KR20200012128A - Layer deposition method and layer deposition apparatus - Google Patents

Abstract

According to a thin film deposition method, a substrate is loaded into a process chamber. The filling volume of at least one variable capacity filling tank is adjusted. The variable capacity filling tank is filled with gas. The filled gas is introduced into the process chamber.

Description

Thin film deposition method and thin film deposition apparatus {LAYER DEPOSITION METHOD AND LAYER DEPOSITION APPARATUS}

The present invention relates to a thin film deposition method and a thin film deposition apparatus. More specifically, the present invention relates to a thin film deposition method for depositing a tungsten thin film and a thin film deposition apparatus for performing the same.

For example, a metal film containing tungsten with low resistance may be used to form a gate electrode of a memory device such as VNAND. As the stacking number of the gate electrodes is increased for high integration of the memory device, the deposition gas for forming the tungsten thin film is pyrolyzed before reaching the bottom of the opening having a high aspect ratio, thereby degrading the step coverage of the tungsten thin film. There is this.

An object of the present invention is to provide a thin film deposition method of a semiconductor device having excellent characteristics.

Another object of the present invention is to provide a thin film deposition apparatus for performing the thin film deposition method described above.

In the thin film deposition method according to the exemplary embodiments for achieving the above object of the present invention, the substrate is loaded in the process chamber. Adjust the fill volume of at least one variable displacement fill tank. Gas is charged to the variable dose filling tank. The filled gas is introduced into the process chamber.

In the thin film deposition method according to the exemplary embodiments for achieving the object of the present invention, a substrate is loaded in the process chamber. Source gas is introduced into the process chamber. Adjust the fill volume of at least one variable displacement fill tank. The reaction gas is charged to the variable dose filling tank. The charged reactant gas is introduced into the process chamber.

According to exemplary embodiments, the gas supplied from the gas source may be filled in at least one variable displacement fill tank and the filled gas may be supplied into the process chamber. At this time, the filling volume in the variable displacement filling tank may be adjusted according to the process conditions.

Thus, by filling a gas into the process chamber after filling the variable displacement filling tank with a larger adjusted fill volume, it is possible to supply a gas having a higher pressure for a relatively longer time. Accordingly, by sufficiently supplying a large amount of gas to the bottom surface of the opening having a high aspect ratio, the reactive gas can be prevented from being thermally decomposed to improve the step coverage characteristics of the thin film and the production per hour UPEH. In addition, by varying the filling volume of the variable capacity fill tank, it is possible to provide various process conditions without modifying or changing the configuration of the facility.

However, the effects of the present invention are not limited to the above-mentioned effects, and may be variously expanded within a range without departing from the spirit and scope of the present invention.

1 is a diagram illustrating a thin film deposition apparatus according to example embodiments.
FIG. 2 is a block diagram illustrating the reactive gas supply of FIG. 1.
3 is a cross-sectional view showing a variable displacement filling tank of the reaction gas supply of FIG. 2.
4 is a graph showing the volume change of the reaction gas in the variable displacement filling tank of FIG.
5 is a graph showing a change in pressure of a reaction gas supplied from a reaction gas supply according to exemplary embodiments.
6A-6C are cross-sectional views illustrating a variable displacement fill tank according to exemplary embodiments.
7 is an exploded perspective view showing the variable displacement filling tank of FIG. 6B.
8 is a diagram illustrating a thin film deposition apparatus according to example embodiments.
FIG. 9 is a block diagram illustrating a reactive gas supplier of FIG. 8.
10 is a flow chart illustrating a thin film deposition method according to exemplary embodiments.
FIG. 11A is a flowchart illustrating a source gas supply process of the thin film deposition method of FIG. 10, and FIG. 11B is a flowchart illustrating a reaction gas supply process of the thin film deposition method of FIG. 10.
12 to 16 are cross-sectional views illustrating a method of manufacturing a semiconductor device in accordance with example embodiments.
17 to 23 are cross-sectional views illustrating a method of manufacturing a semiconductor device in accordance with example embodiments.

Hereinafter, with reference to the accompanying drawings, it will be described in detail a preferred embodiment of the present invention.

1 is a diagram illustrating a thin film deposition apparatus according to example embodiments. FIG. 2 is a block diagram illustrating the reactive gas supply of FIG. 1. 3 is a cross-sectional view showing a variable displacement filling tank of the reaction gas supplier of FIG. 2. 4 is a graph showing the volume change of the reaction gas in the variable displacement filling tank of FIG. FIG. 5 is a graph showing a change in pressure of a reactant gas supplied from a reactant gas supplier according to example embodiments. FIG.

1 to 5, the thin film deposition apparatus may include a process chamber 10, a source gas supplier 100, and a reactive gas supplier 110.

In example embodiments, the process chamber 10 may accommodate a substrate W and provide space for performing a deposition process. The process chamber 10 may be a chamber for an atomic layer deposition (ALD) process.

The substrate W may be an object on which a tungsten-containing thin film is formed. The substrate W may be manufactured from a semiconductor wafer such as, for example, a silicon wafer or a germanium wafer. Meanwhile, various structures (not shown) may be further formed on the substrate W. FIG.

For example, a conductive film (not shown) or an electrode (not shown) containing metal, metal nitride, metal silicide, metal oxide, or the like on the substrate W, or an insulating film containing silicon oxide or silicon nitride ( And the like may be further formed. In some embodiments, the insulating layer including a hole or an opening therein may be formed on the substrate W, and the tungsten-containing thin film may be deposited in the hole or the opening through the processes described below.

The process chamber 10 may include a substrate support 30 as a susceptor disposed inside the chamber 20 and to which the substrate W is loaded. One or a plurality of substrates W may be disposed on the substrate support part 30. The substrate support part 30 may be installed to be elevated. In addition, the substrate support part 30 may be installed to be rotatable.

The substrate support part 30 may include a heater 32 therein. The heater 32 is connected to a heater power source (not shown) and can heat the substrate W to a predetermined temperature.

One side wall of the chamber 20 may be provided with an entrance and exit 22 for carrying in and out of the substrate W, and a gate valve 24 for opening and closing the entrance and exit 22 may be installed. In addition, a heater (not shown) may be installed on the sidewall of the chamber 20 to control the temperature of the chamber 20 during thin film deposition. For example, the temperature inside chamber 20 may be maintained in the range of about 200 ° C to about 600 ° C.

An exhaust port 26 may be formed in the bottom wall of the chamber 20. The exhaust port 26 may be connected to an exhaust device 50 having a vacuum pump, a pressure control valve, or the like through an exhaust pipe. The exhaust device 50 may maintain the temperature inside the chamber 20 at a predetermined reduced pressure.

A shower head 40 may be provided on the upper wall of the chamber 20. The shower head 40 may be installed at an open upper end of the chamber 20. The shower head 40 may include an upper space 44 and a lower space 45. The upper space 44 may be connected to the first introduction path 42, and the first gas discharge paths 46 may extend from the upper space 44 to the bottom surface of the shower head 40. The lower space 45 may be connected to the second introduction path 43, and the second gas discharge paths 47 may extend from the lower space 45 to the bottom surface of the shower head 40.

The shower head 40 may supply a source gas and a reactive gas as the thin film source gas into the chamber 20 through the first gas discharge paths 46 and the second gas discharge paths 47.

In exemplary embodiments, the source gas supplier 100 may fill a source gas supplied from the source gas source 102 by a desired fill volume and then supply the variable capacity fill tank 120 to supply the process chamber 10. ) May be included.

The source gas source 102 may include a bubbler to vaporize the metal precursor to supply the source gas to the process chamber 10. Examples of the source gas include WF6, WCl6, WBr6, W (Co) 6, W (C2H2) 6, W (PF3) 6, (C2H5) WH2 and the like.

The source gas supplier may have a structure substantially the same as or similar to that of the reactive gas supplier described below. For example, it may have a configuration such as a variable capacity fill tank similar to the reactive gas supply described below. Hereinafter, the reactive gas supplier will be described.

In exemplary embodiments, the reaction gas supplier 110 may fill the reaction gas supplied from the reaction gas source 112 by a desired fill volume and then supply the variable capacity fill tank 120 to supply the process chamber 10. ) May be included. The reactant gas supply 110 may have a variable displacement fill tank configuration.

The reaction gas source 112 may include a bubbler to supply the reaction gas to the process chamber 10. Examples of the reaction gas include B2H6, Si2H6, SiH4, H2 and the like.

As shown in FIG. 2, the reaction gas supplier 110 includes a charging line 111 connected to the reaction gas source 112, a variable capacity filling tank 120 connected to the filling line 111, and a variable capacity type. It may include a reaction gas supply line 117 connecting the filling tank 120 and the process chamber 10. The reactive gas supply line 117 may be connected to the second introduction path 43 of the shower head 40.

The reaction gas supplier 110 is installed in the filling line 111 to supply a control valve 116 for controlling the flow of the reaction gas supplied to the variable displacement filling tank 130, and the reaction gas supply line 117. It may further include a second introduction control valve 118 for controlling the flow of the reaction gas supplied to the process chamber 10 is installed in.

Although not shown in the drawings, the reaction gas supplier 110 is installed in front of the variable displacement filling tank 130 to control the flow of the reaction gas to the variable displacement filling tank 130 and a variable displacement valve. It may further include a discharge valve installed at the rear of the type filling tank 130 to control the discharge of the reaction gas from the variable capacity type filling tank 130.

In example embodiments, the thin film deposition apparatus may further include a controller 140 for controlling the charging and discharging of the reaction gas of the reaction gas supplier 110. The controller 140 may control the opening and closing of the supply control valve 116 and the second introduction control valve 118.

The second flow controller 114 may be installed in a gas supply line, that is, the filling line 111 to control a supply flow rate of the reaction gas introduced into the chamber 20 through the filling line 111. For example, the second flow controller 114 may include a mass flow controller (MFC). The second flow controller 114 may be installed between the reaction gas source 112 and the variable displacement filling tank 120 to control the flow of the reaction gas.

As shown in FIG. 3, the variable displacement fill tank 120 may be operable to vary the capacity in which the reactant gas supplied from the reactant gas source 112 is charged. The variable displacement filling tank 120 is installed to be movable in the filling chamber 122 and the filling chamber 122 to which the reaction gas is supplied, and the variable plate 124 and the variable plate varying the filling capacity of the reaction gas. It may include a variable plate driver 126 for driving 124.

The filling chamber 122 may be a tubular structure provided on the base 121. Fill chamber 122 may extend between a proximal end and a distal end that are connected to base 121.

The variable plate 124 may be installed in the filling chamber 122 to define the first and second chamber spaces. The variable plate 124 may be installed to be movable in the filling chamber 122 in a state where the outer side of the variable plate 124 is closed with the inner surface of the filling chamber 122. The space inside the filling chamber 122 between the base 121 and the variable plate 124 may be a volume filled with the reaction gas. For example, between the outer side of the variable plate 124 and the inner side of the filling chamber 122, a sealing member such as an O-ring or a gasket is provided to separate the first and second sides of the variable plate 124. The chamber spaces can be sealed to each other.

When the variable plate 124 is located at the bottom, the minimum filling volume V0 may be defined in the filling chamber 122. When the variable plate 124 is located at the top, it is possible to define the maximum filling volume 3V0 in the filling chamber 122.

The variable plate 124 may be installed to move up and down in the filling chamber 122. The variable plate driver 124 may drive the rod 125 connected to the variable plate 124 in the vertical direction. The variable plate driver 124 may be connected to the controller 140 to control the variable plate 124 to move to a desired position. Accordingly, the filling volume of the variable displacement fill tank 120 can be varied and adjusted to have the desired volume.

As shown in FIG. 4, first, in the volume adjusting step of the variable displacement filling tank 120, the variable displacement filling tank 120 is adjusted to have a desired filling volume by moving the variable plate 124 to a desired position. Can be.

Subsequently, in the filling step of the variable displacement fill tank 120, the supply control valve 116 can be opened and the second introduction control valve 118 can be closed. Accordingly, the filling chamber 122 may be charged by the reaction gas from the reaction gas source 112 to have a preset filling pressure P0. The filling pressure P0 in the filling chamber 122 may be a pressure equilibrating with the flow for a time exposed to the flow of the reaction gas from the reaction gas source 112. In this case, the supply flow rate of the reaction gas introduced into the filling chamber 122 through the second flow controller 114 may be increased to increase the filling pressure in the filling chamber 122.

In the discharge phase of the variable displacement fill tank 120, the supply control valve 116 can be closed and the second introduction control valve 118 can be opened. Accordingly, the reaction gas from the filling chamber 122 flows out to the reaction gas supply line 117 so that the pressure in the filling chamber 122 may be reduced.

As shown in FIG. 5, the graph G1 represents the reaction gas supplied through the reaction gas supply line 117 when the reaction gas is supplied from the variable displacement filling tank 120 having the expanded filling volume 3V0. The change in pressure is shown, and the graph G2 shows the change in pressure when the reaction gas is supplied from the variable displacement filling tank 120 having the smallest filling volume V0. The reaction gas in section A may have a pressure sufficient to be supplied to the bottom of the opening having a high aspect ratio, while the reaction gas in section B may have a pressure not sufficient to be supplied to the bottom of the opening.

Therefore, when supplying the reaction gas from the variable displacement filling tank 120 having an expanded filling volume 3V0 that is larger than the relatively small filling volume V0, the reaction gas having a higher pressure is relatively longer. Can supply for time. Thereby, the said reaction gas can be supplied fully to the bottom face of the opening part which has a high aspect ratio.

In example embodiments, the thin film deposition apparatus may further include a purge gas supplier for supplying a purge gas into the process chamber 10. For example, the purge gas may include nitrogen (N 2) gas, argon (Ar) gas, or the like. The purge gas supply may have a structure substantially the same as or similar to the reaction gas supply. Therefore, description of the purge gas supplier will be omitted.

The thin film deposition apparatus may further include a carrier gas supplier for supplying a carrier gas together with the reaction gas.

As described above, the thin film deposition apparatus includes a variable capacity filling tank 120 for filling the reaction gas supplied from the reaction gas source 112 into a desired filling volume, and from the variable capacity filling tank 120. The released reactant gas may be supplied to the process chamber 10 at a high pressure for a long time.

Accordingly, by adjusting the filling capacity of the filling chamber 122 to a desired volume, the reaction gas supplied from the process chamber 10 can be sufficiently supplied to the bottom surface of the opening having a high aspect ratio. In addition, by varying the filling volume of the variable capacity filling tank 120, it is possible to provide a variety of process conditions without modifying or changing the configuration of the equipment.

6A-6C are cross-sectional views illustrating a variable displacement fill tank according to exemplary embodiments. 7 is an exploded perspective view showing the variable displacement filling tank of FIG. 6B.

6A to 7, the variable displacement filling tank 130 may include a plurality of unit chambers which are coupled to be detachable from each other to adjust the filling volume therein. In detail, the variable displacement filling tank 130 includes a lower chamber 132 and an upper chamber 136 that are detachably coupled to each other to define a first filling volume, and the lower chamber 132 and the upper chamber 136 ) May further include at least one intermediate chamber 134 that is detachably coupled between the plurality of and defines a filling volume larger than the first filling volume.

As shown in FIG. 6A, the variable displacement fill tank 130 may be comprised of a lower chamber 132 and an upper chamber 136. The lower chamber 132 may be a tubular structure provided on the base 121. The upper chamber 136 may be coupled on the lower chamber 132 to define the first filling chamber. The first filling chamber may have a minimum filling volume (V0).

The lower chamber 132 and the upper chamber 136 may be coupled to each other by coupling fastening members such as fixing bolts to the first fastening holes 133a and the second fastening holes 137a corresponding to each other. The first fastening hole 133a may be formed in the first flange portion 133 protruding in the horizontal direction at the open end of the lower chamber 132, and the second fastening hole 137a may be formed in the upper chamber 136. It may be formed in the second flange portion 137 protruding in the horizontal direction at the open end. A gasket 138 for fluid sealing may be interposed between the lower chamber 132 and the upper chamber 136. Gasket fastening holes 138a corresponding to the first and second fastening holes 133a and 137a may be formed in the gasket 138.

As shown in FIG. 6B, the variable displacement fill tank 130 may be composed of a lower chamber 132, an intermediate chamber 134, and an upper chamber 136. The intermediate chamber 134 and the upper chamber 136 may be combined on the lower chamber 132 to define a second filling chamber. The second filling chamber may have a second filling volume V1 that is greater than the minimum filling volume V0.

The lower chamber 132 and the intermediate chamber 134 may be coupled to each other by fastening members, such as fixing bolts, to the first fastening hole 133a and the third fastening hole 135a corresponding to each other. The first fastening hole 133a may be formed in the first flange portion 133 protruding in the horizontal direction at the open end of the lower chamber 132, and the third fastening hole 135a may be formed in the intermediate chamber 136. The lower flange may be formed in the third flange portion 135 protruding in the horizontal direction. A gasket 138 for fluid sealing may be interposed between the lower chamber 132 and the intermediate chamber 134.

The intermediate chamber 134 and the upper chamber 136 may be coupled to each other by fastening members, such as fixing bolts, to the third fastening hole 135a and the second fastening hole 137a corresponding to each other. The third fastening hole 135a may be formed in the third flange portion 135 protruding in the horizontal direction on the open upper end of the intermediate chamber 136, and the second fastening hole 137a may be formed in the upper chamber 136. It may be formed in the second flange portion 133 protruding in the horizontal direction at the open end. A gasket 138 for fluid sealing may be interposed between the intermediate chamber 134 and the upper chamber 136.

As shown in FIG. 6C, the variable displacement fill tank 130 may be comprised of a lower chamber 132, first and second intermediate chambers 134a and 134b, and an upper chamber 136. The first and second intermediate chambers 134a and 134b and the upper chamber 136 may be combined on the lower chamber 132 to define a third filling chamber. The third filling chamber may have a third filling volume V2 that is greater than the minimum filling volume V0.

The lower chamber 132 and the first intermediate chamber 134a may be coupled to fastening members such as fixing bolts. A gasket 138 for fluid sealing may be interposed between the lower chamber 132 and the first intermediate chamber 134a.

The first intermediate chamber 134a and the second intermediate chamber 134b may be coupled to fastening members such as fixing bolts. A gasket 138 for sealing fluid may be interposed between the first intermediate chamber 134a and the second intermediate chamber 134b.

The second intermediate chamber 134b and the upper chamber 136 may be mutually coupled by fastening members such as fixing bolts. A gasket 138 for fluid sealing may be interposed between the second intermediate chamber 134b and the upper chamber 136.

As described above, the variable displacement filling tank 130 may include a plurality of unit chambers which are coupled to be detachably perpendicular to each other. Only some of the unit chambers can be selected and combined to define a desired fill volume. Alternatively, the variable displacement filling tank may include a plurality of unit chambers which are coupled to be detachably horizontal to each other.

8 is a diagram illustrating a thin film deposition apparatus according to example embodiments. FIG. 9 is a block diagram illustrating a reactive gas supplier of FIG. 8. The thin film deposition apparatus is substantially the same as the thin film deposition apparatus described with reference to FIGS. 1 to 5 except for the configuration of the plurality of variable capacitance filling tanks of the reactive gas supplier. Accordingly, like reference numerals refer to like elements, and repeated descriptions of like elements are omitted.

8 and 9, the reactive gas supplier of the thin film deposition apparatus includes a plurality of variable capacity filling tanks 120a, 120b, and 120c which respectively fill the reaction gas supplied from the reaction gas source 112 by a desired fill volume. ) May be included.

As shown in FIG. 9, the reaction gas supplier 110 may include first to third charge distribution lines 113a, 113b, and 113c connected in parallel to a charging line 111 connected to a reaction gas source 112. First to third variable displacement filling tanks 120a, 120b and 120c and first to third variable displacement filling tanks connected to the first to third filling distribution lines 113a, 113b and 113c, respectively. The first to third emission distribution lines 115a, 115b, and 115c may be connected to 120a, 120b, and 120c, respectively, and connected in parallel to a reaction gas supply line 117 connected to the process chamber 10. . The reactive gas supply line 117 may be connected to the second introduction path 43 of the shower head 40.

The reaction gas supplier 110 is installed in the first to third charge distribution lines 113a, 113b, and 113c, respectively, to supply the reaction gas to the first to third variable displacement charge tanks 120a, 120b, and 120c. First to third variable displacement types installed in the first to third filling valves 144a, 144b and 144c and the first to third discharge distribution lines 115a, 115b and 115c to control the flow, respectively. It may include first to third discharge valves (146a, 146b, 146c) for controlling the discharge of the reaction gas from the filling tank (120a, 120b, 120c).

In addition, a reaction gas supply 110 is installed in the filling line 111 to supply a control valve for controlling the flow of the reaction gas supplied to the first to third variable displacement filling tanks (120a, 120b, 120c) 116, and a second introduction control valve 118 installed in the reaction gas supply line 117 to control the flow of the reaction gas supplied to the process chamber 10.

In example embodiments, the thin film deposition apparatus may further include a controller 140 for controlling charging and boosting of the reaction gas of the reaction gas supplier 110. The controller 140 includes the supply control valve 116, the second introduction control valve 118, the first to third filling valves 144a, 144b and 144c and the first to third discharge valves 146a and 146b, The opening and closing of 146c) can be controlled.

The second flow controller may be installed in a gas supply line to control a supply flow rate of the reaction gas introduced into the chamber 20 through the gas supply line. For example, the flow controller may include a mass flow controller (MFC). Specifically, the first to third flow rate controllers 114a, 114b, and 114c are installed in the first to third charge distribution lines 113a, 113b, and 113c, respectively, to first to third variable displacement fill tanks. The flow rate of the reaction gas supplied to the 120a, 120b, 120c can be controlled.

The first to third variable displacement filling tanks 120a, 120b, and 120c may have the same or similar configuration. The first to third variable displacement fill tanks 120a, 120b, 120c may be adjusted to have the same or different fill volumes from each other. After filling the first to third variable displacement filling tanks 120a, 120b, 120c with the reaction gas, respectively, the reaction gases are simultaneously or simultaneously from the first to third filling tanks 120a, 120b, 120c. Emission may be sequentially performed and the reactant gas may be collected and supplied to the process chamber 10. At this time, the pressure of the collected reaction gas may have a pressure greater than that of each of the first to third filling tanks 120a, 120b, and 120c.

Hereinafter, a method of depositing a thin film using the thin film deposition apparatus of FIGS. 1 and 8 will be described.

10 is a flow chart illustrating a thin film deposition method according to exemplary embodiments. 11A is a flowchart illustrating a source gas supply process of the thin film deposition method of FIG. 10, and FIG. 11B is a flowchart illustrating a reaction gas supply process of the thin film deposition method of FIG. 10. The thin film deposition method may be used to form a tungsten thin film on a wafer by an atomic layer deposition process, but is not necessarily limited thereto.

Referring to FIGS. 1, 8, 10, 11a and 11b, first, the substrate W may be loaded into the process chamber 10 (S10).

In example embodiments, the process chamber 10 may be a chamber for an ALD process. The substrate W may be an object on which a tungsten-containing thin film is formed. The substrate W may be manufactured from a semiconductor wafer such as, for example, a silicon wafer or a germanium wafer. Meanwhile, various structures (not shown) may be further formed on the substrate W. FIG.

Subsequently, a source gas may be introduced into the process chamber 10 to form a precursor thin film on the substrate W.

For example, the source gas supplier 100 may vaporize a metal precursor to supply the source gas to the process chamber 10. Examples of the source gas include WF6, WCl6, WBr6, W (Co) 6, W (C2H2) 6, W (PF3) 6, (C2H5) WH2 and the like.

In step S20, the filling volume of at least one variable displacement filling tank (120, 120a, 120b, 120c) is adjusted (S202), the source gas is charged into the variable displacement filling tank (S204), and the filling The source gas charged in the tank may be supplied into the process chamber 10 (S206).

As shown in FIG. 1, the variable plate 124 may be moved such that the pressurized capacity filling tank 120 has a desired filling volume according to the process conditions. After filling the source gas from the source gas source 102 into the pressurized capacitive filling tank 120, the filled source gas may be supplied to the process chamber.

As shown in FIG. 8, after filling the first to third variable displacement filling tanks 120a, 120b, and 120c having the desired filling volume with the source gas, the first to third variable displacement filling tanks. Source gases from the fields 120a, 120b, and 120c may be simultaneously or sequentially released to be supplied into the process chamber 10 through one source gas supply line 107. In this case, the pressure of the source gas supplied through the source gas supply line 107 may have a pressure greater than the filling pressure of each of the first to third variable displacement filling tanks 120a, 120b, and 120c.

Thereafter, a first purging process may be performed (S30).

The purge gas supplier supplies a first purge gas into the process chamber 10 to discharge unabsorbed metal precursors on the surface of the substrate W or metal precursors physically adsorbed on the surface of the substrate W from the process chamber 10. You can. The first purge gas used in the first purging process may include, for example, argon (Ar) gas.

Subsequently, the precursor thin film may be converted into a metal film by introducing a reaction gas into the process chamber 10 (S40).

For example, the reaction gas supplier 100 may supply the reaction gas used as the reducing gas to the process chamber 10. As an example of the said reaction gas, B2H6, Si2H6, SiH4, H2 etc. are mentioned as an example of the said reaction gas.

In step S40, the filling volume of the at least one variable capacity filling tank (120, 120a, 120b, 120c) is adjusted (S202), the variable capacity filling tank is filled with the reaction gas (S204), the filling The reaction gas filled in the tank may be supplied into the process chamber 10 (S206).

As shown in FIG. 1, the variable plate 124 may be moved such that the pressurized capacity filling tank 120 has a desired filling volume according to the process conditions. After filling the reactive gas from the source gas source 102 into the pressurized capacitive filling tank 120, the charged reaction gas may be supplied to the process chamber.

As shown in FIG. 8, after filling the first to third variable displacement filling tanks 120a, 120b and 120c having a desired fill volume with the reaction gas, the first to third variable displacement filling tanks are shown. Reaction gases from the fields 120a, 120b, and 120c may be simultaneously or sequentially released to be supplied into the process chamber 10 through one source gas supply line 107. In this case, the pressure of the reaction gas supplied through the source gas supply line 107 may have a pressure greater than that of each of the first to third variable displacement filling tanks 120a, 120b, and 120c.

A reducing gas, such as B2H6, may pyrolyze before reaching and adsorbing to the bottom of an opening having a high aspect ratio, thereby degrading the step coverage of the tungsten thin film. However, in exemplary embodiments, the reducing gas is supplied into the process chamber 10 after being filled into the variable displacement filling tank having an expanded fill volume, thus providing a greater amount of the reducing gas with higher pressure. It can be sufficiently supplied to the bottom of the opening to prevent thermal decomposition. Accordingly, it is possible to improve the step coverage characteristics of the tungsten thin film and the yield per facility (UPEH) per hour.

Thereafter, a second purging process may be performed (S50).

The purge gas supplier may supply a second purge gas into the process chamber 10 to discharge materials remaining in the process chamber 10.

Subsequently, the above-described steps S20 to S50 may be repeated in a plurality of cycles to form a metal film having a desired thickness.

1 to 11B have been exemplarily described as supplying a source gas or a reactant gas to a process chamber by using a gas supplier having a variable displacement fill tank, but the present invention is not limited thereto. For example, as will be described later, it will be appreciated that a gas supply having the filling tank configuration can be used even when supplying a reducing gas for forming a tungsten nucleation layer in addition to the source gas and the reaction gas.

Hereinafter, a method of manufacturing a semiconductor device using the above-described thin film deposition method will be described.

12 to 16 are cross-sectional views illustrating a method of manufacturing a semiconductor device in accordance with example embodiments. For example, FIGS. 12 through 16 illustrate a method of forming a conductive structure of a semiconductor device using the thin film deposition method according to the exemplary embodiments described above.

Referring to FIG. 12, an interlayer insulating layer 220 may be formed on the lower structure 200 having the conductive pattern 210 formed therein.

In some embodiments, the lower structure 200 may include, for example, a lower insulating layer formed on the substrate W shown in FIG. 1. A circuit element including a word line, a gate structure, a diode, a source / drain layer, a contact, a wiring, and the like may be formed on the substrate W.

In this case, the lower structure 200 may be formed on the substrate 100 to cover the circuit device. The conductive pattern 210 may be formed in the lower structure 200 and may be provided as a plug that is electrically connected to at least a portion of the circuit element.

The lower structure 200 may be formed through, for example, a CVD process to include a silicon oxide based material. The conductive pattern 210 may be formed to include a metal such as tungsten (W), copper (Cu), titanium (Ti), tantalum (Ta), metal nitride, metal silicide, and / or doped polysilicon.

In some embodiments, the lower structure 200 may include a semiconductor substrate. For example, the lower structure 200 may include silicon, germanium, silicon-germanium, or group III-V compounds such as GaP, GaAs, GaSb, or the like. According to some embodiments, the lower structure 200 may be a silicon-on-insulator (SOI) substrate or a germanium-on-insulator (GOI) substrate. In this case, the conductive pattern 210 may be an n-type or p-type impurity region formed in the lower structure 200.

 The interlayer insulating layer 220 may be formed to include a silicon oxide-based material or a low dielectric organic oxide. For example, the interlayer insulating layer 220 may be formed through a CVD process or a spin coating process.

Referring to FIG. 13, an opening 225 may be formed to at least partially expose the conductive pattern 210 by partially removing the interlayer insulating layer 220.

In some embodiments, the opening 225 may have a hole shape that is entirely exposed by the top surface of the conductive pattern 210. In some embodiments, the opening 225 may have a trench shape extending linearly to expose the top surface of the conductive pattern 210.

Referring to FIG. 14, a barrier conductive layer 230 may be formed along the surface of the interlayer insulating layer 220 and the sidewalls and the bottom of the opening 225.

In example embodiments, the barrier conductive layer 230 may be formed using an ALD process or a plasma enhanced ALD process using an organometallic precursor. For example, the barrier conductive film 230 may be formed to include tungsten nitride, tungsten carbide or tungsten carbonitride.

Referring to FIG. 15, a metal film 240 may be formed on the barrier conductive film 230 to sufficiently fill the opening 225.

In example embodiments, the metal layer 240 may be formed using the thin film deposition method described with reference to FIGS. 10, 11A, and 11B.

As illustrated in FIGS. 10, 11A, and 11B, deposition cycles of a source gas supply process, a first purging process, a reaction gas supply process, and a second purging process may be repeatedly performed to form a metal film having a desired thickness. For example, a tungsten thin film can be formed using WF6 as a source gas and B2H6 as a reaction gas.

In this case, the barrier conductive layer 230 and the metal layer 240 may be deposited in-situ in substantially the same deposition chamber.

Referring to FIG. 16, the upper portion of the metal layer 240 and the barrier conductive layer 230 are planarized until a top surface of the interlayer insulating layer 220 is exposed through, for example, a chemical mechanical polishing (CMP) process. can do.

Through the planarization process, a conductive structure electrically connected to the conductive pattern 210 and including a barrier conductive pattern 232 and a metal filling pattern 242 may be formed in the opening 225. In example embodiments, the conductive structure may include a tungsten nitride / tungsten (WNx / W) stacked structure.

In example embodiments, after the barrier conductive layer 230 is formed, a pretreatment process may be performed. The pretreatment process may be formed using a reaction gas process process of the thin film deposition method described with reference to FIGS. 10A and 10B.

For example, B2H6 may be supplied as a reaction gas onto the substrate W on which the barrier conductive film 230 is formed. The reaction gas may be supplied using a reaction gas supply having a variable capacity fill tank configuration to form a nucleation layer. The B2H6 reaction gas is decomposed at the surface of the substrate and adsorbed into a single boron or as a variety of boron hydrides to help the nucleation of the tungsten thin film.

17 to 23 are cross-sectional views illustrating a method of manufacturing a semiconductor device in accordance with example embodiments. For example, FIGS. 17 to 23 illustrate a method of manufacturing a nonvolatile memory device having a three-dimensional structure or a vertical memory device including a vertical channel.

17 to 23, the first direction is a direction extending vertically from the upper surface of the substrate. In addition, two directions parallel to the upper surface of the substrate and crossing each other are defined as a second direction and a third direction. For example, the second direction and the third direction may perpendicularly intersect each other.

Referring to FIG. 17, an interlayer insulating films 302 (for example, 302a to 302g) and sacrificial films 304 (for example, 304a to 304f) are alternately and repeatedly stacked on the substrate 300 to form a mold structure. can do. Thereafter, the mold structure may be partially etched to form channel holes 310 exposing the top surface of the substrate 300.

For example, the interlayer insulating film 302 may be formed to include silicon oxide. The sacrificial layers 304 may have a high etching selectivity with respect to the interlayer insulating layer 302 and may be formed using a material that can be easily removed by a wet etching process. For example, the sacrificial layers 304 may be formed using silicon nitride.

The sacrificial layers 304 may be removed through a subsequent process to provide a space in which a ground selection line (GSL), a word line, and a string selection line (SSL) are formed. Accordingly, the number of the interlayer insulating layers 302 and the sacrificial layers 304 may vary depending on the number of the GSLs, word lines, and SSLs formed thereafter.

For example, the GSL and SSL may be formed in one layer, and the word line may be formed in four layers. In this case, as shown in FIG. 16, the sacrificial layers 304 may be stacked in six layers, and the interlayer insulating layers 302 may be stacked in seven layers. However, the stacking number of the interlayer insulating film 302 and the sacrificial film 304 shown in FIG. 16 is exemplary and may be increased according to the degree of integration of the semiconductor device.

For example, a plurality of channel holes 310 may be formed by partially removing the mold structure through a dry etching process. A plurality of channel holes 310 may be formed along the third direction to form a channel hole column. In addition, a plurality of channel hole columns may be formed along the second direction.

Referring to FIG. 18, a vertical channel structure 320 including a dielectric layer structure 322, a channel 324, and a filling pattern 326 may be formed in each channel hole 310. The capping pad 330 may be formed on the vertical channel structure 320.

For example, a dielectric layer may be formed along the sidewalls and bottoms of the channel holes 310 and the upper surface of the interlayer insulating layer 302g of the uppermost layer. Although not specifically illustrated, the dielectric film may be formed by sequentially stacking a blocking film, a charge storage film, and a tunnel insulating film.

The blocking film may be formed using an oxide such as silicon oxide, the charge storage layer may be formed using a nitride or metal oxide such as silicon nitride, and the tunnel insulating layer may be formed using an oxide such as silicon oxide. Can be. For example, the dielectric layer may be formed to have an oxide-nitride-oxide (ONO) stacked structure.

For example, an etch-back process may partially remove the top and bottom of the dielectric film. Accordingly, the dielectric layer structure 322 may be formed by substantially removing portions formed on the upper surface of the interlayer insulating layer 302g of the dielectric layer and the upper surface of the substrate 300. For example, the dielectric film structure 322 is formed on the sidewall of the channel hole 310 and may have a substantially straw shape or a cylinder shell shape.

Subsequently, a channel film is formed along the upper surfaces of the interlayer insulating film 302g and the dielectric film structure 322 of the uppermost layer, and the upper surface of the substrate 300, and a filling film filling the remaining portions of the channel holes 310 is formed on the channel film. Can be formed.

The channel layer may be formed using polysilicon or amorphous silicon doped with impurities. Meanwhile, the channel film may be formed using polysilicon or amorphous silicon and then converted into monocrystalline silicon by heat treatment or laser beam irradiation. The filling film may be formed using an insulating material such as silicon oxide or silicon nitride.

The fill layer and the channel layer are planarized until the uppermost interlayer insulating layer 302g is exposed to be sequentially stacked from the inner wall of the dielectric layer structure 322 to fill the channel hole 310 and fill the channel 324 and the fill pattern ( 326 may be formed. The planarization process may include a CMP process and / or an etch-back process.

The channel 324 has a substantially cup shape and may be in contact with the top surface of the substrate 300 exposed by the channel hole 310. The filling pattern 326 may have a pillar or a hollow cylindrical shape inserted into the internal space of the channel 324.

As the channel 324 is formed in each channel hole 310, a channel column corresponding to the arrangement form of the channel hole column described above may be formed.

A capping pad 330 may be further formed on the vertical channel structure 320 to cap the upper portion of the channel hole 310. For example, an upper portion of the dielectric layer structure 322, the channel 324, and the filling pattern 326 may be removed through an etch-back process to form a recess. Thereafter, a pad film filling the recess is formed on the uppermost interlayer insulating film 302g, and the upper portion of the pad film is planarized through a CMP process until the upper surface of the uppermost insulating interlayer 302g is exposed, thereby capping pad 330. ) Can be formed. The pad layer may be formed using polysilicon or, for example, polysilicon doped with n-type impurities.

The first upper insulating layer 340 covering the capping pads 330 may be formed on the interlayer insulating layer 302g of the uppermost layer. The first upper insulating layer 440 may be formed through, for example, a CVD process or a spin coating process to include silicon oxide.

Referring to FIG. 19, an opening 350 may be formed by partially etching the first upper insulating layer 340 and the mold structure. For example, the opening 350 may be formed by etching the first upper insulating layer 340 and the mold structure portions between the adjacent neighboring channel rows through a dry etching process.

The opening 350 may pass through the mold structure along the first direction to expose the top surface of the substrate 300. In addition, the opening 350 may extend in the third direction, and a plurality of openings 350 may be formed along the second direction.

The opening 350 may be provided as a gate line cut region. A predetermined number of the channel columns may be arranged between the adjacent openings 350 along the second direction.

On the other hand, as the openings 350 are formed, the interlayer insulating layers 302 and the sacrificial layers 304 may be formed of the interlayer insulating patterns 306 (for example, 306a to 306g) and the sacrificial patterns 308, respectively. For example, 308a to 308f. The interlayer insulating pattern 306 and the sacrificial pattern 308 may have a plate shape that surrounds and extends the vertical channel structures 320 included in the predetermined number of channel rows.

Referring to FIG. 20, sacrificial patterns 308 having sidewalls exposed by the opening 350 may be removed.

When the sacrificial pattern 308 includes silicon nitride and the interlayer insulating pattern 306 includes silicon oxide, the sacrificial patterns 308 may be wet-etched using an etchant such as phosphoric acid having a selectivity to silicon nitride. Can be removed via

As the sacrificial layer patterns 308 are removed, a gap 360 is formed between the interlayer insulating patterns 306 of each layer, and the outer wall of the dielectric layer structure 322 is exposed by the gap 360. Can be.

21, the outer wall of the exposed dielectric film structure 322 and the inner wall of the gap 360, the surface of the interlayer insulating patterns 306, the surface of the first upper insulating film 340, and the exposed substrate 300. A barrier conductive layer 363 may be formed along the upper surface of the substrate. A metal gate film 365 may be formed on the barrier conductive film 363. The metal gate layer 365 may be formed to completely fill the gaps 360 of each layer, and the opening 350 may also be at least partially filled.

For example, the barrier conductive layer 363 may be formed by an ALD process or a plasma enhanced ALD process using an organometallic precursor. For example, the barrier conductive film 363 may be formed to include tungsten nitride, tungsten carbide or tungsten carbonitride.

In example embodiments, a nucleation layer may be formed by supplying a reaction gas such as B2H6 on the substrate 400 on which the barrier conductive layer 363 is formed. The reaction gas may be supplied using a reaction gas supply having a variable displacement fill tank configuration described with reference to FIGS. 1-11B. The B2H6 reaction gas is decomposed at the surface of the substrate and adsorbed into a single boron or as a variety of boron hydrides to help the nucleation of the tungsten thin film.

The opening 350 may have a high aspect ratio according to the degree of integration of the semiconductor device. A reducing gas such as B2H6 may pyrolyze before reaching and adsorbing to the bottom of the opening 350 having a high aspect ratio, thereby degrading the step coverage of the tungsten thin film. However, in the exemplary embodiments, as the reaction gas is boosted to a pressure higher than the filling pressure P0, a large amount of the reaction gas may be sufficiently supplied to the inside of the gap 360 at the bottom of the opening 350. have.

Subsequently, the metal gate layer 365 may be formed on the barrier conductive layer 363 using the thin film deposition method described with reference to FIGS. 10, 11A, and 11B.

As illustrated in FIGS. 10, 11A, and 11B, deposition cycles of a source gas supply process, a first purging process, a reaction gas supply process, and a second purging process may be repeatedly performed to form a metal film having a desired thickness. For example, a tungsten thin film can be formed using WF6 as a source gas and B2H6 as a reaction gas.

Referring to FIG. 22, the barrier conductive layer 363 and the metal gate layer 365 are partially etched to expose the barrier conductive pattern 367 and the metal gate 370 (for example, 370a to 370) in the gap 360 of each layer. 370f) can be formed. The metal gate 370 may have a line shape or a plate shape that surrounds and extends sidewalls of the vertical channel structures 320 included in the predetermined number of channel columns.

For example, the upper portions of the barrier conductive layer 363 and the metal gate layer 365 may be planarized through, for example, a CMP process until the upper surface of the first upper insulating layer 340 is exposed. Thereafter, portions of the barrier conductive layer 363 and the metal gate layer 365 formed in the opening 350 are partially etched through, for example, an isotropic etching process, thereby forming the barrier conductive pattern in the gap 360 of each layer. 367 and the metal gate 370 may be formed. The barrier conductive pattern 367 may be formed along the inner wall of the gap 360, and the metal gate 370 may be formed on the barrier conductive pattern 367 to fill the gap 360 of each layer.

The metal gates 370 may include a GSL, a word line, and an SSL that are sequentially spaced apart from the upper surface of the substrate 300 along the first direction. For example, the lowermost metal gate 370a may be provided as the GSL. Four layers of metal gates 370b to 370e on the GSL may be provided to the word line. The uppermost metal gate 370f on the word line may be provided by the SSL.

Referring to FIG. 23, an impurity region 305 may be formed on the substrate 300 exposed by the opening 350, and a spacer 380 and a cutting pattern 385 may be formed to fill the opening 305. .

For example, the impurity region 305 may be formed by implanting n-type impurities such as phosphorous or arsenic through the opening 350 through an ion implantation process. The impurity region 305 may be formed on the upper portion of the substrate 300 and extend in the third direction.

The spacer 380 may be formed on the sidewall of the opening 350. For example, a spacer film including an insulating material such as silicon oxide may be formed through an ALD process along the upper surface of the first upper insulating layer 340 and the sidewalls and the bottom surface of the opening 350. For example, the spacer layer 380 may be selectively formed on the sidewall of the opening 350 by partially removing the spacer layer through an anisotropic etching process or an etch-back process.

Thereafter, a cutting pattern 385 may be formed to fill the remaining portion of the opening 350. For example, a conductive film that sufficiently fills the opening 350 may be formed on the first upper insulating film 340. A cutting pattern 385 may be formed by planarizing the upper portion of the conductive layer through the CMP process until the upper surface of the first upper insulating layer 340 is exposed to extend in the opening 350.

The conductive layer may be formed through an ALD process or a sputtering process to include metal, metal nitride, metal silicide and / or doped polysilicon. The cutting pattern 385 may be provided to the CSL of the semiconductor device.

In some example embodiments, the conductive layer may be formed using an organometallic precursor according to the above-described example embodiments. In this case, the cutting pattern 385 may include tungsten.

A second upper insulating layer 390 may be formed on the first upper insulating layer 340 to cover the cutting pattern 385 and the spacer 380. The second upper insulating layer 390 may be formed through, for example, a CVD process so as to include silicon oxide substantially the same as or similar to the first upper insulating layer 340.

Thereafter, a bit line contact 395 may be formed to penetrate the first and second upper insulating layers 390 and 340 to contact the capping pad 330. Subsequently, a bit line 397 electrically connected to the bit line contact 395 may be formed on the second upper insulating layer 390. The bit line contacts 395 and bit lines 397 may be formed through a PVD process, an ALD process, a sputtering process, or the like to include metals, metal nitrides, doped polysilicon, and the like.

A plurality of bit line contacts 395 may be formed to correspond to the capping pad 330 to form a bit line contact array. In addition, the bit line 397 extends in the second direction, for example, and may be electrically connected to the plurality of capping pads 330 through the bit line contact 395. In addition, a plurality of bit lines 397 may be formed along the third direction.

The thin film deposition apparatus and the thin film deposition method according to the above-described exemplary embodiments may be used to form a conductive structure such as a gate pattern of a flash memory device. In addition, the thin film deposition apparatus and the thin film deposition method may be extended to form electrodes, gates, contacts, etc. of various semiconductor devices such as an MRAM device, an ReRAM device, a PRAM device, a logic device, and the like. have.

Although the above has been described with reference to embodiments of the present invention, those skilled in the art will be able to variously modify and change the present invention without departing from the spirit and scope of the invention as set forth in the claims below. It will be appreciated.

10: process chamber 20: chamber
22: outlet 24: gate valve
26: exhaust port 30: substrate support
32: heater 40: shower head
42: first introduction furnace 43: second introduction furnace
44: upper space 45: lower space
46: first gas discharge passage 47: second gas discharge passage
50: exhaust device 100: source gas supply
102: source gas source
104, 104a, 104b, 104c: first flow controller
106, 116: supply control valve 107: source gas supply line
108: first introduction control valve 110: reaction gas supply
111: filling line 112: reaction gas source
113a, 113b, 113c: charge distribution line
114, 114a, 114b, 114c: second flow controller
115a, 115b, 115c: emission distribution lines
117: reaction gas supply line 118: second introduction control valve
120, 120a, 120b, 120c, 130: variable displacement filling tank
121: base 122: filling chamber
124: variable plate 125: rod
126: variable plate drive 132: lower chamber
134, 134a, 134b: intermediate chamber 136: upper chamber
138: gasket 140: controller
144a, 144b, and 144c: filling valves 146a, 146b and 146c: discharge valves
200: substructure
210: conductive pattern 220, 302: interlayer insulating film
225, 350: opening 240: metal film
232, 367: barrier conductive pattern 242: metal filling pattern
304: sacrificial film 305: impurity region
306: interlayer insulation pattern 308: sacrificial pattern
310: channel hole 320: vertical channel structure
322 dielectric layer structure 324 channels
326: filling pattern 330: capping pad
340: first upper insulating film 360: gap
380: spacer 385: cutting pattern
390: second upper insulating film 395: bit line contact

Claims (10)

Load the substrate into the process chamber
Adjust the filling volume of at least one variable displacement filling tank
Charging gas into the variable displacement filling tank and
And introducing said filled gas into said process chamber. The method of claim 1, wherein adjusting the filling volume of the variable displacement filling tank
A variable plate is installed in the filling chamber so that the outer side can be lifted and lowered in a state in which the outer side is closed with the inner surface of the filling chamber, and
Thin film deposition method comprising moving said variable plate to have a desired fill volume. The method of claim 1, wherein adjusting the filling volume of the variable displacement filling tank
Providing a plurality of unit chambers detachably coupled to each other, and
And depositing some of said unit chambers to have a desired fill volume. 2. The method of claim 1, wherein charging the gas into the variable capacity fill tank comprises filling the gas supplied from a gas source into a plurality of variable capacity fill tanks, respectively. 5. The method of claim 4, wherein the variable displacement fill tanks are each connected to charge distribution lines connected in parallel to a charge line connected to the gas source. 5. The method of claim 4, wherein introducing the filled gas into the process chamber
Simultaneously or sequentially discharging the gas from the plurality of variable displacement fill tanks and
Introducing the released gases into a supply line connected with the process chamber. 7. The method of claim 6 wherein the variable fill tanks are each connected to discharge distribution lines connected in parallel to the supply line. The method of claim 1, wherein the gas comprises at least one of a source gas, a reactive gas, and a purge gas. 9. The method of claim 8, wherein the source gas comprises a tungsten precursor and the reaction gas comprises boron. The method of claim 1, wherein the gas is introduced into the filling tank through a flow controller installed in a filling line connected to a gas source.

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