench depth to width2) vol%: The percentage of metal filling in the trench based on the total volume of the trench3) MoO2Cl2: FUNCMATER, 42081700pd.

[0206]

[0207] Experimental example

[0208] Experimental Example 1 - Porosity

[0209] The porosity of the gap fill layers manufactured in Examples 1 to 8 and Comparative Examples 1 to 4 was measured. The porosity was calculated as the volume ratio of the pore area to the total area of ​​the gap fill layer using a transmission electron microscope (TEM), and the results are shown in Table 2 below.

[0210]

[0211] Experimental Example 2 - Surface Resistance

[0212] Using a 4-Point probe device (AIT CMT SR-5000), the surface resistance of the gap fill layers manufactured in Examples 1 to 8 and Comparative Examples 1 to 4 was measured, and the results are shown in Table 2 below.

[0213]

[0214] Experimental Example 3 - Non-resistance

[0215] Using a transmission electron microscope (TEM), the thickness of the gap fill layers manufactured in Examples 1 to 8 and Comparative Examples 1 to 4 was measured, and the specific resistance value was calculated from the thickness of the measured gap fill layer × the surface resistance value of Experimental Example 2. The results are shown in Table 2 below.

[0216]

[0217] Porosity Surface Resistance Ratio Resistance Unit vol%Ω / □μΩ·cmExample 1< 0.00135.2670.52Example 2< 0.00128.5257.04Example 3< 0.00138.2576.50Example 4< 0.00127.5655.12Example 5< 0.00137.1274.24Example 6< 0.00129.5159.02Example 7< 0.00136.3672.72Example 8< 0.00128.3356.66Comparative Example 1N.A. 1) Comparative Example 20.015105.23210.46 Comparative Example 3N.A. 2) Comparative example 41.5352.64705.281),2) NA: Gap fill layer is not formed up to the top of the trench

[0218]

[0219] As can be seen in Tables 1 and 2 above, Examples 1 to 8, which included molybdenum fluoride as a metal precursor and were adjusted to reduce the flow rate of the metal precursor introduced into the reaction chamber, showed that a molybdenum gapfill layer was smoothly formed inside the trench and electrical characteristics were improved compared to Comparative Examples 1 to 4.

[0220] In the case of Comparative Examples 1 and 3, even when molybdenum fluoride was used as a metal precursor, if the flow rate of the metal precursor introduced into the reaction chamber was not controlled, it was confirmed that the etching action on the thin film formed inside the trench increased, and a molybdenum gapfill layer was not formed up to the top of the trench.

[0221] In Comparative Examples 2 and 4, when molybdenum chloride was used as a metal precursor, the porosity was greatly increased and the electrical characteristics were deteriorated. This could be inferred to be due to the formation of an overhang or protrusion on the top of the trench, which caused a void to be generated inside the trench.

[0222]

[0223] The embodiment can provide a method for manufacturing a semiconductor device having improved processability and electrical characteristics.

Claims

1. A step of introducing a semiconductor substrate including a structure in which a trench or via hole is formed into a reaction chamber; A step of introducing a metal precursor containing molybdenum fluoride into the reaction chamber to deposit a thin film on the structure; and A step of filling the structure with the thin film by repeatedly performing the above deposition step, wherein at least a portion of the thin film is etched in-situ by the molybdenum fluoride during the deposition step; A method for manufacturing a semiconductor device, wherein the flow rate of the metal precursor introduced into the reaction chamber is reduced as the above deposition step is repeatedly performed.

2. In paragraph 1, A method for manufacturing a semiconductor device, wherein the above structure has an aspect ratio of 2:1 or more and 20:1 or less.

3. In paragraph 2, A semiconductor manufacturing method wherein the flow rate of the metal precursor is reduced when the filling ratio of the thin film is 30 vol% or more to 90 vol% or less based on the total volume of the structure.

4. In paragraph 3, A semiconductor manufacturing method wherein the reduced flow rate of the metal precursor is 10% or more and 90% or less compared to the initial flow rate of the metal precursor introduced into the reaction chamber.

5. In paragraph 2, A semiconductor manufacturing method wherein the flow rate of the metal precursor is reduced stepwise when the filling ratio of the thin film is 30 vol% or more to 90 vol% or less based on the total volume of the structure.

6. In paragraph 5, When the filling ratio of the thin film is 30 vol% or more and less than 50 vol% based on the total volume of the structure, the reduced first flow rate of the metal precursor is 50% or more and less than 90% of the initial flow rate of the metal precursor introduced into the reaction chamber. A semiconductor manufacturing method, wherein, when the filling ratio of the thin film is 50 vol% or more and 90 vol% or less, the reduced second flow rate of the metal precursor is 10% or more and less than 50% of the initial flow rate of the metal precursor introduced into the reaction chamber.

7. In paragraph 1, A method for manufacturing a semiconductor device, wherein the above structure has an aspect ratio of more than 20:1 and less than or equal to 100:

1.

8. In paragraph 7, A semiconductor manufacturing method wherein the flow rate of the metal precursor is reduced when the filling ratio of the thin film is 10 vol% or more to 90 vol% or less based on the total volume of the structure.

9. In paragraph 8, A semiconductor manufacturing method wherein the reduced flow rate of the metal precursor is 5% or more and 90% or less compared to the initial flow rate of the metal precursor introduced into the reaction chamber.

10. In paragraph 7, A semiconductor manufacturing method wherein the flow rate of the metal precursor is reduced stepwise when the filling ratio of the thin film is 10 vol% or more to 90 vol% or less based on the total volume of the structure.

11. In paragraph 10, When the filling ratio of the thin film is 10 vol% or more and less than 40 vol% based on the total volume of the structure, the reduced first flow rate of the metal precursor is 50% or more and less than 90% of the initial flow rate of the metal precursor introduced into the reaction chamber. A semiconductor manufacturing method, wherein, at a filling ratio of the thin film of 40 vol% or more and 90 vol% or less, the reduced second flow rate of the metal precursor is 5% or more and less than 50% of the initial flow rate of the metal precursor introduced into the reaction chamber.

12. In paragraph 1, A method for manufacturing a semiconductor device, comprising the step of introducing a reducing precursor into the reaction chamber before or after introducing the metal precursor.

13. In paragraph 12, A method for manufacturing a semiconductor device, wherein the flow rate of the reducing precursor introduced into the reaction chamber is reduced as the above deposition step is repeatedly performed.

14. In paragraph 1, The above semiconductor device manufacturing method is a semiconductor device manufacturing method using atomic layer deposition (ALD).

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