Dry etchable organic-inorganic hybrid thin film and manufacturing method therefor

Abstract

A manufacturing method for an organic-inorganic hybrid thin film is provided. The manufacturing method for an organic-inorganic hybrid thin film may comprise the steps of: preparing a substrate; forming, on the substrate, a first inorganic film containing silicon nitride (SiNx, where x>0) by means of plasma-enhanced atomic layer deposition (PEALD); forming, on the first inorganic film, a second inorganic film containing silicon oxide (SiOx, where x>0) by means of PEALD; and forming, on the second inorganic film, an organic film containing tin (Sn) by means of molecular layer deposition (MLD).

Description

Organic-inorganic hybrid thin film capable of dry etching and method for manufacturing the same

[0001] The present invention relates to an organic-inorganic hybrid thin film and a method for manufacturing the same, and more specifically, to an organic-inorganic hybrid thin film capable of dry etching and a method for manufacturing the same.

[0002] Conventional inorganic / organic stacked structures for OLED encapsulation require a thickness of several micrometers or more to block moisture and oxygen, but they have the disadvantage of being vulnerable to contaminants on the underside or step height compensation. To overcome these drawbacks, technologies using organic films of a certain thickness or greater as thick films have been proposed; however, a problem has arisen where flexibility decreases as the thickness of the organic film used as a thick film increases.

[0003] More specifically, physical vapor deposition (PVD) methods, such as evaporation or inkjet, have been primarily used to form organic films in OLED encapsulations with inorganic / organic stacked structures. While these PVD methods offer the advantage of high deposition rates, they suffer from poor step coverage. Furthermore, since PVD performance is achievable only above a certain thickness, a problem of reduced flexibility has arisen as the thickness increases.

[0004] Consequently, Atomic Layer Deposition (ALD) and Molecular Layer Deposition (MLD) have been introduced to maintain film performance while reducing thickness. However, organic thin films (metal alkoxide films) studied in organic-inorganic hybrid structures using ALD and MLD present a problem in that they cannot be dry-etched, requiring complex processes to expose the pads.

[0005] Accordingly, the present invention aims to provide a method for manufacturing a metal alkoxide film using atomic layer deposition and molecular layer deposition, wherein the manufacturing method enables dry etching.

[0006] The technical problem that the present invention aims to solve is to provide an organic-inorganic hybrid thin film and a method for manufacturing the same.

[0007] Another technical problem that the present invention aims to solve is to provide an organic-inorganic hybrid thin film capable of dry etching and a method for manufacturing the same.

[0008] Another technical problem that the present invention aims to solve is to provide an organic-inorganic hybrid thin film using molecular layer deposition and plasma atomic layer deposition, and a method for manufacturing the same.

[0009] The technical problems that the present invention aims to solve are not limited to those described above.

[0010] To solve the technical problems described above, the present invention provides a method for manufacturing an organic-inorganic hybrid thin film.

[0011] According to one embodiment, the method for manufacturing the organic-inorganic hybrid thin film comprises the step of preparing a substrate, and then depositing silicon nitride (SiN) on the substrate by plasma atomic layer deposition (PEALD). x A step of forming a first inorganic material film comprising , x>0), and forming silicon oxide (SiO₂) on the first inorganic material film by plasma atomic layer deposition (PEALD). x The method may include the step of forming a second inorganic material film containing , x>0), and the step of forming an organic material film containing tin (Sn) on the second inorganic material film by molecular layer deposition (MLD).

[0012] According to one embodiment, the step of forming the first inorganic material film may be performed prior to the step of forming the second inorganic material film, and the step of forming the organic material film may be performed after the step of forming the second inorganic material film.

[0013] According to one embodiment, the steps of forming the first inorganic material film, forming the second inorganic material film, and forming the organic material film may be performed sequentially.

[0014] According to one embodiment, the step of forming the first inorganic material film may include the step of providing a first precursor containing silicon (Si) on the substrate, and the step of providing a first reaction material containing nitrogen plasma (N2) on the substrate on which the first precursor is provided.

[0015] According to one embodiment, the step of forming the second inorganic material film may include the step of providing a second precursor containing silicon (Si) on the first inorganic material film, and the step of providing a second reaction material containing oxygen plasma (O2) on the first inorganic material film on which the second precursor is provided.

[0016] According to one embodiment, the first precursor and the second precursor may include an aminosilane-based precursor.

[0017] According to one embodiment, the step of forming the organic material film may include providing a third precursor containing tin (Sn) on the second inorganic material film, and providing a third reaction material containing a benzene ring on the second inorganic material film on which the third precursor is provided.

[0018] According to one embodiment, the third precursor may include TDMASn (Tetrakis(dimethylamino)tin).

[0019] According to one embodiment, the third reaction material may include hydroquinone.

[0020] According to one embodiment, the first inorganic material film, the second inorganic material film, and the organic material film may be formed in-situ.

[0021]

[0022] To solve the technical problems described above, the present invention provides an organic-inorganic hybrid thin film.

[0023] According to one embodiment, the organic-inorganic hybrid thin film is silicon nitride (SiN x A first inorganic material film comprising ( , x>0), disposed on the first inorganic material film, and silicon oxide (SiO x It may include a second inorganic material film comprising , x>0), and an organic material film disposed on the second inorganic material film and comprising tin (Sn), wherein dry etching is possible.

[0024] According to one embodiment, the organic-inorganic hybrid thin film may include a gas capable of dry etching by a mixture of tetrafluorocarbon (CF4) and oxygen (O2).

[0025] According to one embodiment, the first inorganic material film, the second inorganic material film, and the organic material film may be stacked sequentially and repeatedly, wherein the first inorganic material film is disposed on the upper side of the organic material film and the second inorganic material film is disposed on the lower side.

[0026] A method for manufacturing an organic-inorganic hybrid thin film according to an embodiment of the present invention comprises the steps of: preparing a substrate; and depositing silicon nitride (SiN) on the substrate by plasma atomic layer deposition (PEALD). xA step of forming a first inorganic material film comprising , x>0), and forming silicon oxide (SiO₂) on the first inorganic material film by plasma atomic layer deposition (PEALD). x The method may include the step of forming a second inorganic material film containing (x > 0), and the step of forming an organic material film containing tin (Sn) on the second inorganic material film by molecular layer deposition (MLD). Accordingly, an organic-inorganic hybrid thin film capable of dry etching by a mixed gas of tetrafluorocarbon (CF4) and oxygen (O2) may be provided. In addition, since the organic-inorganic hybrid thin film prepared by the above method may have a low moisture permeability, it can be easily applied as a passivation to protect an OLED light-emitting device.

[0027] FIG. 1 is a flowchart illustrating a method for manufacturing an organic-inorganic hybrid thin film according to an embodiment of the present invention.

[0028] FIG. 2 is a schematic diagram illustrating the manufacturing process of an organic-inorganic hybrid thin film according to an embodiment of the present invention.

[0029] FIG. 3 is a diagram for specifically explaining step S200 of the method for manufacturing an organic-inorganic hybrid thin film according to an embodiment of the present invention.

[0030] FIG. 4 is a diagram for specifically explaining step S300 of the method for manufacturing an organic-inorganic hybrid thin film according to an embodiment of the present invention.

[0031] FIG. 5 is a diagram for specifically explaining step S400 of the method for manufacturing an organic-inorganic hybrid thin film according to an embodiment of the present invention.

[0032] FIG. 6 is a diagram illustrating a state in which a first inorganic material film, a second inorganic material film, and an organic material film are alternately and repeatedly stacked according to an embodiment of the present invention.

[0033] FIG. 7 is a drawing illustrating an example of a deposition apparatus used in the process of manufacturing an organic material film according to an embodiment of the present invention.

[0034] FIG. 8 is a drawing illustrating an example of a deposition apparatus used in the manufacturing process of a first inorganic material film and a second inorganic material film according to an embodiment of the present invention.

[0035] FIG. 9 is a diagram comparing the moisture permeability prevention characteristics of material films according to experimental examples and comparative examples of the present invention.

[0036] FIG. 10 is a diagram comparing the flexibility of material films according to experimental examples and comparative examples of the present invention.

[0037] Figures 11 and 12 are diagrams illustrating the effect of O2 plasma on a Tincone material film.

[0038] FIG. 13 is an image of the lower part of a material film according to Comparative Example 3 of the present invention.

[0039] Figure 14 is an image of the upper part of a material film according to Comparative Example 3 of the present invention.

[0040] Figure 15 is an image of the lower part of a material film according to Experimental Example 3 of the present invention.

[0041] Figure 16 is an image of the upper part of a material film according to Experimental Example 3 of the present invention.

[0042] FIG. 17 is a diagram illustrating the dry etching characteristics of a material film according to experimental examples and comparative examples of the present invention.

[0043] 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 ensure that the concept of the present invention is sufficiently conveyed to those skilled in the art.

[0044] In this specification, when a component is described as being on another component, it means that it may be formed directly on the other component or that a third component may be interposed between them. Additionally, in the drawings, the thicknesses of the films and regions are exaggerated for the effective description of the technical content.

[0045] Additionally, although terms such as first, second, third, etc., have been used to describe various components in the various embodiments of this specification, these components should not be limited by such terms. These terms are used merely to distinguish one component from another. Accordingly, what is referred to as the first component in one embodiment may be referred to as the second component in another embodiment. Each embodiment described and illustrated herein also includes its complementary embodiment. Furthermore, in this specification, "and / or" is used to mean including at least one of the components listed before and after it.

[0046] In the specification, singular expressions include plural expressions unless the context clearly indicates otherwise. Furthermore, terms such as "include" or "have" are intended to specify the existence of the features, numbers, steps, components, or combinations thereof described in the specification, and should not be understood as excluding the existence or addition of one or more other features, numbers, steps, components, or combinations thereof. Additionally, in this specification, "connection" is used to include both indirectly connecting multiple components and directly connecting them.

[0047] In addition, in describing the present invention below, if it is determined that a detailed description of related known functions or configurations could unnecessarily obscure the essence of the invention, such detailed description will be omitted.

[0048]

[0049] FIG. 1 is a flowchart for explaining a method for manufacturing an organic-inorganic hybrid thin film according to an embodiment of the present invention, FIG. 2 is a schematic diagram for explaining a process for manufacturing an organic-inorganic hybrid thin film according to an embodiment of the present invention, FIG. 3 is a diagram for specifically explaining step S200 of a method for manufacturing an organic-inorganic hybrid thin film according to an embodiment of the present invention, FIG. 4 is a diagram for specifically explaining step S300 of a method for manufacturing an organic-inorganic hybrid thin film according to an embodiment of the present invention, FIG. 5 is a diagram for specifically explaining step S400 of a method for manufacturing an organic-inorganic hybrid thin film according to an embodiment of the present invention, FIG. 6 is a diagram for explaining a state in which a first inorganic material film, a second inorganic material film, and an organic material film are alternately and repeatedly stacked according to an embodiment of the present invention, FIG. 7 is a diagram for explaining an example of a deposition apparatus used in the process of manufacturing an organic material film according to an embodiment of the present invention, and FIG. 8 is a diagram for explaining an example of a deposition apparatus used in the process of manufacturing a first inorganic material film and a second inorganic material film according to an embodiment of the present invention.

[0050] Referring to FIGS. 1 to 5, a substrate (S) may be prepared (S100). According to one embodiment, the substrate (S) may be a silicon semiconductor substrate. Alternatively, according to another embodiment, the substrate (S) may be any one of a compound semiconductor substrate, a glass substrate, or a plastic substrate. The type of the substrate (S) is not limited.

[0051] Silicon nitride (SiN) is deposited on the above substrate (S) by Plasma Enhanced Atomic Layer Deposition (PEALD). x A first inorganic material film (110) including , x>0) can be formed (S200).

[0052] According to one embodiment, the step of forming the first inorganic material film (110) comprises, as shown in FIG. 3, a first precursor (1 st A step of providing a Precursor (S210), a purge step (S220) for removing unreacted material on the substrate (S), and a first reactant (1) on the substrate (S) provided with the first precursor. st It may include a step (S230) of providing a reactant, and a purge step (S240) for removing unreacted materials on the substrate (S).

[0053] According to one embodiment, the first precursor may include silicon (Si). For example, the first precursor may include an aminosilane-based precursor. According to one embodiment, the first reactant may include nitrogen (N). For example, the first reactant may include nitrogen plasma (N2 plasma).

[0054] The above steps S210, S220, S230, and S240 are first unit processes (1 st It can be defined as a Unit Process. The first unit process can be repeated multiple times. The thickness of the first inorganic material film (110) can be controlled according to the number of times the first unit process is repeated.

[0055] Silicon oxide (SiO₂) is deposited on the first material film (110) by plasma enhanced atomic layer deposition (PEALD). x A second inorganic material film (120) including , x>0) can be formed (S300).

[0056] According to one embodiment, the step of forming the second inorganic material film (120) comprises, as shown in FIG. 4, a second precursor (2 nd A step of providing a precursor (S310), a purge step (S320) for removing unreacted materials on the first inorganic material film (110), and a second reactant (2) on the first inorganic material film (110) provided with the second precursor. nd It may include a step (S330) of providing a reactant, and a purge step (S340) for removing unreacted materials on the first inorganic material film (110).

[0057] According to one embodiment, the second precursor may include silicon (Si). For example, the second precursor may include an aminosilane-based precursor. According to one embodiment, the second reactant may include oxygen (O). For example, the second reactant may include oxygen plasma (O2plasma).

[0058] The above steps S310, S320, S330, and S340 are second unit processes (2 nd It can be defined as a Unit Process. The second unit process can be repeated multiple times. The thickness of the second inorganic material film (120) can be controlled according to the number of times the second unit process is repeated.

[0059] An organic material film (200) containing tin (Sn) can be formed on the second material film (120) by molecular layer deposition (MLD) (S400). For example, the organic material film (200) may contain tin alkoxide.

[0060] According to one embodiment, the step of forming the organic material film (200) comprises, as shown in FIG. 5, a third precursor (3) on the second inorganic material film (120). rd A step of providing a Precursor (S410), a purge step (S420) for removing unreacted materials on the second inorganic material film (120), and a third reactant (3) on the second inorganic material film (120) provided with the third precursor. rd It may include a step (S430) of providing a reactant, and a purge step (S440) for removing unreacted materials on the second inorganic material film (120).

[0061] According to one embodiment, the third precursor may include tin (Sn). For example, the third precursor may include TDMASn (Tetrakis(dimethylamino)tin). According to one embodiment, the third reactant may include a benzene ring. For example, the third reactant may include hydroquinone.

[0062] The above steps S410, S420, S430, and S440 are third unit processes (3 rd It can be defined as a Unit Process. The third unit process can be repeated multiple times. The thickness of the organic material film (200) can be controlled according to the number of times the third unit process is repeated.

[0063] As described above, the step (S200) of forming the first inorganic material film (110) may be performed prior to the step (S300) of forming the second inorganic material film (120), and the step (S400) of forming the organic material film (200) may be performed after the step (S300) of forming the second inorganic material film (120). Additionally, the step (S200) of forming the first inorganic material film (110), the step (S300) of forming the second inorganic material film (120), and the step (S400) of forming the organic material film (200) may be repeated sequentially.

[0064] Accordingly, as illustrated in FIG. 6, the first inorganic material film (110), the second inorganic material film (120), and the organic material film (200) can be stacked sequentially and repeatedly, and the reliability of the organic-inorganic hybrid thin film in which the first inorganic material film (110), the second inorganic material film (120), and the organic material film (200) are stacked sequentially and repeatedly can be improved.

[0065] In contrast, if the second inorganic material film (120) is formed on the organic material film (200) after the formation of the organic material film (200), the thickness of the organic material film (200) may decrease, which may result in a problem of reduced reliability of the organic-inorganic hybrid thin film. More specifically, the organic material film (200) may react with the second reactant (e.g., oxygen plasma) used in the process of forming the second inorganic material film (120), and as a result, the thickness of the organic material film (200) may decrease. However, as described above, when the first inorganic material film (110), the second inorganic material film (120), and the organic material film (200) are formed sequentially and repeatedly, the reaction between the organic material film (200) and the second reactant (e.g., oxygen plasma) can be minimized, so the problem of thickness reduction caused by the reaction of the organic material film (200) with the second reactant (e.g., oxygen plasma) can be minimized.

[0066] The above organic-inorganic hybrid thin film can be dry-etched. More specifically, the above organic-inorganic hybrid thin film can be dry-etched by a mixed gas of tetrafluorocarbon (CF4) and oxygen (O2). In addition, the above organic-inorganic hybrid thin film can have a low moisture permeability. Accordingly, the above organic-inorganic hybrid thin film can be easily applied as a passivation to protect an OLED light-emitting device. Unlike the above, if aluminum alkoxide or indium alkoxide is used as the organic thin film instead of tin alkoxide, there is a problem that it is difficult to apply to an OLED light-emitting device because dry-etching is not possible.

[0067] Referring to FIG. 7, the organic material film (200) can be formed through a molecular layer deposition machine. According to one embodiment, the molecular layer deposition machine may include a reaction chamber (11), a stage heater (12) disposed at the bottom of the reaction chamber (11), a rotary pump (13) for forming a vacuum inside the reaction chamber (11), an inert gas supply module (14) for supplying an inert gas (e.g., Ar gas) into the reaction chamber (11), a precursor supply module (15) for supplying the third precursor into the reaction chamber (10), and a reactant supply module (16) for supplying the third reactant into the reaction chamber (10).

[0068] Referring to FIG. 8, the first inorganic material film (110) and the second inorganic material film (120) can be formed through a plasma atomic layer deposition system. According to one embodiment, the plasma atomic layer deposition apparatus may include a main chamber (21), a load lock chamber (22) connected to the main chamber (21), a shower head (23) disposed above the main chamber (21), an RF module (24) for plasma formation, a precursor supply module (25) for providing the first and second precursors within the main chamber (21), a reactant supply module (26) for providing the first and second reactants within the main chamber (21), a first ATM (27a) connected to the main chamber (21), a second ATM (27b) connected to the load lock chamber, a dry pump (28a) connected to the first ATM, a booster pump (28b) disposed between the first ATM (27a) and the dry pump (28a), and a rotary pump (28c) connected to the second ATM.

[0069] The organic-inorganic hybrid thin film and the method for manufacturing the same according to the embodiments of the present invention have been described above. Below, specific experimental examples and characteristic evaluation results of the organic-inorganic hybrid thin film and the method for manufacturing the same according to the embodiments of the present invention are described.

[0070] Experimental Example 1: Verification of Moisture Permeation Immunity and Flexibility of SiNx / SiO2 / Tincone Hybrid Thin Films

[0071] SiN on a substrate by plasma atomic layer deposition using an aminosilane-based precursor and nitrogen plasma (N2 plasma). x Forms a material film, and SiN x A SiO2 material film is formed on the material film using plasma atomic layer deposition with an aminosilane-based precursor and oxygen plasma (O2 plasma), and a Tincone material film is formed on the SiO2 material film using molecular layer deposition with TDMASn (Tetrakis(dimethylamino)tin) and Hydroquinone to form SiN x A / SiO2 / Tincone organic-inorganic hybrid thin film was fabricated. The fabricated SiN x The / SiO2 / Tincone organic-inorganic hybrid thin film is defined as the material film (Ex 1) according to Experimental Example 1. In addition, SiN x A single film, a SiO2 single film, and a Tincone single film were prepared, and each was defined as the material film according to Comparative Example 1-1 (Cx 1-1), the material film according to Comparative Example 1-2 (Cx 1-2), and the material film according to Comparative Example 1-3 (Cx 1-3).

[0072] Segmentation structure Ex 1SiN x / SiO2 / TinconeCx 1-1SiN x Single film Cx 1-2SiO2 single film Cx 1-3Tincone single film

[0073] FIG. 9 is a diagram comparing the moisture permeability prevention characteristics of material films according to experimental examples and comparative examples of the present invention, and FIG. 10 is a diagram comparing the flexibility of material films according to experimental examples and comparative examples of the present invention.

[0074] Referring to FIG. 9, the water vapor transmission rate (WVTR, g / m²) for each material film according to Experimental Example 1 (Ex 1) and Comparative Examples 1-1 to 1-3 (Cx 1-1, Cx 1-2, Cx 1-3) is 2 (day) is measured and indicated. As can be seen in Fig. 9, it can be confirmed that the moisture permeability of the material film according to Experimental Example 1 (Ex 1) is significantly lower than that of the material films according to Comparative Examples (Cx 1-1, Cx 1-2, Cx 1-3).

[0075] Referring to FIG. 10, the flexibility of each material film according to Experimental Example 1 (Ex 1) and Comparative Examples 1-1 to 1-2 (Cx 1-1, Cx 1-2) is measured and shown. As can be seen in FIG. 10, the material film according to Experimental Example 1 (Ex 1) has a significantly lower WVTR Ratio (After / Before bending) than the material films according to Comparative Examples (Cx 1-1, Cx 1-2).

[0076]

[0077] Experimental Example 2: Verification of the effect of O2 plasma on a Tincone material film

[0078] Tincone film was formed on a substrate using molecular layer deposition with TDMASn (Tetrakis(dimethylamino)tin) and hydroquinone. Subsequently, O2 plasma was applied to the tincone film, and changes in the tincone film were observed.

[0079] Figures 11 and 12 are diagrams illustrating the effect of O2 plasma on a Tincone material film.

[0080] Referring to Figure 11, the thickness change (%) and refractive index (Refractive Index @ 550 nm) of the Tincone material film are measured and shown as the number of cycles of O2 plasma supplied to the Tincone material film increases. As can be seen in Figure 11, it can be observed that the thickness of the Tincone material film decreases as O2 plasma is supplied. Furthermore, it can be observed that while the decrease in thickness becomes more significant with increasing cycles of O2 plasma supply, the refractive index remains practically constant.

[0081] Referring to Figure 12, the change in thickness (%) and refractive index (Refractive Index @ 550 nm) of the Tincone material film are measured and shown as the power (Plasma Power, W) of the O2 plasma supplied to the Tincone material film increases. As can be seen in Figure 12, it can be observed that the thickness of the Tincone material film decreases as O2 plasma is supplied. In addition, it can be observed that when the power of the O2 plasma is relatively low (50W), the decrease in thickness occurs relatively significantly.

[0082]

[0083] Experimental Example 3: Verification of Deposition Uniformity of SiNx / SiO2 / Tincone Hybrid Thin Films

[0084] SiN on a substrate by plasma atomic layer deposition using an aminosilane-based precursor and nitrogen plasma (N2 plasma). x Forms a material film, and SiN xA SiO2 material film is formed on a material film using plasma atomic layer deposition with an aminosilane-based precursor and oxygen plasma (O2 plasma), and a Tincone material film is formed on the SiO2 material film using molecular layer deposition with TDMASn (Tetrakis(dimethylamino)tin) and Hydroquinone to form SiN x Fabricate a / SiO2 / Tincone organic-inorganic hybrid thin film, repeating the fabrication process to obtain SiN x / SiO2 / Tincone / SiN x / SiO2 / Tincone / SiN x / SiO2 / Tincone / SiN x An organic-inorganic hybrid material film with a / SiO2 structure was prepared. The organic-inorganic hybrid material film prepared as described above is defined as the material film according to Experimental Example 3 (Ex 3).

[0085] SiN on a substrate by plasma atomic layer deposition using an aminosilane-based precursor and nitrogen plasma (N2 plasma). x Forms a material film, and SiN x SiN x Fabricate a Tincone organic-inorganic hybrid thin film, repeating the fabrication process to obtain SiN x / Tincone / SiN x / Tincone / SiN x / Tincone / SiN x An organic-inorganic hybrid material film of the structure was prepared. The organic-inorganic hybrid material film prepared as described above is defined as the material film according to Comparative Example 3 (Cx 3).

[0086] Segmentation structure Ex 3SiN x / SiO2 / Tincone / SiN x / SiO2 / Tincone / SiN x / SiO2 / Tincone / SiN x / SiO2Cx 3SiN x / Tincone / SiN x / Tincone / SiN x / Tincone / SiN x

[0087] FIG. 13 is an image of the lower part of a material film according to Comparative Example 3 of the present invention, FIG. 14 is an image of the upper part of a material film according to Comparative Example 3 of the present invention, FIG. 15 is an image of the lower part of a material film according to Experimental Example 3 of the present invention, and FIG. 16 is an image of the upper part of a material film according to Experimental Example 3 of the present invention.

[0088] Referring to FIGS. 13 to 16, the thickness of each material film according to Comparative Example 3 (Cx 3) and Experimental Example 3 (Ex 3) was measured by photographing the bottom and top. In addition, the Step Coverage was calculated using the measured thickness. The thickness measurement results and the calculated Step Coverage are summarized in Tables 3 and 4 below.

[0089] Cx 3Top85 nmBottom91.8 nmStep Coverage92.6%

[0090] Ex 3Top104.7 nmBottom107.6 nmStep Coverage97.3%

[0091] As can be seen in FIGS. 13 to 16 and Tables 3 and 4, the material film (Ex 3) according to Experimental Example 3 can be seen to have high deposition uniformity and high step coverage.

[0092]

[0093] Experimental Example 4: Verification of Dry Etching Characteristics of SiNx / SiO2 / Tincone Hybrid Thin Films

[0094] SiN on a substrate by plasma atomic layer deposition using an aminosilane-based precursor and nitrogen plasma (N2 plasma). x Forms a material film, and SiN x A SiO2 material film is formed on the material film using plasma atomic layer deposition with an aminosilane-based precursor and oxygen plasma (O2 plasma), and a Tincone material film is formed on the SiO2 material film using molecular layer deposition with TDMASn (Tetrakis(dimethylamino)tin) and Hydroquinone to form SiN x A / SiO2 / Tincone organic-inorganic hybrid thin film was fabricated. The fabricated SiN x The / SiO2 / Tincone organic-inorganic hybrid thin film is defined as the material film (Ex 4) according to Experimental Example 4. In addition, SiN x A single film, a SiO2 single film, and a Tincone single film were prepared, and each was defined as the material film according to Comparative Example 4-1 (Cx 4-1), the material film according to Comparative Example 4-2 (Cx 4-2), and the material film according to Comparative Example 4-3 (Cx 4-3).

[0095] Each of the prepared material films (Ex 4, Cx 4-1, Cx 4-2, Cx 4-3) was dry-etched, and the etching rate was measured. More specifically, dry etching was performed by mixing CF4 gas and O2 gas in a 1:1 ratio and exposing the mixture to an environment with a plasma power of 150W and a process pressure of 0.2 torr.

[0096] Segmentation structure Ex 4SiN x / SiO2 / TinconeCx 4-1SiN x Single film Cx 4-2SiO2 single film Cx 4-3Tincone single film

[0097] FIG. 17 is a diagram illustrating the dry etching characteristics of a material film according to experimental examples and comparative examples of the present invention.

[0098] Referring to FIG. 17, the dry etch rate (Dray Etch Rate, A / s) of the material film according to Experimental Example 4 (Ex 4) and the material films according to Comparative Examples 4-1 to 4-3 (Cx 4-1, Cx 4-2, Cx 4-3) is measured and shown. As can be seen in FIG. 17, it can be confirmed that the material film according to Experimental Example 4 (Ex 4) can be dry etched using CF4+ O2 gas, just like the material films according to Comparative Examples 4-1 to 4-3 (Cx 4-1, Cx 4-2, Cx 4-3).

[0099]

[0100] Although the present invention has been described in detail using preferred embodiments, the scope of the invention is not limited to specific embodiments and should be interpreted by the appended claims. Furthermore, those skilled in the art will understand that many modifications and variations are possible without departing from the scope of the invention.

[0101] The present invention can be used in the semiconductor industry.

Claims

1. Step of preparing the substrate; Silicon nitride (SiN) on the above substrate by plasma atomic layer deposition (PEALD) x A step of forming a first inorganic material film including , x>0); Silicon oxide (SiO₂) is deposited on the first inorganic material film by plasma atomic layer deposition (PEALD). x A step of forming a second inorganic material film including , x>0); and A method for manufacturing an organic-inorganic hybrid thin film comprising the step of forming an organic material film containing tin (Sn) on the second inorganic material film by molecular layer deposition (MLD).

2. In Paragraph 1, The step of forming the first inorganic material film is performed prior to the step of forming the second inorganic material film, and A method for manufacturing an organic-inorganic hybrid thin film, comprising the step of forming the organic material film being performed after the step of forming the second inorganic material film.

3. In Paragraph 2, A method for manufacturing an organic-inorganic hybrid thin film comprising the steps of forming the first inorganic material film, forming the second inorganic material film, and forming the organic material film, which are repeated sequentially.

4. In Paragraph 1, The step of forming the first inorganic material film is, A step of providing a first precursor comprising silicon (Si) on the substrate; and A method for manufacturing an organic-inorganic hybrid thin film comprising the step of providing a first reaction material including nitrogen plasma (N2) on the substrate provided with the first precursor.

5. In Paragraph 4, The step of forming the second inorganic material film is, A step of providing a second precursor containing silicon (Si) on the first inorganic material film; and A method for manufacturing an organic-inorganic hybrid thin film comprising the step of providing a second reaction material including oxygen plasma (O2) on the first inorganic material film provided with the second precursor.

6. In Paragraph 5, A method for manufacturing an organic-inorganic hybrid thin film in which the first precursor and the second precursor are aminosilane-based precursors.

7. In Paragraph 1, The step of forming the above organic material film is, A step of providing a third precursor containing tin (Sn) on the second inorganic material film; and A method for manufacturing an organic-inorganic hybrid thin film comprising the step of providing a third reaction material containing a benzene ring on the second inorganic material film provided with the third precursor.

8. In Paragraph 7, The above third precursor is a method for manufacturing an organic-inorganic hybrid thin film containing TDMASn(Tetrakis(dimethylamino)tin).

9. In Paragraph 7, The above third reaction material is a method for manufacturing an organic-inorganic hybrid thin film containing hydroquinone.

10. In Paragraph 1, A method for manufacturing an organic-inorganic hybrid thin film comprising forming the first inorganic material film, the second inorganic material film, and the organic material film in-situ.

11. Silicon Nitride (SiN x A first inorganic material film comprising , x>0); A silicon oxide (SiO₂) is disposed on the first inorganic material film above. x A second inorganic material film comprising , x>0); and The organic material film comprising tin (Sn) is disposed on the second inorganic material film above, and comprises: Organic-inorganic hybrid thin film including one capable of dry etching (dray etch).

12. In Paragraph 11, An organic-inorganic hybrid thin film comprising a mixture of tetrafluorocarbon (CF4) and oxygen (O2) that can be dry-etched.

13. In Paragraph 11, The first inorganic material film, the second inorganic material film, and the organic material film are stacked sequentially and repeatedly, An organic-inorganic hybrid thin film comprising a first inorganic material film disposed on the upper side of the organic material film and a second inorganic material film disposed on the lower side.

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