Sionc thin film and method for manufacturing same

Abstract

Provided is a method for manufacturing a SiONC thin film. The method for manufacturing a SiONC thin film may comprise the steps of: preparing a substrate; and providing a silicon precursor, an organic precursor, and plasma on the substrate to manufacture a SiONC thin film from a reaction of the silicon precursor, the organic precursor, and the plasma.

Description

SIONC thin film and its manufacturing method

[0001] The present invention relates to a method for manufacturing a SiONC thin film using a molecular layer deposition method.

[0002] In order to realize ultra-high-speed logic chips and ultra-high-density (ULSI: Ultra Large-Scale Integration) semiconductor devices, it has become necessary for the interconnection structure applied to the integrated circuit to have a multi-layer metal wiring structure and a wiring spacing of less than several tens of nm. Until now, the speed of general chips has been greatly influenced by the switching speed of the transistor, but the speed of the high-density chip mentioned above is determined by the RC delay (R: resistance of the metal conductor wiring, C: capacitance of the insulating material between the metal conductor wiring) by the wiring rather than the switching speed.

[0003] That is, when the wiring spacing is reduced below a certain level (<180 nm), the switching speed of the device is reduced due to cross-talk noise and RC delay between the wiring. A technical solution to reduce RC delay is to replace the existing conductor and insulating materials that make up the multilayer wiring system with materials that have low resistance and low dielectric constant. Accordingly, the metal conductor part is replaced from the existing Al to Cu with higher electrical conductivity, while the insulating material is replaced and applied from SiO2 (dielectric constant value 3.9~4.3), which was used as the existing insulating material, to a low-k material (dielectric constant value less than 4), which is a lower dielectric material.

[0004] Traditionally, SiC-based materials deposited via PECVD have been used as low-k materials. However, this requires high heat treatment temperatures during deposition and introduces carbon impurities. To address these issues, spin coating, a solution-based process, is currently being used. However, this method also fails to form a proper thin film on fine, complex semiconductor devices, resulting in a high defect rate. Therefore, new materials and deposition methods are needed to address these issues.

[0005] The technical problem to be solved by the present invention is to provide a SiONC thin film and a method for manufacturing the same.

[0006] Another technical problem to be solved by the present invention is to provide a SiONC thin film and a method for manufacturing the same using a molecular layer deposition method.

[0007] Another technical problem to be solved by the present invention is to provide a SiONC thin film having a low dielectric constant and a method for manufacturing the same.

[0008] Another technical problem to be solved by the present invention is to provide a SiONC thin film with easy composition control and a method for manufacturing the same.

[0009] Another technical problem that the present invention seeks to solve is to provide a SiONC thin film with fewer defects and a method for manufacturing the same.

[0010] Another technical problem that the present invention seeks to solve is to provide a SiONC thin film and a method for manufacturing the same, which can ensure uniform thickness and composition even over a large area.

[0011] Another technical problem to be solved by the present invention is to provide a SiONC thin film with improved physical durability and a method for manufacturing the same.

[0012] Another technical problem to be solved by the present invention is to provide a SiONC thin film with improved chemical durability and a method for manufacturing the same.

[0013] The technical problems to be solved by the present invention are not limited to those described above.

[0014] To solve the technical problems described above, the present invention provides a method for manufacturing a SiONC thin film.

[0015] According to one embodiment, the method for manufacturing the SiONC thin film may include the steps of preparing a substrate, and providing a silicon precursor, an organic precursor, and plasma on the substrate, thereby manufacturing a SiONC thin film in which the silicon precursor, the organic precursor, and the plasma are reacted.

[0016] According to one embodiment, the step of manufacturing the SiONC thin film may include the step of providing the silicon precursor on the substrate, the step of providing the plasma on the substrate on which the silicon precursor is provided, and the step of providing the organic precursor on the substrate on which the plasma is provided.

[0017] According to one embodiment, the plasma may include nitrogen (N2) plasma, and as the plasma is provided on the substrate on which the silicon precursor is provided, a ligand of the silicon precursor adsorbed on the substrate is substituted with an amino group, and as the organic precursor is provided on the substrate on which the plasma is provided, the organic precursor may be bonded with the amino group.

[0018] According to one embodiment, the step of providing the silicon precursor on the substrate, the step of providing the plasma on the substrate on which the silicon precursor is provided, and the step of providing the organic precursor on the substrate on which the plasma is provided are defined as a unit process, and the unit process may include being repeated a plurality of times.

[0019] According to one embodiment, the method for manufacturing the SiONC thin film may include linearly increasing the thickness of the SiONC thin film as the unit process is repeated multiple times.

[0020] According to one embodiment, the method for manufacturing the SiONC thin film may include controlling the growth rate of the SiONC thin film according to the power of the plasma provided on the substrate.

[0021] According to one embodiment, the method for manufacturing the SiONC thin film may include controlling the contents of silicon (Si), oxygen (O), carbon (C), and nitrogen (N) in the SiONC thin film according to the power of the plasma provided on the substrate.

[0022] In one embodiment, the silicon precursor may include Tetraisocyanatosilane (TICS).

[0023] In one embodiment, the organic precursor may comprise Phloroglucinol (PhI).

[0024] According to one embodiment, the plasma may include any one of nitrogen (N2) plasma, hydrogen (H2) plasma, nitrogen / argon (N2 / Ar) plasma, hydrogen / nitrogen (H2 / N2) plasma, and hydrogen / argon (H2 / Ar) plasma.

[0025]

[0026] To solve the above-described technical problems, the present invention provides a SiONC thin film.

[0027] According to one embodiment, the SiONC thin film may include silicon (Si), oxygen (O), nitrogen (N), and carbon (C), but having a lower dielectric constant value than a silicon oxide (SiO2) thin film.

[0028] According to one embodiment, the SiONC thin film may include a dielectric constant value of 3.5 k or less.

[0029] According to one embodiment, the SiONC thin film may have a thickness change of 11% or less even after heat treatment at 600°C.

[0030] According to one embodiment, the SiONC thin film may be used as an interlayer insulating film in an integrated circuit.

[0031] A method for manufacturing a SiONC thin film according to an embodiment of the present invention comprises the steps of preparing a substrate, and the steps of providing a silicon precursor (e.g., TICS), an organic precursor (e.g., Phl), and plasma (e.g., N2plasma) on the substrate to manufacture a SiONC thin film by a molecular layer deposition method, wherein the plasma (N2plasma) may be provided before the organic precursor (Phl).

[0032] The SiONC thin film manufactured by the above-described method can have a lower dielectric constant value (3.5 k or less) compared to conventional silicon oxide (SiO2) thin films, and thus can be easily applied as an interlayer insulating film for integrated circuits. In addition, the SiONC thin film has high physical and chemical stability, and can have a uniform thickness and composition even over a large area.

[0033] FIG. 1 is a flowchart for explaining a method for manufacturing a SiONC thin film according to an embodiment of the present invention.

[0034] FIG. 2 is a flowchart specifically explaining step S200 of a method for manufacturing a SiONC thin film according to an embodiment of the present invention.

[0035] FIG. 3 is a process flow diagram specifically explaining step S200 of a method for manufacturing a SiONC thin film according to an embodiment of the present invention.

[0036] FIG. 4 is a drawing for explaining a silicon precursor used in a method for manufacturing a SiONC thin film according to an embodiment of the present invention.

[0037] FIG. 5 is a drawing for explaining an organic precursor used in a method for manufacturing a SiONC thin film according to an embodiment of the present invention.

[0038] FIG. 6 is a drawing for explaining the formation mechanism of a SiONC thin film according to an embodiment of the present invention.

[0039] FIG. 7 is a process flow diagram for explaining a method for manufacturing a SiONC thin film according to another embodiment of the present invention.

[0040] FIG. 8 is a drawing for explaining the formation mechanism of a SiONC thin film according to another embodiment of the present invention.

[0041] FIG. 9 is a process flow diagram for explaining a method for manufacturing a SiONC thin film according to another embodiment of the present invention.

[0042] FIG. 10 is a drawing for explaining the formation mechanism of a SiONC thin film according to another embodiment of the present invention.

[0043] FIG. 11 is a drawing for explaining a device for manufacturing a SiONC thin film according to an embodiment of the present invention.

[0044] FIG. 12 is a drawing comparing the growth rate and refractive index of a SiONC thin film according to experimental examples of the present invention and a SiON thin film according to a comparative example.

[0045] FIG. 13 is a drawing comparing the thickness change according to the number of cycles of a SiONC thin film according to experimental examples of the present invention and a SiON thin film according to a comparative example.

[0046] Figure 14 is a diagram showing the growth rate and refractive index according to the power of plasma used in the manufacturing process of a SiONC thin film according to Experimental Example 1-1 of the present invention.

[0047] Figure 15 is a drawing showing the composition change according to the power of plasma used in the manufacturing process of a SiONC thin film according to Experimental Example 1-1 of the present invention.

[0048] Figure 16 is a drawing showing changes in electrical characteristics according to the power of plasma used in the manufacturing process of a SiONC thin film according to Experimental Example 1-1 of the present invention.

[0049] Fig. 17 is a schematic diagram of a structure for measuring IV characteristics of a SiONC thin film according to Experimental Example 1-1 of the present invention.

[0050] Fig. 18 is a schematic diagram of a structure for measuring CV characteristics of a SiONC thin film according to Experimental Example 1-1 of the present invention.

[0051] Figure 19 is a diagram showing the change in dielectric constant according to the power of plasma used in the manufacturing process of a SiONC thin film according to Experimental Example 1-1 of the present invention.

[0052] Figure 20 is a drawing showing the thickness change according to heat treatment of a SiONC thin film according to Experimental Example 1-1 of the present invention.

[0053] Figure 21 is a drawing showing the composition change according to heat treatment of a SiONC thin film according to Experimental Example 1-1 of the present invention.

[0054] Figure 22 is a drawing showing changes in electrical characteristics according to heat treatment of a SiONC thin film according to Experimental Example 1-1 of the present invention.

[0055] Figure 23 is a drawing showing a change in dielectric constant according to heat treatment of a SiONC thin film according to Experimental Example 1-1 of the present invention.

[0056] Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the attached drawings. However, the technical concept of the present invention is not limited to the embodiments described herein and may be embodied in other forms. Rather, the embodiments introduced herein are provided to ensure that the disclosed content is thorough and complete and to sufficiently convey the spirit of the present invention to those skilled in the art.

[0057] In this specification, when a component is referred to as being on another component, it means that it can be formed directly on the other component, or a third component may be interposed between them. In addition, in the drawings, the thicknesses of films and regions are exaggerated for the purpose of effectively explaining the technical contents.

[0058] Also, although terms such as first, second, and third have been used to describe various components in various embodiments of this specification, these components should not be limited by these terms. These terms are only used to distinguish one component from another. Thus, what is referred to as a first component in one embodiment may be referred to as a second component in another embodiment. Each embodiment described and illustrated herein also includes its complementary embodiments. Also, the term "and / or" has been used herein to mean including at least one of the components listed before and after.

[0059] In the specification, singular expressions include plural expressions unless the context clearly dictates otherwise. In addition, terms such as "comprise" or "have" are intended to specify the presence of a feature, number, step, component, or combination thereof described in the specification, and should not be construed as excluding the presence or addition of one or more other features, numbers, steps, components, or combinations thereof. In addition, the term "connection" is used in the present specification to mean both indirectly connecting multiple components and directly connecting them.

[0060] In addition, when describing the present invention below, if it is determined that a detailed description of a related known function or configuration may unnecessarily obscure the gist of the present invention, the detailed description will be omitted.

[0061]

[0062] FIG. 1 is a flowchart for explaining a method for manufacturing a SiONC thin film according to an embodiment of the present invention, FIG. 2 is a flowchart for specifically explaining step S200 of a method for manufacturing a SiONC thin film according to an embodiment of the present invention, FIG. 3 is a process flowchart for specifically explaining step S200 of a method for manufacturing a SiONC thin film according to an embodiment of the present invention, FIG. 4 is a drawing for explaining a silicon precursor used in a method for manufacturing a SiONC thin film according to an embodiment of the present invention, FIG. 5 is a drawing for explaining an organic precursor used in a method for manufacturing a SiONC thin film according to an embodiment of the present invention, FIG. 6 is a drawing for explaining a formation mechanism of a SiONC thin film according to an embodiment of the present invention, FIG. 7 is a process flowchart for explaining a method for manufacturing a SiONC thin film according to another embodiment of the present invention, FIG. 8 is a drawing for explaining a formation mechanism of a SiONC thin film according to another embodiment of the present invention, FIG. 9 is a process flowchart for explaining a method for manufacturing a SiONC thin film according to another embodiment of the present invention, and FIG. 10 is a drawing for explaining a method for manufacturing a SiONC thin film according to another embodiment of the present invention. This is a drawing for explaining the formation mechanism of a SiONC thin film according to an embodiment.

[0063] Referring to FIGS. 1 to 6, a substrate is prepared (S100). In one embodiment, the substrate may be a silicon semiconductor substrate. Alternatively, in another embodiment, the substrate may be any one of a compound semiconductor substrate, a glass substrate, or a plastic substrate. The type of the substrate is not limited.

[0064] A silicon precursor, an organic precursor, and a plasma are provided on the substrate to manufacture a SiONC thin film in which the silicon precursor, the organic precursor, and the plasma are reacted (S200). For example, the silicon precursor may include TICS (Tetraisocyanatosilane) having a chemical structure as illustrated in FIG. 4. For example, the organic precursor may include PhI (Phloroglucinol) having a chemical structure as illustrated in FIG. 5. For example, the plasma may include any one of nitrogen (N2) plasma, hydrogen (H2) plasma, nitrogen / argon (N2 / Ar) plasma, hydrogen / nitrogen (H2 / N2) plasma, and hydrogen / argon (H2 / Ar) plasma.

[0065] More specifically, the step (S200) of manufacturing the SiONC thin film may include a step (S210) of providing the silicon precursor (TICS) on the substrate, a first purge step (S215), a step (S220) of providing the plasma (N2plasma) on the substrate on which the silicon precursor (TICS) is provided, a second purge step (S225), a step (S230) of providing the organic precursor (Phl) on the substrate on which the plasma (N2plasma) is provided, and a third purge step (S235).

[0066] According to one embodiment, steps S210, S215, S220, S225, S230, and S235 may be defined as a unit process. In addition, the unit process may be repeatedly performed multiple times, and as the unit process is repeated multiple times, the thickness of the SiONC thin film may increase.

[0067] According to one embodiment, the growth rate of the SiONC thin film can be controlled depending on the power of the plasma provided on the substrate. For example, as the power of the plasma provided on the substrate increases, the growth rate of the SiONC thin film can increase.

[0068] According to one embodiment, the content of silicon (Si), oxygen (O), carbon (C), and nitrogen (N) in the SiONC thin film can be controlled depending on the power of the plasma provided on the substrate. For example, as the power of the plasma provided on the substrate increases, the C / Si ratio in the SiONC thin film can increase.

[0069] As described above, when nitrogen plasma (N2plasma) is used to manufacture the SiONC thin film, the step of providing the nitrogen plasma (N2plasma) may be performed before the step of providing the organic precursor (Phl). Accordingly, the SiONC thin film can be easily manufactured, and the thickness of the SiONC thin film can be linearly increased as the unit process is repeated multiple times.

[0070] More specifically, as illustrated in FIG. 6, when nitrogen plasma (N2plasma) is provided on the substrate on which the silicon precursor (TICS) is provided, the ligand (-OCN) of the silicon precursor (TICS) adsorbed on the substrate can be replaced with an amino group (-NH2). Then, when the organic precursor (Phl) is provided on the substrate on which the nitrogen plasma (N2plasma) is provided, the organic precursor (Phl) can bond with the amino group (-NH2). Accordingly, the SiONC thin film can be easily manufactured, and when the unit process is repeated multiple times, a characteristic in which the thickness of the thin film linearly increases, similar to a general molecular layer deposition (MLD) method and an atomic layer deposition (ALD) method, can be exhibited.

[0071] Unlike the above, if the step of providing the organic precursor (Phl) is performed before the step of providing the nitrogen plasma (N2plasma), the SiONC thin film may not be easily manufactured. That is, as shown in FIG. 7, if the step of providing the silicon precursor (TICS) on the substrate, the first purge step, the step of providing the organic precursor (Phl) on the substrate on which the silicon precursor (TICS) is provided, the second purge step, the step of providing the nitrogen plasma (N2plasma) on the substrate on which the organic precursor (Phl) is provided, and the third purge step are performed sequentially, the SiONC thin film may not be manufactured.

[0072] More specifically, as illustrated in Fig. 8, when the organic precursor (Phl) is provided before the nitrogen plasma (N2plasma), the organic precursor (Phl) cannot bind to the ligand (-OCN) of the silicon precursor (TICS), and thus adsorption of the organic precursor (Phl) may not occur. As a result, the SiONC thin film may not be manufactured.

[0073] In addition, as illustrated in FIG. 9, even if the step of providing the nitrogen plasma (N2plasma) is performed before the step of providing the organic precursor (Phl), if the step of providing the nitrogen plasma (N2plasma) is additionally performed after the step of providing the organic precursor (Phl), linear growth of the SiONC thin film thickness may not occur as the number of unit process repetitions increases. That is, if the step of providing the nitrogen plasma (N2plasma) is performed after the step of providing the organic precursor (Phl), linear growth of the SiONC thin film thickness may not occur as the number of unit process repetitions increases.

[0074] More specifically, when the step of providing the nitrogen plasma (N2plasma) is performed after the step of providing the organic precursor (Phl), as illustrated in FIG. 10, the benzene ring of the organic precursor (Phl) is destroyed, and thus carbon fragments on the surface are re-adsorbed, which may cause a problem in that the silicon precursor (TICS) injected in the next unit process is not adsorbed. As a result, linear growth of the SiONC thin film thickness may not occur even if the number of unit process repetitions increases.

[0075] Consequently, a method for manufacturing a SiONC thin film according to an embodiment of the present invention comprises the steps of preparing a substrate, and providing a silicon precursor (e.g., TICS), an organic precursor (e.g., Phl), and plasma (e.g., N2plasma) on the substrate to manufacture a SiONC thin film by a molecular layer deposition method, wherein the plasma (N2plasma) may be provided before the organic precursor (Phl).

[0076] The SiONC thin film manufactured by the above-described method can have a lower dielectric constant value (3.5 k or less) compared to conventional silicon oxide (SiO2) thin films, and thus can be easily applied as an interlayer insulating film for integrated circuits. In addition, the SiONC thin film has high physical and chemical stability, and can have a uniform thickness and composition even over a large area.

[0077] FIG. 11 is a drawing for explaining a device for manufacturing a SiONC thin film according to an embodiment of the present invention.

[0078] Referring to FIG. 11, the apparatus for manufacturing a SiONC thin film according to an embodiment of the present invention may include a main chamber, an RF module (RF), a first precursor supply module (TICS), a second precursor supply module (Phl), a nitrogen supply module (N2), an argon supply module (Ar), and a pump (Rotary Pump). The apparatus for manufacturing a SiONC thin film may further include other components in addition to the above-described components, or some of the above-described components may be omitted.

[0079]

[0080] Above, the SiONC thin film, manufacturing method, and manufacturing apparatus according to an embodiment of the present invention have been described. Below, specific experimental examples and characteristic evaluation results of the SiONC thin film and manufacturing method according to an embodiment of the present invention are described.

[0081] Experimental Example 1: Fabrication of SiONC Thin Film

[0082] SiONC thin films were manufactured on a substrate using plasma-assisted molecular layer deposition (PLM) technology. Three different SiONC thin films were manufactured by varying the process sequence. The three manufactured SiONC thin films are defined as a SiONC thin film according to Experimental Example 1-1, a SiONC thin film according to Experimental Example 1-2, and a SiONC thin film according to Experimental Example 1-3, respectively.

[0083] More specifically, the SiONC thin film according to Experimental Example 1-1 was manufactured at a temperature of 300°C by sequentially performing a step of providing a silicon precursor (TICS) on a substrate, a first purge step, a step of providing nitrogen plasma (N2plasma) on the substrate on which the silicon precursor (TICS) was provided, a second purge step, a step of providing an organic precursor (Phl) on the substrate on which the nitrogen plasma (N2plasma) was provided, and a third purge step, as illustrated in FIG. 3. That is, the SiONC thin film according to Experimental Example 1-1 was manufactured by providing the nitrogen plasma (N2plasma) before the organic precursor (Phl).

[0084] In contrast, the SiONC thin film according to Experimental Example 1-2 was manufactured at a temperature of 300°C by sequentially performing a step of providing a silicon precursor (TICS) on a substrate, a first purge step, a step of providing an organic precursor (Phl) on the substrate on which the silicon precursor (TICS) was provided, a second purge step, a step of providing nitrogen plasma (N2Plasma) on the substrate on which the organic precursor (Phl) was provided, and a third purge step, as illustrated in FIG. 7. That is, the SiONC thin film according to Experimental Example 1-2 was manufactured by providing the organic precursor (Phl) before the nitrogen plasma (N2plasma).

[0085] In contrast, the SiONC thin film according to Experimental Example 1-3 was manufactured at a temperature of 300°C by sequentially performing a step of providing a silicon precursor (TICS) on a substrate, a first purge step, a step of providing nitrogen plasma (N2plasma) on the substrate on which the silicon precursor (TICS) was provided, a second purge step, a step of providing an organic precursor (Phl) on the substrate on which the nitrogen plasma (N2plasma) was provided, a third purge step, a step of providing the nitrogen plasma (N2plasma) on the substrate on which the organic precursor was provided, and a fourth purge step, as illustrated in FIG. 8. That is, the SiONC thin film according to Experimental Example 1-3 was manufactured by providing the nitrogen plasma (N2plasma) before the organic precursor (Phl), but additionally performing a step of providing the nitrogen plasma.

[0086] In addition, as a comparative example, a step of providing a silicon precursor (TICS) on a substrate, a first purge step, a step of providing nitrogen plasma (N2plasma) on the substrate provided with the silicon precursor (TICS), and a second purge step were sequentially performed to manufacture a SiON thin film at a temperature of 300°C.

[0087] The multiple steps for manufacturing each thin film can be defined as a unit process, and the unit process can also be defined as a cycle.

[0088] Thin film type Process sequence Experimental example 1-1 SiONCTICS-N2 plasma-Phl Experimental example 1-2 SiONCTICS-Phl-N2 plasma Experimental example 1-3 SiONCTICS-N2 plasma-Phl-N2 plasma Comparative example SiONTICS-N2 plasma

[0089] Experimental Example 2: Confirming Changes in Characteristics According to Process Sequence

[0090] FIG. 12 is a drawing comparing the growth rate and refractive index of a SiONC thin film according to experimental examples of the present invention and a SiON thin film according to a comparative example.

[0091] Referring to Fig. 12, the growth rate (Growth per cycle, Å / cycle) and refractive index (Refractive index @550 nm) are measured and shown for each of the SiONC thin film (MLD #1) according to Experimental Example 1-1, the SiONC thin film (MLD #2) according to Experimental Example 1-2, the SiONC thin film (MLD #3) according to Experimental Example 1-3, and the SiON thin film according to the comparative example. The measured results are summarized in below.

[0092] Growth rate [Å / cycle] Refractive index (@550 nm) Comparative example (SiON, ALD) 0.12 1.77 Experimental example 1-1 (SiONC, MLD #1) 0.20 1.46 Experimental example 1-2 (SiONC, MLD #2) 0.14 1.42 Experimental example 1-3 (SiONC, MLD #3) 0.23 1.49

[0093] As can be seen in Fig. 12 and , the SiONC thin films according to the above experimental examples have a faster growth rate and a lower refractive index compared to the SiON thin films according to the comparative examples.

[0094] FIG. 13 is a drawing comparing the thickness change according to the number of cycles of a SiONC thin film according to experimental examples of the present invention and a SiON thin film according to a comparative example.

[0095] Referring to FIG. 13, the change in film thickness (nm) according to the increase in the number of cycles is measured and shown for each of the SiONC thin film (MLD SiONC #1) according to Experimental Example 1-1, the SiONC thin film (MLD SiONC #2) according to Experimental Example 1-2, the SiONC thin film (MLD SiONC #3) according to Experimental Example 1-3, and the SiON thin film (ALD SiON) according to the comparative example.

[0096] As can be seen in Fig. 13, the SiON thin film according to the comparative example and the SiONC thin film according to experimental example 1-1 show a linear increase in the film thickness as the number of cycles increases, whereas the SiONC thin films according to experimental examples 1-2 and 1-3 show a parabolic change in the film thickness even as the number of cycles increases.

[0097] That is, when manufacturing a SiONC thin film by a molecular layer deposition method using TICS, Phl, and N2plasma, it can be seen that N2plasma should be provided before Phl, and no additional N2plasma should be provided after Phl.

[0098]

[0099] Experimental Example 3: Confirming Changes in Characteristics According to Plasma Power

[0100] Figure 14 is a diagram showing the growth rate and refractive index according to the power of plasma used in the manufacturing process of a SiONC thin film according to Experimental Example 1-1 of the present invention.

[0101] Referring to Fig. 14, the growth rate (Growth per cycle, Å / cycle) and refractive index (Refractive index @550 nm) according to the power (Plasma Power, W) of N2 plasma used in the manufacturing process of the SiONC thin film according to the above Experimental Example 1-1 are measured and shown. As can be seen in Fig. 14, it can be confirmed that the growth rate of the SiONC thin film also increases as the plasma power increases (100 W -> 300 W). In addition, it can be confirmed that the refractive index is maintained substantially constant despite the increase in plasma power.

[0102] Figure 15 is a drawing showing the composition change according to the power of plasma used in the manufacturing process of a SiONC thin film according to Experimental Example 1-1 of the present invention.

[0103] Referring to Fig. 15, the composition change in the SiONC thin film according to the power (Plasma Power, W) of the N2 plasma used in the manufacturing process of the SiONC thin film according to the above Experimental Example 1-1 is measured and shown. As can be seen in Fig. 15, it can be confirmed that as the plasma power increases (100 W -> 300 W), the C / Si ratio in the SiONC thin film also increases.

[0104] FIG. 16 is a drawing showing changes in electrical characteristics according to the power of plasma used in the manufacturing process of a SiONC thin film according to Experimental Example 1-1 of the present invention, FIG. 17 is a schematic diagram of a structure for measuring IV characteristics of a SiONC thin film according to Experimental Example 1-1 of the present invention, and FIG. 18 is a schematic diagram of a structure for measuring CV characteristics of a SiONC thin film according to Experimental Example 1-1 of the present invention.

[0105] Referring to Fig. 16, the electrical characteristics of the SiONC thin film are measured and shown according to the power (Plasma Power, W) of the N2 plasma used in the manufacturing process of the SiONC thin film according to the above Experimental Example 1-1. The measured results are summarized in below. The Breakdown Voltage was measured through the structure illustrated in Fig. 17, and the Leakage Current was measured through the structure illustrated in Fig. 18.

[0106] CategoryBreakdown Voltage[MV / cm]Leakage current @ 1MV / cm[nA / cm 2 ]200 W8.3 ± 0.513.5 ± 1.1250 W9.4 ± 0.322.4 ± 9.0300 W6.4 ± 0.514.4 ± 2.8

[0107] As can be seen in Fig. 16 and , when the power of N2 plasma is controlled to 250 W, the breakdown voltage and leakage current are the highest.

[0108] Figure 19 is a diagram showing the change in dielectric constant according to the power of plasma used in the manufacturing process of a SiONC thin film according to Experimental Example 1-1 of the present invention.

[0109] Referring to Fig. 19, the hysteresis (V) and dielectric constant (k) of the SiONC thin film are measured and shown according to the power (Plasma Power, W) of the N2 plasma used in the manufacturing process of the SiONC thin film according to the above Experimental Example 1-1. The measured results are summarized in below.

[0110] ClassificationHysteresis [V]Dielectric constant (k)200 W0.30 ± 0.043.46 ± 0.38250 W0.43 ± 0.023.37 ± 0.13300 W0.58 ± 0.083.12 ± 0.27

[0111] As can be seen in Fig. 19 and , it can be confirmed that the SiONC thin film according to the experimental example 1-1 has a dielectric constant value of less than 4 k. In particular, it can be confirmed that the SiONC thin film manufactured through a plasma power of 250 W or more has a low dielectric constant value of less than 3.5 k.

[0112]

[0113] Experimental Example 4: Confirming Changes in Properties Due to Heat Treatment

[0114] Figure 20 is a drawing showing the thickness change according to heat treatment of a SiONC thin film according to Experimental Example 1-1 of the present invention.

[0115] Referring to Fig. 20, the thickness change (Thickness change, %) according to the heat treatment temperature (Annealing Temperature, ℃) of the SiONC thin film according to Experimental Example 1-1 is measured and shown. As can be seen in Fig. 20, it can be confirmed that the SiONC thin film according to Experimental Example 1-1 exhibits a thickness change of 11% or less even at a high heat treatment temperature of 600℃.

[0116] Figure 21 is a drawing showing the composition change according to heat treatment of a SiONC thin film according to Experimental Example 1-1 of the present invention.

[0117] Referring to Fig. 21, the composition change (Atomic concentration, %) according to the heat treatment temperature (Annealing Temperature, ℃) of the SiONC thin film according to Experimental Example 1-1 is measured and shown. As can be confirmed in Fig. 21, it can be confirmed that the composition of the SiONC thin film according to Experimental Example 1-1 is maintained substantially constant despite the heat treatment.

[0118] Figure 22 is a drawing showing changes in electrical characteristics according to heat treatment of a SiONC thin film according to Experimental Example 1-1 of the present invention.

[0119] Referring to Fig. 22, the change in electrical characteristics according to the annealing temperature (℃) of the SiONC thin film according to the experimental example 1-1 is measured and shown. The measurement results are summarized in below. The breakdown voltage was measured through the structure illustrated in Fig. 17, and the leakage current was measured through the structure illustrated in Fig. 18.

[0120] CategoryBreakdown Voltage[MV / cm]Leakage current @ 1MV / cm[nA / cm 2 ]400 ℃5.2 ± 0.312.1 ± 1.08500 ℃8.1 ± 0.413.3 ± 0.95600 ℃6.3 ± 0.116.5 ± 1.72

[0121] As can be seen in Fig. 22 and , it can be confirmed that the SiONC thin film according to the above experimental example 1-1 maintains the breakdown voltage and leakage current substantially constant despite the heat treatment.

[0122] Figure 23 is a drawing showing a change in dielectric constant according to heat treatment of a SiONC thin film according to Experimental Example 1-1 of the present invention.

[0123] Referring to Fig. 23, the change in dielectric constant according to the annealing temperature (℃) of the SiONC thin film according to the experimental example 1-1 is measured and shown. The measurement results are summarized in below.

[0124] ClassificationHysteresis [V]Dielectric constant (k)400 ℃0.21 ± 0.033.43 ± 0.38500 ℃0.25 ± 0.043.32 ± 0.38600 ℃0.19 ± 0.023.21 ± 0.38

[0125] As can be seen in Fig. 23 and , it can be confirmed that the SiONC thin film according to the above experimental example 1-1 maintains the hysteresis and dielectric constant substantially constant despite the heat treatment.

[0126]

[0127] While the present invention has been described in detail using preferred embodiments, the scope of the present invention is not limited to the specific embodiments described above, and should be interpreted in accordance with the appended claims. Furthermore, those skilled in the art will appreciate that numerous modifications and variations are possible without departing from the scope of the present invention.

[0128] The present invention can be used in the semiconductor industry.

Claims

1. Step of preparing the substrate; and A method for manufacturing a SiONC thin film, comprising the step of providing a silicon precursor, an organic precursor, and a plasma on the substrate, and manufacturing a SiONC thin film in which the silicon precursor, the organic precursor, and the plasma are reacted.

2. In paragraph 1, The step of manufacturing the above SiONC thin film is: A step of providing the silicon precursor on the substrate; providing the plasma on the substrate provided with the silicon precursor; and A method for manufacturing a SiONC thin film, comprising the step of providing the organic precursor on the substrate to which the plasma is provided.

3. In paragraph 2, The above plasma includes nitrogen (N2) plasma, As the plasma is provided on the substrate to which the silicon precursor is provided, the ligand of the silicon precursor adsorbed on the substrate is substituted with an amino group, A method for manufacturing a SiONC thin film, comprising providing the organic precursor on the substrate to which the plasma is provided, and bonding the organic precursor with the amino group.

4. In paragraph 2, The step of providing the silicon precursor on the substrate, the step of providing the plasma on the substrate on which the silicon precursor is provided, and the step of providing the organic precursor on the substrate on which the plasma is provided are defined as a unit process. A method for manufacturing a SiONC thin film, wherein the above unit process is repeated multiple times.

5. In paragraph 4, A method for manufacturing a SiONC thin film, comprising linearly increasing the thickness of the SiONC thin film as the above unit process is repeated multiple times.

6. In paragraph 1, A method for manufacturing a SiONC thin film, comprising controlling the growth rate of the SiONC thin film according to the power of the plasma provided on the substrate.

7. In paragraph 1, A method for manufacturing a SiONC thin film, comprising controlling the contents of silicon (Si), oxygen (O), carbon (C), and nitrogen (N) in the SiONC thin film according to the power of the plasma provided on the substrate.

8. In paragraph 1, A method for manufacturing a SiONC thin film, wherein the silicon precursor comprises TICS (Tetraisocyanatosilane).

9. In paragraph 1, A method for manufacturing a SiONC thin film, wherein the organic precursor comprises PhI (Phloroglucinol).

10. In paragraph 1, A method for manufacturing a SiONC thin film, wherein the plasma comprises any one of nitrogen (N2) plasma, hydrogen (H2) plasma, nitrogen / argon (N2 / Ar) plasma, hydrogen / nitrogen (H2 / N2) plasma, and hydrogen / argon (H2 / Ar) plasma.

11. Contains silicon (Si), oxygen (O), nitrogen (N), and carbon (C), A SiONC thin film having a lower dielectric constant value than a silicon oxide (SiO2) thin film.

12. In paragraph 11, A SiONC thin film, comprising a dielectric constant value of 3.5 k or less.

13. In paragraph 11, A SiONC thin film having a thickness change of less than 11% even after heat treatment at 600°C.

14. In paragraph 11, SiONC thin film, including that used as an interlayer insulating film in integrated circuits.

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