KR101180778B1 - Method of manufacturing a semicondcutor device - Google Patents

Abstract

The present invention relates to a method for manufacturing a semiconductor device, by introducing a nitrogen-containing gas with a low dielectric precursor to form a low dielectric film, it is possible to improve the mechanical properties such as hardness and tensile strength of the low dielectric film, and thus CMP, etc. It is possible to prevent damage to the low dielectric film in the process of.

Low Dielectric Film, DEMS, Nitrogen, Hardness, Tensile Strength

Description

Method of manufacturing a semiconductor device {Method of manufacturing a semicondcutor device}

The present invention relates to a method for manufacturing a semiconductor device, and more particularly, to a method of forming a low dielectric insulating film using a low dielectric precursor and a nitrogen-containing gas.

In recent years, in order to realize high speed and high integration of semiconductor devices, miniaturization and multilayering of metal wirings have been made. In addition, in order to reduce the RC signal delay, copper is used as the wiring material, and a material having a low dielectric constant k is used as the insulating layer material. In addition, a damascene process, which does not perform a metal etching and an insulating layer gap fill process, has been developed in the wiring forming process due to the difficulty of metal patterning due to the reduction of a design rule.

Dielectric constants of various insulating films generally used are 3.5 to 4.5 for the interlayer insulating film and 5 to 7 for the etch stop film, and the characteristics are steadily improved.

In general, a low dielectric film having a low dielectric constant is formed by vaporizing a precursor into the reaction chamber. However, since the conventional low dielectric film has poor mechanical properties such as hardness and tensile strength, dishing occurs during chemical mechanical polishing (CMP) process for planarization after deposition of the low dielectric film. Therefore, not only the flatness of the low dielectric film is lowered, but also the characteristics of the metal wiring formed thereon are lowered, and the electrical characteristics of the device are also lowered.

The present invention provides a method of manufacturing a semiconductor device that can improve the mechanical properties of the low dielectric film as well as improve the electrical properties.

The present invention provides a method for manufacturing a semiconductor device capable of improving the mechanical and electrical properties of a low dielectric film by introducing a nitrogen source with a precursor to form a low dielectric film.

A method of manufacturing a semiconductor device according to an aspect of the present invention includes the steps of providing a semiconductor substrate; And forming a low dielectric film on the semiconductor substrate by using a precursor and a nitrogen-containing gas.

The precursor and nitrogen-containing gas are excited in a plasma state and deposited on the semiconductor substrate.

The precursor is introduced into the nitrogen-containing gas in a ratio of 1: 0.1 to 1:10.

The low dielectric film maintains the inflow of the precursor, and repeats the inflow and interruption of the nitrogen-containing gas to form at least two layers of films.

The low dielectric layer is formed by simultaneously introducing the precursor and the nitrogen-containing gas at the top layer.

According to another aspect of the present invention, a method of forming a thin film includes preparing a substrate; Simultaneously supplying a reaction gas and a nitrogen containing gas vaporized from a precursor onto the substrate; And exciting the supplied gases into a plasma state to form a thin film on the substrate.

The precursor is introduced into the nitrogen-containing gas in a ratio of 1: 0.1 to 1:10.

According to the present invention, a nitrogen-containing gas is introduced together with a low dielectric precursor to form a low dielectric film, whereby nitrogen captures hydrogen that is not involved in the reaction of the low dielectric precursor, thereby improving the film quality of the low dielectric film. That is, mechanical properties such as hardness and tensile strength of the low dielectric film can be improved, and thus damage to the low dielectric film can be prevented in a process such as CMP. Therefore, it is possible to improve the reliability of the metal wiring to be formed later, thereby improving the electrical characteristics of the device.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings. However, the present invention is not limited to the embodiments disclosed below, but may be implemented in various forms, and only the embodiments are intended to complete the disclosure of the present invention and to those skilled in the art. It is provided for complete information. In the drawings, the thickness of layers, films, panels, regions, etc., may be exaggerated for clarity, and like reference numerals designate like elements. In addition, if a part such as a layer, film, area, etc. is expressed as “upper” or “on” another part, each part is different from each part as well as being “right up” or “directly above” another part. This includes the case where there is another part between parts.

1 is a schematic cross-sectional view of a deposition apparatus used in the method of manufacturing a semiconductor device according to the present invention, and a schematic cross-sectional view of a chemical vapor deposition (CVD) apparatus, for example, plasma enhanced CVD (PECVD). to be.

Referring to FIG. 1, the CVD apparatus used in the present invention includes a reaction chamber 100 having a reaction space therein, a substrate support 110 provided below the reaction chamber 100 to support the substrate 10. A shower head 120 provided above the inside of the reaction chamber 100 facing the substrate support 110 to inject the supply gas, a reaction gas supply unit 130 to supply the reaction gas to the shower head 120, and Clean gas is supplied to the precursor supply unit 140 for vaporizing the liquid precursor and supplying it to the shower head 120, the first plasma generating unit 150 for exciting the reaction gas and the vaporized precursor, and the shower head 120. A clean gas supply unit 160 for supplying and a second plasma generating unit 170 for exciting the clean gas are included.

The reaction chamber 100 provides a predetermined reaction zone and keeps it airtight. The reaction chamber 100 includes a reaction part having a predetermined space, including a substantially circular flat part and a side wall part extending upwardly from the planar part, and positioned on the reaction part in a substantially circular shape to keep the reaction chamber 100 airtight. It may include a cover. Of course, the reaction unit and the cover may be manufactured in various shapes in addition to the circular, for example, may be manufactured in a shape corresponding to the shape of the substrate 10.

The substrate support 110 is provided below the reaction chamber 100 and is installed at a position facing the shower head 120. The substrate support 110 may be provided with, for example, an electrostatic chuck so that the substrate 10 introduced into the reaction chamber 100 may be seated. In addition, the substrate support 110 may be provided in a substantially circular shape, but may be provided in a shape corresponding to the shape of the substrate 10 and may be made larger than the substrate 10. A substrate lift 111 is provided below the substrate support 110 to move the substrate support 110 up and down. When the substrate 10 is seated on the substrate support 110, the substrate lift 111 moves the substrate support 110 to approach the showerhead 120. In addition, a heater (not shown) is mounted in the substrate support 110. The heater generates heat to a predetermined temperature to heat the substrate 10 so that a predetermined film using a precursor, such as a low dielectric interlayer insulating film, is easily deposited on the substrate 10. Meanwhile, a cooling tube (not shown) may be further provided in the substrate support 110 in addition to the heater. The cooling tube allows the coolant to circulate in the substrate support 110 so that the cooling heat is transferred to the substrate 10 through the substrate support 110 to control the temperature of the substrate 10 to a desired temperature.

The shower head 120 is installed at a position facing the substrate support 110 at an upper portion of the reaction chamber 100, and sprays the reaction gas, the vaporized precursor, and the clean gas to the lower side of the reaction chamber 100. The shower head 120 has an upper portion connected to the reaction gas supply unit 130, the precursor supply unit 140, and the clean gas supply unit 150, and the lower portion of the shower head 120 has a plurality of injection holes 122 for injecting these gases into the substrate 10. ) Is formed. The shower head 120 may be manufactured in a substantially circular shape, but may also be manufactured in the shape of a substrate 10. In addition, the shower head 120 may be manufactured to the same size as the substrate support (110).

The reaction gas supply unit 130 is connected to an upper portion of the shower head 120 and includes a reaction gas supply pipe 132 for supplying the reaction gas to the shower head 120, and a reaction gas storage unit 134 for storing the reaction gas. do. The reactive gas storage unit 134 may include at least one reactive gas supplied with a precursor during deposition of the low dielectric interlayer insulating film according to the present invention, for example, a nitrogen-containing gas such as nitrogen (N ₂ ) gas and ammonia (NH ₃ ) gas. Save more. This nitrogen-containing gas is supplied with the precursor to improve the mechanical and electrical properties of the low dielectric interlayer insulating film.

The precursor supply unit 140 is connected to the upper portion of the shower head 120 to vaporize the liquid precursor to supply to the shower head 120. The precursor supply unit 140 is separated from the reaction gas supply pipe 132, the precursor supply pipe 142 for supplying the vaporized precursor to the shower head 120, the vaporizer 144 for vaporizing the liquid precursor, and the precursor storage for storing the precursor. It may include a portion 146. Accordingly, the liquid precursor stored in the precursor storage unit 146 is vaporized through the vaporizer 144 and supplied to the showerhead 120 through the precursor supply pipe 142. The precursor storage unit 146 stores a precursor for depositing a low dielectric interlayer insulating layer, for example, a silicon hydrocarbon such as diethoxymethylsilane (DEMS) having a structural formula shown in FIG. 2. Also, tetraethoxysilane, dimethyldiethoxysilane, dimethyldimethoxysilane, dimethylethoxysilane, methyldiethoxysilane, triethoxysilane, Trimethylphenoxysilane, phenoxysilane, hexamethyldisiloxane, 1,1,2,2-tetramethyldisiloxane (1,1,2,2-tetramethyldisiloxane), octamethyltri Materials such as siloxane (octamethyltrisiloxane) can be used as a precursor for depositing a low dielectric interlayer insulating film.

The first plasma generator 150 is installed to excite the reaction gas and the vaporized precursor to the plasma state. The first plasma generating unit 150 is the first plasma generating coil 152, which may be installed on any one of the upper and side of the reaction chamber 100, or may be installed at the same time on the upper and side of the reaction chamber 100, It includes a first power supply unit 154 for supplying a predetermined power to the first plasma generating coil 152. Here, when the first plasma generating coil 152 is installed at the top and side of the reaction chamber 100 at the same time, these first plasma generating coils 152 may be connected in parallel. In addition, the first plasma generating coil 152 installed on the upper portion of the reaction chamber 100 has an outer diameter larger than that of the shower head 120 to completely ionize the reaction gas and the vaporized precursor injected from the shower head 120. It is desirable to be.

The clean gas supply unit 160 includes a clean gas supply pipe 162 that supplies clean gas to the shower head 120, and a clean gas storage unit 164 that stores the clean gas. Here, the clean gas supply pipe 162 is separated from the reaction gas supply pipe 132 and the precursor supply pipes 132 and 142 and is connected to the shower head 120 and the upper part. The gas stored in the clean gas storage unit 164 is used to purge the unreacted gas after deposition of the interlayer insulating film, and an inert gas may be used as the clean gas.

The second plasma generator 170 excites the clean gas supplied through the clean gas supply unit 160 to a plasma state, thereby generating radicals. The second plasma generating unit 170 includes a second plasma generating coil 172 provided at a predetermined portion of the clean gas supply pipe 162 and a second power supply unit supplying predetermined power to the second plasma generating coil 172 ( 174). Therefore, a predetermined power is supplied from the second power supply unit 174 to the second plasma generating coil 172, thereby generating a predetermined electric field to excite the clean gas into the plasma state, and thereby radical of the reaction gas. Is generated.

Although not shown, an impurity supply unit may be further included to add impurities to the interlayer insulating layer when the low dielectric interlayer insulating layer is formed. The impurity supply unit stores a carbon-containing gas, such as CH ₄ , used as an impurity when an impurity is added to the interlayer insulating film, for example, when the SiOCH film is formed from the interlayer insulating film. The impurity supply part may include an impurity storage part for storing impurity gas and an impurity gas supply pipe for supplying impurities to the reaction chamber. Such an impurity supply part may be included in a reaction gas supply part or a precursor supply part. That is, the impurity storage unit may be configured separately from the reaction gas storage unit or the precursor storage unit, and the impurity gas may be supplied through the reaction gas supply pipe or the precursor supply pipe. However, the impurity supply part may be configured separately from the reaction gas supply part or the precursor supply part by providing a separate impurity storage part and a separate impurity supply pipe separated from the reaction gas supply pipe or the precursor supply pipe. Here, the impurity storage unit is provided with a valve (not shown) between the impurity supply pipes to control the supply of the impurity source.

3 to 6 are cross-sectional views of devices sequentially illustrating a method of manufacturing a semiconductor device according to an embodiment of the present invention. In this embodiment, a damascene process using a low dielectric interlayer insulating film will be described as an example.

Referring to FIG. 3, a lower conductive layer 210 is formed on a semiconductor substrate 200 on which a predetermined structure is formed. For example, individual elements such as transistors and memory cells may be formed on the semiconductor substrate 200, and the lower conductive layer 210 may be formed of copper. An etch stop layer 220 is formed on the semiconductor substrate 200 on which the lower conductive layer 210 is formed. The etch stop layer 220 is formed of a material having a high etch selectivity with the interlayer insulating layer formed thereafter. For example, when the silicon oxide-based material is used as the interlayer insulating layer, the etch stop layer 220 is etched with the interlayer insulating layer. For example, the selectivity may be formed of a silicon nitride film-based material having a difference of 1:10 or more. On the other hand, the etch stop layer 220 may be formed of a multilayer not only a single layer but also two or more layers. When the etch stop layer 220 having the double structure is formed, the first layer has a denser film quality than the second layer, and thus the etching rate may be lower than that of the second layer. To this end, the first layer of the etch stop layer 220 may be formed of a silicon nitride film doped with carbon impurities, and the second layer may be formed of a silicon nitride film doped with impurities. In addition, the etch stop layer 220 may be formed in a three-layer structure. In this case, the first layer and the third layer may be formed of, for example, silicon nitride, and the second layer may be doped with carbon impurity in the silicon nitride. It may be formed of a carbonitride film. Of course, even if the etch stop film 220 is formed in two or more layers can be formed in-situ in the same deposition equipment.

Referring to FIG. 4, an interlayer insulating layer 230 is formed on the etch stop layer 220. The interlayer insulating layer 230 is formed of a material having a high etching selectivity and a low dielectric constant with the etch stop layer 220. The deposition apparatus of FIG. 1 may be used to form the interlayer insulating layer 230. A method of forming the interlayer insulating layer 230 using the deposition apparatus of FIG. 1 will be described below. First, the semiconductor substrate 200 on which the lower conductive layer 210 and the etch stop layer 220 are formed is loaded into the reaction chamber 100 and seated on the substrate support 110. Subsequently, the inside of the reaction chamber 100 is maintained in a vacuum state, for example, 1 to 5.5 Torr, and the temperature of the semiconductor substrate 200 is 350 to 550 ° C using a heater of the substrate support 110. Keep it. Subsequently, a plasma is generated by applying an RF power source of 500 to 700 W having a frequency of 13.56 MHz through the first plasma generating unit 150. At the same time, the precursor of the liquid phase is vaporized and supplied to the shower head 120 through the precursor supply unit 140, and the reaction gas is supplied to the shower head 120 through the reaction gas supply unit 130. At this time, the vaporized precursor is introduced together with a carrier gas containing an inert gas such as helium (He). Accordingly, the vaporized precursor and the reactant gas injected into the reaction chamber 100 through the shower head 120 are excited in a plasma state and are deposited on the semiconductor substrate 200 to form the low dielectric interlayer insulating film 230. Is formed. In this case, DEMS having the structural formula of FIG. 2 may be used as a precursor of the low dielectric interlayer insulating film 230, and at least one of a nitrogen-containing gas such as nitrogen gas and ammonia gas may be used as the reaction gas. have. Here, DEMS and nitrogen-containing gas may be supplied at a ratio of 1: 0.1 to 1:10, depending on the process conditions, but nitrogen-containing gas is supplied at a flow rate of 1 to 5000 sccm, for example, DEMS Can flow at a flow rate of 10 ~ 500sccm. In addition, oxygen gas may also be introduced along with the precursor and the nitrogen-containing gas. When oxygen gas is introduced, DEMS and oxygen gas may be introduced at a ratio of 1: 0.5 to 1: 2. As in the present invention, for example, when nitrogen-containing gas is introduced together with a low dielectric precursor such as DEMS, nitrogen (N) captures hydrogen (H) of DEMS that does not contribute to the film quality. Can improve. Accordingly, mechanical properties such as hardness and tensile strength of the interlayer insulating film 230 may be improved, and accordingly, electrical characteristics of the semiconductor device may be improved.

Referring to FIG. 5, the interlayer insulating film 230 is planarized by performing a CMP process. At this time, since the hardness and tensile strength of the interlayer insulating film 230 according to the present invention are improved compared with the related art, dishing may be performed and flatness may be improved. Subsequently, predetermined regions of the interlayer insulating layer 230 and the etch stop layer 220 are etched to form the trench 242 and the via hole 244. That is, a predetermined region of the interlayer insulating layer 230 is etched to form a trench 242 extending in one direction, and a predetermined region of the interlayer insulating layer 230 and the etch stop layer 220 under the trench 242 is etched. A via hole 244 exposing the lower conductive layer 210 is formed. The trench 242 and the via hole 244 may first form the trench 242 and then form the via hole 244, or after etching the region where the via hole 244 is to be formed, to form the trench 242. The via hole 244 may be formed in the etching process. The etching process for forming the trench 242 and the via hole 244 may be performed by a plasma dry etching process using CxHy or N ₂ / H ₂ gas as the stock angle gas when the interlayer insulating film 230 is formed of an organic low dielectric material. In the case of an inorganic low dielectric material, CxFy, CO, N ₂ , Ar, and a combination thereof may be performed by a plasma dry etching process using at least one selected from the group. In addition, the etch stop layer 220 may be etched by, for example, a plasma dry etching process using at least one selected from CF ₄ , CHF ₃ , Ar, and a combination thereof.

Referring to FIG. 6, the barrier metal layer 250 is formed on the interlayer insulating layer 230 including the trench 242 and the via hole 244. The barrier metal layer 250 may be formed using, for example, atomic layer deposition (ALD) or RF sputtering. The ALD method or RF sputtering improves the step coverage property, and the film quality can be deposited more uniformly. Thus, the barrier metal layer 250 is deposited on the inner wall of the interlayer insulating film 230 without discontinuous portions. The barrier metal layer 250 may be formed in a single layer or multiple layers using materials such as TaN, Ta, TiN, TaSiN, TiSiN, and the like. In addition, the metal wiring 260 is formed to fill the trench 242 and the via hole 244 on the barrier metal layer 250. The metal wire 260 may be formed using copper. In this case, the seed layer may be formed on the barrier metal layer 250 and then formed by a CVD method or a plating method. Thereafter, the metal wire 260 and the barrier metal layer 250 are polished to expose the interlayer insulating film 240.

In the method of manufacturing a semiconductor device according to an embodiment of the present invention described above, a low dielectric precursor and a nitrogen-containing gas are simultaneously supplied to form a single low dielectric interlayer insulating film. However, the low dielectric interlayer insulating film according to the present invention may be formed by various methods in addition to the above method. Hereinafter, a method of manufacturing a semiconductor device according to other embodiments of the present invention will be described.

7 to 9 are cross-sectional views of devices sequentially illustrated to explain a method of manufacturing a semiconductor device according to another embodiment of the present invention. Here, description overlapping with the embodiment of the present invention will be omitted, and the same process conditions will be omitted.

Referring to FIG. 7, a lower conductive layer 210 and an etch stop layer 220 are formed on a semiconductor substrate 200 on which a predetermined structure is formed. After loading the semiconductor substrate 200 into the reaction chamber 100, the first interlayer insulating layer 232 is formed on the etch stop layer 220 of the semiconductor substrate 200. The first interlayer insulating film 232 is formed by simultaneously supplying a low dielectric precursor and a nitrogen-containing gas. That is, the nitrogen-containing gas is supplied to the shower head 120 through the reaction gas supply unit 130, and the precursor, for example, DEMS, is vaporized and supplied to the shower head 120 through the precursor supply unit 140. They are injected through the shower head 120 to the bottom of the reaction chamber (100). In this case, the plasma is generated from the first plasma generator 150 to excite the nitrogen-containing gas and the vaporized precursor injected from the showerhead 120, and use the same to form a first interlayer insulating film on the etch stop layer 220. Form 232.

Referring to FIG. 8, a second interlayer insulating film 234 is formed on the first interlayer insulating film 232. The second interlayer insulating layer 234 is formed by stopping supply of the reaction gas and supplying only the vaporized precursor from the precursor supply unit 140. At this time, the plasma is continuously generated by maintaining the operation of the first plasma generator 150.

Referring to FIG. 9, a third interlayer insulating film 236 is formed on the second interlayer insulating film 234. The third interlayer insulating film 234 is formed by maintaining the supply of the vaporized precursor from the precursor supply unit 140 and resuming the supply of the reaction gas from the reaction gas supply unit 130. At this time, the operation of the first plasma generator 150 is maintained to continuously generate the plasma. Therefore, the third interlayer insulating film 236 is formed of the same film quality as the first interlayer insulating film 232. That is, the first and third interlayer insulating films 232 and 236 are formed of a low dielectric film having improved mechanical properties by allowing nitrogen to capture hydrogen that is not involved in the film quality of the low dielectric precursor using a nitrogen-containing gas together with the low dielectric precursor. do.

10 is a cross-sectional view illustrating a method of manufacturing a semiconductor device in accordance with still another embodiment of the present invention.

Referring to FIG. 10, a multilayer structure in which a plurality of first interlayer insulating layers 232 and second interlayer insulating layers 234 are stacked on a semiconductor substrate 200 on which a lower conductive layer 210 and an etch stop layer 220 are formed. An interlayer insulating film 230 is formed. In this case, the first interlayer insulating film 232 is formed using a vaporized low dielectric precursor and a nitrogen-containing gas, and the second interlayer insulating film 234 is formed using only a vaporized low dielectric precursor. That is, the first interlayer insulating layer 232 is formed by supplying the reaction gas through the reaction gas supply unit 130 and vaporizing and supplying a liquid precursor through the precursor supply unit 140. In addition, the second interlayer insulating layer 232 is formed by stopping supply of the reaction gas from the reaction gas supply unit 130 and vaporizing and supplying a liquid precursor through the precursor supply unit 140. That is, the supply of the vaporized precursor is maintained through the precursor supply unit 140, and the supply and stop of the reaction gas through the reaction gas supply unit 130 are repeated, so that the first and second interlayer insulating films 232 and 234 are provided in plurality. The stacked interlayer insulating film 230 is formed. Here, the lowermost layer and the uppermost layer of the interlayer insulating film 230 are preferably formed of the first interlayer insulating film 232, and at least the uppermost layer is preferably formed of the first interlayer insulating film 232. Since the first interlayer insulating film 232 formed using the precursor and nitrogen at the same time has better mechanical properties than the second interlayer insulating film 234 formed using only the precursor, the CMP process is performed by forming the first interlayer insulating film 232 on the uppermost layer. The electrical and mechanical properties of the interlayer insulating film 230 can be maintained at.

Experimental Example

The method according to the present invention, that is, the low dielectric film formed by supplying DEMS and nitrogen gas and the low dielectric film formed by supplying only conventional DEMS were compared to compare the low dielectric film according to the present invention and the conventional low dielectric film. In both cases the precursors were vaporized using a vaporizer or bubbler and a low dielectric film was deposited in the PECVD apparatus using helium gas as the carrier gas. At this time, the substrate temperature was maintained at 350 ° C, 500W RF power having a frequency of 13.56 MHz was supplied, and the pressure of the reaction chamber was maintained at 5.5 Torr. In addition, the precursor was supplied in an amount of 2000 sccm.

Table 1 compares the electrical and mechanical properties of the low dielectric film according to the embodiment of the present invention and the low dielectric film according to the conventional comparative example. Examples 1, 2, 3 and 4 are characteristics of the low dielectric film formed by controlling the inflow of carrier gas and introducing DEMS and nitrogen-containing gas, and Comparative Examples 1, 2, 3 and 4 are controlling the inflow of carrier gas and DEMS It is characteristic of low dielectric film formed by inflow of bay.

Precursor
(sccm) Carrier gas (sccm) Nitrogen gas
(sccm) Dielectric constant Longitude (GPa) The tensile strength
(GPa) Comparative Example 1 2000 500 0 2.22 2.4 16 Comparative Example 2 2000 1500 0 2,24 2.5 18 Comparative Example 3 2000 2500 0 2.41 2.6 19 Comparative Example 4 2000 5000 0 2.58 2.9 24 Example 1 2000 500 8000 2.47 4.3 33 Example 2 2000 1500 8000 2.71 4.6 39 Example 3 2000 2500 8000 2.78 5.2 44 Example 4 2000 5000 8000 2.81 5.6 44

As shown in [Table 1], the dielectric constants (K) of the low dielectric films according to the embodiments in which DEMS and nitrogen gas were introduced at the same time and deposited were slightly higher than those of the comparative examples, but it can be seen that the hardness and tensile strength were greatly improved. . In addition, the dielectric constant, hardness, and tensile strength are adjusted according to the inflow amount of the carrier gas. As the amount of the carrier gas increases, the dielectric constant increases, and the hardness and tensile strength also increase.

On the other hand, although the technical spirit of the present invention has been described in detail according to the above embodiment, it should be noted that the above embodiment is for the purpose of explanation and not for the limitation. In addition, those skilled in the art will understand that various embodiments are possible within the scope of the technical idea of the present invention.

1 is a schematic cross-sectional view of a vapor deposition apparatus used in the method of manufacturing a semiconductor device according to the present invention.

2 is a chemical structural formula of DEMS used in the present invention.

3 to 6 are cross-sectional views of devices sequentially illustrating a method of manufacturing a semiconductor device in accordance with an embodiment of the present invention.

7 to 9 are cross-sectional views of devices sequentially shown to explain a method of manufacturing a semiconductor device according to another embodiment of the present invention.

10 is a cross-sectional view of a device for describing a method of manufacturing a semiconductor device according to still another embodiment of the present invention.

<Explanation of symbols for the main parts of the drawings>

200 semiconductor substrate 210 lower conductive layer

220: etch stop film 230: interlayer insulating film

242 trench 244 via hole

250: barrier metal layer 260: metal wiring

Claims (13)

Providing a substrate into a reaction chamber having a reaction space; And Maintaining the supply of the precursor in the supplying of the precursor and the nitrogen-containing gas into the reaction chamber, and repeatedly maintaining or stopping the supply of the nitrogen-containing gas to form at least two layers of the low dielectric film on the substrate. Including; The lowest or uppermost layer of the low dielectric film is formed by simultaneously introducing the precursor and the nitrogen-containing gas; The precursor is a method of manufacturing a semiconductor device is formed so that the lowermost layer or the uppermost layer of the low dielectric film has a hardness of 4 to 6GPa by adjusting the ratio with the nitrogen-containing gas. Providing a substrate into a reaction chamber having a reaction space; And Maintaining the supply of the precursor in the supplying of the precursor and the nitrogen-containing gas into the reaction chamber, and maintaining or stopping the supply of the nitrogen-containing gas to form at least two layers of the low dielectric film on the substrate. Including; The lowest or uppermost layer of the low dielectric film is formed by simultaneously introducing the precursor and the nitrogen-containing gas; The precursor is a method of manufacturing a semiconductor device to form a lower layer or the uppermost layer of the low dielectric film having a tensile strength of 30 to 50 GPa by adjusting the inflow rate with the nitrogen-containing gas. The method of claim 1, wherein the precursor and the nitrogen-containing gas are introduced at a ratio of 1: 0.1 to 1:10. The method of claim 1, wherein the precursor and the nitrogen-containing gas are excited in a plasma state and deposited on the semiconductor substrate. delete delete delete The low dielectric film according to claim 1 or 2, wherein the low dielectric film is diethoxymethylsilane, tetraethoxysilane, dimethyldiethoxysilane, dimethyldimethoxysilane, dimethylethoxysilane, methyldiethoxysilane, triethoxysilane, trimethyl A method for manufacturing a semiconductor device, which is formed of a precursor composed of any one of phenoxysilane, phenoxysilane, hexamethyldisiloxane, 1,1,2,2-tetramethyldisiloxane, and octamethyltrisiloxane. delete delete The method of manufacturing a semiconductor device according to claim 1, wherein a carrier gas is further supplied to adjust the hardness of the low dielectric film. The method of manufacturing a semiconductor device according to claim 2, wherein a carrier gas is further supplied to adjust the tensile strength of the low dielectric film. The method of manufacturing a semiconductor device according to claim 11 or 12, wherein the carrier gas comprises He.

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