Method for forming graphene layer and method for manufacturing electronic device using same

Abstract

The present invention provides a method for forming a graphene layer, the method comprising the steps of: spraying hydrocarbon gas on a substrate and forming first plasma; and forming second plasma on the substrate, wherein the step of spraying hydrocarbon gas and forming the first plasma is performed without the supply of hydrogen gas.

Description

Method for forming a graphene layer and method for manufacturing an electronic device using the same

[0001] The present invention relates to a method for forming a graphene layer, and more specifically, to a method for forming a graphene layer by a deposition method.

[0002] Graphene is one of carbon isotopes, in which carbon atoms are present at the vertices of hexagons and form a two-dimensional planar crystal structure in the shape of a widely spread hexagonal honeycomb. Such graphene can have electrical properties and can be used as various components of an electronic device.

[0003] As methods for manufacturing graphene, physical exfoliation method, chemical vapor deposition method, chemical exfoliation method, epitaxial growth method, etc. have been studied, but there is still a limit in manufacturing efficiently up to now.

[0004] The present invention is devised to solve the above-described conventional problems, and an object of the present invention is to provide an efficient method for forming graphene.

[0005] To achieve the above object, the present invention includes the steps of injecting a hydrocarbon gas onto a substrate and forming a first plasma; and forming a second plasma on the substrate, and the step of injecting the hydrocarbon gas and forming the first plasma is performed without supplying a hydrogen gas, and provides a method for forming a graphene layer.

[0006] The process of injecting the hydrocarbon gas and the process of forming the first plasma can be performed simultaneously.

[0007] The step of forming the second plasma may include a process of removing the hydrocarbon gas remaining on the substrate.

[0008] The step of forming the second plasma can be performed while supplying a hydrogen gas onto the substrate.

[0009] The step of forming the second plasma while supplying the hydrogen gas may include a process of removing carbon remaining on the substrate by combining it with the hydrogen gas.

[0010] The step of forming the second plasma may be composed of a process of stopping the injection of the hydrocarbon gas and continuously performing the formation of the first plasma.

[0011] The RF power of the first plasma may be greater than the RF power of the second plasma.

[0012] At least one of the first plasma and the second plasma may be an Ar plasma.

[0013] The hydrocarbon gas is injected through a plurality of first injection holes of the first gas injection unit, the gas for forming the first plasma is injected through a plurality of second injection holes of the second gas injection unit, the hydrocarbon gas is supplied to the plurality of first injection holes through a first gas flow path, the gas for forming the first plasma is supplied to the plurality of second injection holes through a second gas flow path, and the first gas flow path and the second gas flow path may be provided independently of each other.

[0014] It further includes a plurality of third injection holes communicating with the plurality of first injection holes or the plurality of second injection holes, and the hydrocarbon gas may be injected through the first injection holes and the third injection holes, or the gas for forming the first plasma may be injected through the second injection holes and the third injection holes.

[0015] It includes a first electrode and a second electrode to which RF power is applied to have different potentials, and the third injection holes are provided by the space between the first electrode and the second electrode, and plasma may be formed in the plurality of third injection holes.

[0016] A first plate having the plurality of first injection holes and second injection holes, and a second plate spaced apart from the first plate and having a plurality of openings arranged错开 from the first injection holes and second injection holes, the openings may include a first opening formed on the first plate side and a second opening connected to the first opening, having a diameter larger than that of the first opening, and having a length longer than that of the first opening.

[0017] The second opening includes a connection part connected to the first opening, and the connection part may have a diameter increasing from one end connected to the first opening to the other end.

[0018] The present invention also provides a method for forming a graphene layer in a chamber including an upper dome and a lower dome, the method comprising the steps of injecting a hydrocarbon gas into the chamber and forming a first plasma; and forming a second plasma in the chamber, and the step of injecting the hydrocarbon gas and forming the first plasma is performed without hydrogen gas supply.

[0019] The hydrocarbon gas is injected from a first gas injection part provided in the chamber, the gas for forming the first plasma is injected from a second gas injection part provided in the chamber, and the gas for forming the second plasma may be injected from the second gas injection part.

[0020] The first gas injection part includes a first gas flow path, the second gas injection part includes a second gas flow path, and the first gas flow path and the second gas flow path may be separated from each other.

[0021] The present invention also provides a method for manufacturing an electronic device, which includes a process of forming a semiconductor layer on a substrate; and a process of forming an electrode on the substrate, wherein at least one of the process of forming the semiconductor layer and the process of forming the electrode includes a method for forming a graphene layer.

[0022] The electronic device is a solar cell including a first electrode, a photoelectric conversion layer, and a second electrode, and the process of forming at least one of the first electrode and the second electrode may include the above-described method for forming a graphene layer.

[0023] According to the present invention as described above, the graphene layer can be formed through an atomic layer deposition method, so that the film quality of the graphene layer can be improved and the electrical properties of the graphene layer can be improved.

[0024] Therefore, the graphene layer can be utilized as an electrode for a solar cell or a thin film transistor, etc., and can also be utilized as a semiconductor layer such as an active layer of a thin film transistor.

[0025] FIG. 1 is a schematic process flow diagram of a method for forming a graphene layer according to an embodiment of the present invention.

[0026] FIG. 2 is a schematic process flow diagram of a method for forming a graphene layer according to another embodiment of the present invention.

[0027] FIG. 3 is a schematic process flow diagram of a method for forming a graphene layer according to another embodiment of the present invention.

[0028] FIG. 4 is a schematic diagram of a graphene layer forming apparatus according to an embodiment of the present invention.

[0029] FIG. 5 is a schematic diagram of a graphene layer forming apparatus according to another embodiment of the present invention.

[0030] FIG. 6 is a schematic perspective view of a substrate support unit provided in a graphene layer forming apparatus according to another embodiment of the present invention.

[0031] FIG. 7 is a schematic side cross-sectional view of a gas injection unit provided in a graphene layer forming apparatus according to another embodiment of the present invention.

[0032] FIG. 8 is a schematic bottom view of a gas injection unit provided in a graphene forming apparatus according to another embodiment of the present invention.

[0033] FIG. 9 is a schematic diagram of a graphene layer forming apparatus according to another embodiment of the present invention.

[0034] FIG. 10 is a view showing an arrangement structure of openings in a graphene layer forming apparatus according to another embodiment of the present invention.

[0035] FIG. 11 is a view showing a state in which a supply port and openings are formed in a graphene layer forming apparatus according to another embodiment of the present invention.

[0036] FIG. 12 is a schematic diagram of an electronic device according to an embodiment in which a graphene layer according to the present invention is applied, and relates to a solar cell according to an embodiment.

[0037] FIG. 13 is a schematic diagram of an electronic device according to another embodiment in which a graphene layer according to the present invention is applied, and relates to a solar cell according to another embodiment.

[0038] FIG. 14 is a schematic diagram of an electronic device according to another embodiment in which a graphene layer according to the present invention is applied, and relates to a solar cell according to another embodiment.

[0039] Advantages and features of the present invention, and methods for achieving them, will become clear by referring to the embodiments described in detail below together with the accompanying drawings. However, the present invention is not limited to the embodiments disclosed below and will be implemented in various different forms. Only these embodiments are provided to make the disclosure of the present invention complete and to fully inform those with ordinary knowledge in the technical field to which the present invention pertains of the scope of the invention. The present invention is only defined by the scope of the claims.

[0040] The shapes, sizes, ratios, angles, numbers, etc. disclosed in the drawings for explaining the embodiments of the present invention are exemplary, and thus the present invention is not limited to what is shown. Throughout the specification, the same reference numerals refer to the same components. In addition, in describing the present invention, when it is determined that a detailed description of related known technologies may unnecessarily obscure the gist of the present invention, the detailed description thereof is omitted. When terms such as 'comprises', 'has', 'constitutes', etc. are used in this specification, unless 'only' is used, other parts may be added. When a component is expressed in the singular, it includes the case of including a plurality unless otherwise explicitly stated.

[0041] In interpreting a component, even if there is no separate explicit description, it is interpreted as including an error range.

[0042] In the case of a description of a positional relationship, for example, when the positional relationship between two parts is described as 'on', 'above', 'below', 'next to', etc., unless 'directly' or 'immediately' is used, one or more other parts may be located between the two parts.

[0043] [[ID=z10]]In the case of a description of a temporal relationship, for example, when the temporal precedence relationship is described as 'after', 'following', 'next', 'before', etc., unless 'directly' or 'immediately' is used, it may include cases that are not continuous.

[0044] The first, second, etc. are used to describe various components, but these components are not limited by these terms. These terms are only used to distinguish one component from another. Therefore, the first component mentioned below may be the second component within the technical idea of the present invention.

[0045] Each feature of the various embodiments of the present invention can be partially or entirely combined or combined with each other, and various interlocks and drives are technically possible, and each embodiment may be independently implemented with respect to each other or may be implemented together in an associated relationship.

[0046] Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the drawings.

[0047] FIG. 1 is a schematic process flowchart of a method for forming a graphene layer according to an embodiment of the present invention.

[0048] The method for forming a graphene layer according to an embodiment of the present invention can be performed using atomic layer deposition (ALD).

[0049] First, a substrate is loaded into a chamber, a hydrocarbon gas is supplied onto the substrate, and plasma is generated to form a graphene layer (S10). Throughout this specification, the supply of gas includes the injection of gas.

[0050] The hydrocarbon gas is a gas that can be represented as CxHy (where x and y are each greater than 0) including carbon and hydrogen. For example, methane (CH4) gas, ethane (C2H6) gas, propane (C3H8) gas, butane (C4H 40 ) gas, ethylene (C2H4) gas, propene (C3H6) gas, and acetylene (C2H2) gas may be included, but is not necessarily limited thereto.

[0051] The plasma may be made of Ar plasma, but is not necessarily limited thereto. The process of generating the plasma may be performed simultaneously with the process of supplying the hydrocarbon gas.

[0052] No separate hydrogen gas is supplied into the chamber during the process of supplying the hydrocarbon gas and generating the plasma.

[0053] Therefore, a graphene layer composed only of carbon can be formed on the substrate by supplying the hydrocarbon gas and generating plasma without supplying separate hydrogen gas.

[0054] Next, hydrocarbons and carbon remaining on the substrate in the chamber are removed (S20).

[0055] As described above, when the hydrocarbon gas is supplied and plasma is generated without supplying separate hydrogen gas, a graphene layer composed only of carbon is formed on the substrate. However, residues remaining in the form of hydrocarbons may exist on the substrate without breaking the bond between carbon (C) and hydrogen (H). Therefore, a process for removing the residues present on the substrate is necessary.

[0056] The process for removing the residues present on the substrate may be a process of generating plasma in the chamber. For example, by generating Ar plasma in the chamber, residues in the form of hydrocarbons can be removed from the substrate.

[0057] After performing the process (S10) of supplying the hydrocarbon gas and generating plasma to form a graphene layer, by stopping the supply of the hydrocarbon gas and continuously performing the plasma generation, the process (S20) of removing the residues in the form of hydrocarbons can be performed.

[0058] Therefore, the plasma during the graphene formation process (S10) and the plasma during the residue removal process (S20) can be formed identically.

[0059] In addition, in some cases, when the hydrocarbon gas is supplied and plasma is generated without separately supplying hydrogen gas as described above, a graphene layer composed only of carbon is formed on the substrate. However, along with this, after the bond between carbon (C) and hydrogen (H) is broken, carbon may exist in the form of floating substances on the substrate instead of being laminated as a graphene layer on the substrate. Therefore, a process for removing the carbon substance existing in the form of floating substances on the substrate is required.

[0060] The process for removing the carbon substance existing in the form of floating substances on the substrate may be composed of a process of supplying hydrogen gas into the chamber and generating plasma. For example, when hydrogen gas is supplied into the chamber and Ar plasma is generated, the hydrogen can combine with the carbon substance to become a hydrocarbon and can be removed from the substrate.

[0061] After performing the process (S10) of supplying the hydrocarbon gas and generating plasma to form a graphene layer, the supply of the hydrocarbon gas is stopped, and while continuously generating the plasma, hydrogen gas is additionally supplied, thereby performing the process (S20) of removing the carbon substance existing in the form of floating substances.

[0062] The process (S10) of forming the graphene layer and the process (S20) of removing the hydrocarbon and carbon are repeatedly performed.

[0063] FIG. 2 is a schematic process flow diagram of a method for forming a graphene layer according to another embodiment of the present invention.

[0064] First, a substrate is loaded into the chamber, a hydrocarbon gas is supplied onto the substrate, and first plasma is generated to form a graphene layer (S11).

[0065] Since the hydrocarbon gas is the same as described above, repeated description will be omitted.

[0066] The first plasma may be an Ar plasma, but is not necessarily limited thereto. The process of generating the first plasma may be performed simultaneously with the process of supplying the hydrocarbon gas.

[0067] During the process of supplying the hydrocarbon gas and generating the first plasma, no separate hydrogen gas is supplied into the chamber.

[0068] Therefore, by supplying the hydrocarbon gas and generating the first plasma without supplying a separate hydrogen gas, a graphene layer composed only of carbon can be formed on the substrate.

[0069] Next, a second plasma is generated in the chamber to remove the hydrocarbon remaining on the substrate (S21).

[0070] The second plasma may be an Ar plasma, but is not necessarily limited thereto.

[0071] After performing the process (S11) of supplying the hydrocarbon gas and generating the first plasma to form the graphene layer, the supply of the hydrocarbon gas is stopped and the generation of the first plasma is continuously performed, thereby performing the process (S21) of removing the residue in the form of hydrocarbon.

[0072] Therefore, the first plasma during the graphene formation process (S11) and the second plasma during the residue removal process (S21) can be formed identically.

[0073] However, the first RF power for forming the first plasma and the second RF power for forming the second plasma may be different. Specifically, the first RF power may be greater than the second RF power.

[0074] The process (S11) of forming the graphene layer and the process (S21) of removing the hydrocarbon are repeatedly performed.

[0075] FIG. 3 is a schematic process flow diagram of a graphene layer forming method according to another embodiment of the present invention.

[0076] First, a substrate is loaded into a chamber, a hydrocarbon gas is supplied onto the substrate, and a first plasma is generated to form a graphene layer (S12).

[0077] This process (S12) is the same as the S11 process of FIG. 2 described above, so a repeated description will be omitted.

[0078] Next, hydrogen is supplied into the chamber, a second plasma is generated to remove the hydrocarbon remaining on the substrate, and at the same time, the carbon remaining on the substrate is combined with hydrogen and removed (S22).

[0079] The second plasma may be an Ar plasma, but is not necessarily limited thereto.

[0080] After performing the process (S12) of supplying the hydrocarbon gas and generating the first plasma to form a graphene layer, the supply of the hydrocarbon gas is stopped, and while additionally supplying hydrogen gas, the generation of the first plasma is continuously performed, thereby removing the hydrocarbon remaining on the substrate and combining and removing the carbon remaining on the substrate with hydrogen, and the process (S22) can be performed.

[0081] Therefore, the first plasma during the graphene formation process (S12) and the second plasma during the residue removal process (S22) can be formed identically.

[0082] However, the first RF power for forming the first plasma and the second RF power for forming the second plasma may be different. Specifically, the first RF power may be greater than the second RF power.

[0083] The process of forming the graphene layer (S12) and the process of removing the remaining hydrocarbons and combining and removing the remaining carbon with hydrogen (S22) are repeatedly performed.

[0084] FIG. 4 is a schematic diagram of a graphene layer forming apparatus according to an embodiment of the present invention.

[0085] Referring to FIG. 2, the substrate processing apparatus 1 according to the first embodiment may include a chamber 2. Inside the chamber 2, a processing process for the substrate 100 may be performed. The chamber 2 may include an upper dome 2a and a lower dome 2b.

[0086] The upper dome 2a may be disposed above the lower dome 2b. The upper dome 2a may block the upper side of the processing space PS. The processing space PS may be a space disposed inside the chamber 2. A processing process for the substrate 100 may be performed in the processing space PS. The upper dome 2a may be formed of quartz. The upper dome 2a may be formed in a dome shape that is entirely open at the bottom.

[0087] The lower dome 2b may be disposed below the upper dome 2a. The lower dome 2b may block the lower side of the processing space PS. The lower dome 2b may be formed of quartz. The lower dome 2b may be formed in an open-top shape. An exhaust unit 221 for exhausting gas, impurities, etc. from the processing space PS may be provided in the lower dome 2b. The exhaust unit 221 may include a turbo molecular pump (TMP) 222. The chamber 2 including the turbo molecular pump 222 may be adjusted to a high vacuum pressure of 10 mTorr or more and 50 mTorr or less.

[0088] The chamber (2) may include a heating unit (23). The heating unit (23) may heat the substrate (100) located inside the chamber (2). The heating unit (23) may also heat the substrate (100) by heating the processing space (PS). The heating unit (23) may include a plurality of lamp heaters. The lamp heaters may heat the substrate (100) by emitting heating light toward the processing space (PS). The heating unit (23) may be disposed outside the lower dome (2b). The heating unit (23) may also be disposed outside the upper dome (2a).

[0089] The chamber (2) may include a chamber body (2c). The chamber body (2c) may be disposed between the upper dome (2a) and the lower dome (2b). The upper dome (2a) and the lower dome (2b) may be coupled to the chamber body (2c) respectively.

[0090] A substrate support (3) may be installed in the chamber (2). The substrate support (3) may support one or more substrates (100). A processing process for the substrate (100) may be performed while the substrate (100) is supported by the substrate support (3) and located in the processing space (PS). A driving unit (30a) may be coupled to the substrate support (3). The driving unit (30a) may raise and lower the substrate support (3). The driving unit (30a) may also rotate the substrate support (3).

[0091] A gas injection unit (4) may be installed in the chamber (2). The gas injection unit (4) may inject gas. A processing process for the substrate (100) may be performed using the gas injected by the gas injection unit (4). The gas injection unit (4) may inject gas into the processing space (PS). The gas injection unit (4) may inject gas toward the substrate support (3).

[0092] The gas injection unit (4) may include a first gas injection unit (41) and a second gas injection unit (42). The first gas injection unit (41) can inject a first gas. The second gas injection unit (42) can inject a second gas. The first gas and the second gas may be different types of gases. The first gas may include a hydrocarbon gas, and the second gas may include an Ar gas. The first gas injection unit (41) and the second gas injection unit (42) may inject gases toward different parts of the substrate support unit (3). The first gas injection unit (41) may include a first gas flow path for the first gas to be injected. The second gas injection unit (42) may include a second gas flow path for the second gas to be injected. In this case, a gas injection unit (4) having the first gas flow path and the second gas flow path may be provided above the chamber (2). The first gas flow path and the second gas flow path are spatially separated so that the first gas and the second gas are not mixed until they are injected into the processing space (PS).

[0093] The first gas injection unit (41) may be connected to the first supply unit (51). The first supply unit (51) stores the first gas and can supply the first gas to the first gas injection unit (41). The first gas injection unit (41) may be connected to the first filling tank (52). The first filling tank (52) fills the first gas and can temporarily inject the first gas into the processing space (PS) through the first gas injection unit (41). The first filling tank (52) may be connected to each of the first supply unit (51) and the first gas injection unit (41) between the first supply unit (51) and the first gas injection unit (41). The first supply unit (51) may also supply a purge gas for purging the processing space (PS), a gas for forming plasma in the processing space (PS), etc. to the first gas injection unit (41).

[0094] The second gas injection unit (42) may be connected to the second supply unit (53). The second supply unit (53) stores the second gas and can supply the second gas to the second gas injection unit (42). The second gas injection unit (42) may be connected to the second filling tank (54). The second filling tank (54) fills the second gas and can temporarily inject the second gas into the processing space (PS) through the second gas injection unit (42). The second filling tank (54) may be connected to each of the second supply unit (53) and the second gas injection unit (42) between the second supply unit (53) and the second gas injection unit (42). The second supply unit (53) may also supply a purge gas for purging the processing space (PS), a gas for forming plasma in the processing space (PS), etc. to the second gas injection unit (42).

[0095] An antenna (40) may be installed in the chamber (2). The antenna (40) may be used to form plasma in the processing space (PS). The antenna (40) may include a coil that induces an electric field inside the chamber (2) for plasma formation. The antenna (40) may be disposed outside the upper dome (2a). The antenna (40) may be coupled to the upper surface of the upper dome (2a).

[0096] The antenna (40) may be connected to a power supply device (400). The power supply device (400) may apply RF (Radio Frequency) power to the antenna (40). Accordingly, the antenna (40) may form plasma inside the chamber (2). In this case, the gas injection unit (4) may also inject a gas for forming plasma into the processing space (PS). For example, the gas injection unit (4) may inject argon (Ar).

[0097] FIG. 5 is a schematic diagram of a graphene layer forming apparatus according to another embodiment of the present invention.

[0098] As can be seen in FIG. 5, a graphene layer forming apparatus (1) according to another embodiment of the present invention includes a chamber (2), a substrate support unit (3), a gas injection unit (4), a gas storage unit (5), and a power supply unit (6).

[0099] The chamber (2) provides a processing space (PS) for the graphene layer forming process.

[0100] An exhaust port (not shown) for exhausting the process gas remaining from the processing space (PS) may be coupled to the chamber (2). In addition, inside the chamber (2), for example, a heater (not shown) for adjusting the temperature inside the chamber (2) may be additionally installed on the substrate support unit (3).

[0101] The substrate support unit (3) may be coupled to the chamber (2) inside the chamber (2).

[0102] The substrate support part (3) supports the substrate (10) on which the graphene layer is formed. The substrate support part (3) can support one or more substrates (10), and accordingly, a graphene layer can be formed on a plurality of substrates (10) at once.

[0103] The gas injection part (4) is disposed inside the chamber (2) to face the substrate support part (3) and injects gas toward the substrate support part (3). For example, the gas injection part (4) can be disposed above the substrate support part (3) and inject process gas downward toward the substrate support part (3). The processing space (PS) is provided between the gas injection part (4) and the substrate support part (3). Throughout this specification, gas supply includes gas injection.

[0104] The gas injection part (4) can be coupled to a chamber lead (not shown). The chamber lead can be coupled to the chamber (2) to cover the upper part of the chamber (2).

[0105] The gas injection part (4) can be connected to the gas storage part (5). Accordingly, the gas injection part (4) can receive process gas from the gas storage part (5) and inject the received process gas toward the substrate support part (3).

[0106] The gas injection part (4) can be connected to the power supply part (6). Accordingly, plasma can be generated inside the chamber (2) using the plasma power supplied from the power supply part (6).

[0107] The gas injection part (4) can include a first gas injection part (ma) and a second gas injection part (4b).

[0108] The first gas injection unit (4a) is for injecting the first gas. One side of the first gas injection unit (4a) is connected to the gas storage unit (5) through a pipe, a hose, or the like, and the other side of the first gas injection unit (4a) may communicate with the processing space (PS). Accordingly, the first gas supplied from the gas storage unit (5) can be injected into the processing space (PS) after moving along the first gas flow path of the first gas injection unit (4a).

[0109] The first gas injection unit (4a) can function as a passage for the first gas to flow and also as an injection port for injecting the first gas into the processing space (PS).

[0110] The second gas injection unit (4b) is for injecting the second gas. The second gas and the first gas may be different gases. For example, the first gas may include a hydrocarbon gas, and the second gas may include an Ar gas.

[0111] One side of the second gas injection unit (4b) is connected to the gas storage unit (5) through a pipe, a hose, or the like, and the other side of the second gas injection unit (4b) may communicate with the processing space (PS). Accordingly, the second gas supplied from the gas storage unit (5) can be injected into the processing space (PS) after moving along the second gas flow path of the second gas injection unit (4b).

[0112] The second gas injection unit (4b) can function as a passage for the second gas to flow and also as an injection port for injecting the second gas into the processing space (PS).

[0113] The first gas path of the first gas injection unit (4a) and the second gas path of the second gas injection unit (4b) may be arranged to be spatially separated from each other. Accordingly, the first gas supplied from the gas storage unit (5) to the first gas injection unit (4a) can be injected into the processing space (PS) without passing through the second gas path of the second gas injection unit (4b). Similarly, the second gas supplied from the gas storage unit (5) to the second gas injection unit (4b) can be injected into the processing space (PS) without passing through the first gas path of the first gas injection unit (4a).

[0114] In this way, according to one embodiment of the present invention, since the first gas path of the first gas injection unit (4a) and the second gas path of the second gas injection unit (4b) are arranged to be spatially separated from each other, the first gas and the second gas cannot mix with each other within the first gas injection unit (4a) and the second gas injection unit (4b).

[0115] The first gas injection unit (4a) and the second gas injection unit (4b) can inject gas toward different areas in the processing space (PS).

[0116] The above gas storage unit (5) stores process gas and supplies the stored process gas to the gas injection unit (4). Although one gas storage unit (5) is shown in the drawing, a plurality of gas storage units (5) may be provided.

[0117] Meanwhile, although not shown, a third gas injection unit of a third gas injection unit is additionally provided so as to be spatially separated from the first gas path of the first gas injection unit (4a) and the second gas path of the second gas injection unit (4b), so that a third gas including hydrogen gas can be injected into the processing space (PS) from the third gas injection unit.

[0118] The above power supply unit (6) can apply plasma power to the gas injection unit (4). For example, the plasma power supply can be RF power.

[0119] Figure 6 is a schematic perspective view of a substrate support provided in a graphene layer forming device according to another embodiment of the present invention.

[0120] As can be seen in Fig. 6, the substrate support member (3) may include a support surface (31) that supports a plurality of substrates (10). The support surface (31) may be a surface facing the gas injection member (reference numeral 4 in Fig. 5).

[0121] While the graphene layer formation process is in progress, the substrate support member (3) can be rotated around the central axis (30).

[0122] The above substrate support member (3) may include a central region (32) and an outer region (33) arranged outside the central region (32).

[0123] When the central region (32) is formed in a circular shape, the outer region (33) can be formed in a circular ring shape surrounding the central region (32).

[0124] The plurality of substrates (10) may be arranged to be spaced apart from each other along the outer region (33). At this time, the plurality of substrates (10) may be spaced apart from each other at the same angle with respect to the central axis (30) of the substrate support member (3) in the outer region (33).

[0125] The above plurality of substrates (10) may be arranged in the outer region (33) and may not be arranged in the central region (32), but this is not necessarily limited to the case, and at least one substrate (10) may be arranged in the central region (32).

[0126] Figure 7 is a schematic cross-sectional side view of a gas injection unit provided in a graphene layer forming device according to another embodiment of the present invention.

[0127] As can be seen in Fig. 7, the gas injection unit (4) may include a first electrode (43) and a second electrode (44).

[0128] The first electrode (43) and the second electrode (44) may be arranged in a vertical direction. The first electrode (43) is positioned above the second electrode (44), and therefore, the first electrode (43) may be an upper electrode, and the second electrode (44) may be a lower electrode. In addition, the first electrode (43) may be grounded and function as a ground electrode.

[0129] The first electrode (43) may include a first gas injection unit (4a) and a second gas injection unit (4b). Accordingly, the first electrode (43) may inject a first gas through the first gas injection unit (4a) and a second gas through the second gas injection unit (4b). The first gas injection unit (4a) and the second gas injection unit (4b) may be arranged to be spatially separated from each other within the first electrode (43).

[0130] The first gas injection unit (4a) may include a first connection hole (41a) connected to the gas storage unit (reference numeral 5 in FIG. 5) and a plurality of first injection holes (42a) connected to the first connection hole (41a). The first connection hole (41a) and the first injection holes (42a) may be formed inside the first electrode (43). One side of the first injection hole (42a) may be connected to the first connection hole (41a), and the other side of the first injection hole (42a) may be connected to the processing space (PS). Accordingly, the first gas supplied from the gas storage unit (reference numeral 5 in FIG. 5) may move along the first connection hole (41a) and then be injected into the processing space (PS) through the first injection holes (42a). The movement path of the first gas from the above gas storage unit (reference numeral 5 in FIG. 5) to the plurality of first injection holes (42a) can become the first gas path.

[0131] The second gas injection unit (4b) may include a second connection hole (41b) connected to the gas storage unit (reference numeral 5 in FIG. 5) and a plurality of second injection holes (42b) connected to the second connection hole (41b). The second connection hole (41b) and the second injection holes (42b) may be formed inside the first electrode (43). One side of the second injection holes (42b) may be connected to the second connection hole (41b), and the other side of the second injection holes (42b) may be connected to the processing space (PS). Accordingly, the second gas supplied from the gas storage unit (reference numeral 5 in FIG. 5) may move along the second connection hole (41b) and then be injected into the processing space (PS) through the second injection holes (42b). The movement path of the second gas from the above gas storage unit (reference numeral 5 in FIG. 5) to the plurality of second injection holes (42b) can become a second gas path.

[0132] The second connecting hole (41b) and the second injection holes (42b) are separated from the first connecting hole (41a) and the first injection holes (42a). Therefore, the first gas path is provided independently from the second gas path.

[0133] The first electrode (43) may include a base member (43a) extending in a horizontal direction and a protruding member (43b) extending downwardly from the lower surface of the base member (43a).

[0134] The above protruding member (43b) can extend from the lower surface of the base member (43a) to the processing space (PS). A plurality of such protruding members (43b) can be provided, and the plurality of protruding members (43b) can be arranged to be spaced apart from each other.

[0135] Each of the first connecting hole (41a), the second connecting hole (41b), and the second injection hole (42b) may be provided in the base member (43a).

[0136] At this time, the first connecting hole (41a) and the second connecting hole (41b) can extend in the extension direction of the base member (43a), specifically, in the horizontal direction. The first connecting hole (41a) and the second connecting hole (41b) are separated from each other. The second injection hole (42b) can extend in the vertical direction from the second connecting hole (41b).

[0137] The first injection hole (42a) may be provided to extend from the base member (43a) to the protruding member (43b). The first injection hole (42a) may be provided to vertically penetrate the inside of the protruding member (43b).

[0138] The second electrode (44) may have a hole (44a) into which the protruding member (43b) may be inserted. The hole (44a) may be formed to penetrate the second electrode (44) in a vertical direction. The hole (44a) may function as a passage for passing gas discharged from the first electrode (43). The holes (44a) may correspond one-to-one with the protruding members (43b) in the same number. Accordingly, the plurality of protruding members (43b) may be inserted one-to-one into the plurality of holes (44a). To this end, the diameter of the hole (44a) is formed to be larger than the diameter of the protruding member (43b).

[0139] When the protruding member (43b) of the first electrode (43) is inserted into the hole (44a) of the second electrode (44), the height of the lower surface of the protruding member (43b) and the height of the lower surface of the second electrode (44) may be the same.

[0140] The lower surface of the base member (43a) of the first electrode (43) and the upper surface of the second electrode (44) are spaced apart from each other, and the spaced apart space is connected to the second injection hole (42b).

[0141] In addition, when the protruding member (43b) of the first electrode (43) is inserted into the hole (44a) of the second electrode (44), the outer surface of the protruding member (43b) is spaced apart from the inner surface of the second electrode (44) surrounding the hole (44a). Accordingly, the hole (44a) area between the outer surface of the protruding member (43b) and the inner surface of the second electrode (44), in other words, the hole (44a) area corresponding to the outer space of the protruding member (43b), is in communication with the space between the lower surface of the base member (43a) of the first electrode (43) and the upper surface of the second electrode (44).

[0142] In addition, the hole (44a) area corresponding to the outer space of the protruding member (43b) is connected to the processing space (PS).

[0143] Accordingly, the second gas discharged from the second injection hole (42b) can be injected into the processing space (PS) through the space between the first electrode (43) and the second electrode (44). Specifically, the second gas discharged from the second injection hole (42b) can pass through the space between the lower surface of the base member (43a) of the first electrode (43) and the upper surface of the second electrode (44), pass through the hole (44a) area corresponding to the outer space of the protruding member (43b), and be injected toward the processing space (PS). That is, the second gas discharged from the second injection hole (42b) can pass through the space between the lower surface of the base member (43a) and the upper surface of the second electrode (44), and then pass through the hole (44a) provided in the second electrode (44) along the outer space of the protruding member (43b) and be injected toward the lower side of the hole (44a). Accordingly, the portion of the hole (44a) corresponding to the space between the outer side of the protruding member (43b) and the second electrode (44) becomes the third injection hole, so that the second gas can be injected into the processing space (PS) through the third injection hole via the second injection hole (42b).

[0144] Meanwhile, the first gas may be injected into the processing space (PS) through the third injection hole via the second injection hole (42b), and the second gas may be injected into the processing space (PS) through the first injection hole (42a).

[0145] Additionally, an insulating member (not shown) may be additionally placed between the second electrode (44) and the first electrode (43) to partially insulate them.

[0146] RF power may be applied to the second electrode (44). When the first electrode (43) is grounded, the RF power may be applied to the second electrode (44) to generate plasma. Plasma may be generated in the space between the first electrode (43) and the second electrode (44). More specifically, plasma may be generated in the space between the lower surface of the base member (43a) of the first electrode (43) and the upper surface of the second electrode (44) and within the hole (44a) provided in the second electrode (44), and accordingly, the process gas may be activated using the plasma, and the activated process gas may be injected into the processing space (PS).

[0147] As described above, plasma can be formed by grounding the first electrode (43) and applying RF power to the second electrode (44), but the present invention is not limited thereto, and plasma can also be formed by applying RF power to the first electrode (43) and grounding the second electrode (44). In addition, plasma can be formed by applying a positive (+) voltage to one of the first electrode (43) and the second electrode (44) and connecting a negative (-) electrode to the other electrode.

[0148] In addition, as described above, since the first electrode (43) has a protruding member (43b), the lower surface of the first electrode (43) is not flat and its height varies depending on the position. However, the first electrode (43) is not limited thereto and may not have the protruding member (43b). That is, the first electrode (43) may only have the base member (43a) and may not have the protruding member (43b) extending downward from the base member (43a). In this case, the lower surface of the first electrode (43) may have a flat shape.

[0149] When the lower surface of the first electrode (43) and the upper surface of the second electrode (44) are each formed flat, some of the holes (44a) are arranged at positions corresponding to the first gas injection portion (4a) so that the first gas injected from the first gas injection portion (4a) can pass through them, and the rest of the holes (44a) are arranged at positions corresponding to the second gas injection portion (4b) so that the second gas injected from the second gas injection portion (4b) can pass through them.

[0150] Although not shown, the second electrode (44) may have a smaller number of holes (44a) formed than the sum of the number of first injection holes (42a) of the first gas injection unit (4a) and the number of second injection holes (42b) of the second gas injection unit (4b).

[0151] Figure 8 is a schematic bottom view of a gas injection unit provided in a graphene formation device according to another embodiment of the present invention.

[0152] Referring to Fig. 8, the hole (44a) and the protruding member (43b) are formed in the entire area of ​​the lower surface of the gas injection part (4), and thus, gas can be injected into the entire central area (reference numeral 32 of Fig. 6) and outer area (reference numeral 33 of Fig. 6) of the substrate support part (reference numeral 3 of Fig. 6).

[0153] FIG. 9 is a schematic diagram of a graphene layer forming device according to another embodiment of the present invention, FIG. 10 is a diagram showing the arrangement structure of an opening in a graphene layer forming device according to another embodiment of the present invention, and FIG. 11 is a diagram showing how a supply port and an opening are formed in a graphene layer forming device according to another embodiment of the present invention.

[0154] Referring to FIGS. 9 to 11, a graphene layer forming apparatus according to another embodiment of the present invention includes a chamber (10), a substrate support unit (20) provided within the chamber (10) and installed within the chamber (10) to support a substrate (S) provided within the chamber (10), a gas supply unit (300) installed within the chamber (10) to spray gas to the substrate support unit (20), and a power supply unit (400) connected to the gas supply unit (300) to supply power to the gas supply unit (300) to generate plasma within the chamber (10). The graphene layer forming apparatus may further include a control unit (not shown) for controlling the power supply unit (400).

[0155] The chamber (10) provides a predetermined reaction space and maintains the reaction space airtight. The chamber (10) may include a body (14) having a predetermined reaction space, including a circular or rectangular flat surface and a side wall extending upward from the flat surface, and a lid (12) positioned on the body (14) to maintain the reaction space airtight. However, the chamber (10) is not limited thereto and may be manufactured in various shapes corresponding to the shape of the substrate (S).

[0156] An exhaust port (not shown) may be formed in a predetermined area at the bottom of the chamber (10), and an exhaust pipe (not shown) connected to the exhaust port may be provided on the outside of the chamber (10). In addition, the exhaust pipe may be connected to an exhaust device (not shown). A vacuum pump such as a turbo molecular pump may be used as the exhaust device. Therefore, the inside of the chamber (10) may be vacuum-sucked to a predetermined reduced pressure atmosphere, for example, a predetermined pressure of 0.1 mTorr or less, by the exhaust device. The exhaust pipe may be installed not only on the lower surface of the chamber (10) but also on the side surface of the chamber (10). In addition, a plurality of exhaust pipes and corresponding exhaust devices may be further installed to reduce the exhaust time.

[0157] The substrate (S) provided into the chamber (10) for the graphene formation process can be mounted on the substrate support member (20). The substrate support member (20) can be equipped with, for example, an electrostatic chuck to hold the substrate (S) by electrostatic force so that the substrate (S) can be mounted and supported, or the substrate (S) can be supported by vacuum suction or mechanical force.

[0158] The substrate support member (20) may be provided in a shape corresponding to the shape of the substrate (S), for example, a circle or a square. The substrate support member (20) may include a substrate support member (22) on which the substrate (S) is mounted, and an elevator (24) disposed below the substrate support member (22) to move the substrate support member (22) up and down. Here, the substrate support member (22) may be manufactured to be larger than the substrate (S), and the elevator (24) may be provided to support at least one area, for example, the center, of the substrate support member (22), so that when the substrate (S) is mounted on the substrate support member (22), the substrate support member (22) may be moved closer to the gas injection device (300). A heater (not shown) may be installed inside the substrate support member (22). The above heater generates heat to a predetermined temperature to heat the substrate support (22) and the substrate (S) mounted on the substrate support (22) so that a graphene layer is uniformly deposited on the substrate (S).

[0159] A gas supply unit may be installed in the lid (12) of the chamber (10). The gas supply unit may be installed to penetrate the lid (12) of the chamber (10), and may include a first gas supply unit (110) and a second gas supply unit (120) to provide a first gas and a second gas to the gas supply unit (300), respectively. The first gas may include hydrocarbon gas, and the second gas may include Ar gas. However, the present invention is not limited thereto, and the first gas may include Ar gas and the second gas may include hydrocarbon gas. In addition, at least one of the first gas and the second gas may include a purge gas. The first gas supply unit (110) and the second gas supply unit (120) may not be configured to provide only one gas, but may be configured to provide a plurality of gases simultaneously.

[0160] The gas supply unit (300) is installed inside the chamber (10), for example, on the lower surface of the lid (12), and a first gas path for spraying a first gas onto a substrate and a second gas path for spraying a second gas onto the substrate are formed inside the gas supply unit (300). The first gas path and the second gas path are provided to be independent and separate from each other, so that the first gas and the second gas can be supplied onto the substrate separately without being mixed within the gas supply unit (300).

[0161] More specifically, the gas supply unit (300) includes a first plate (310, 320) having a first gas injection hole (312) capable of supplying a first gas and a second gas injection hole (322) capable of supplying a second gas, and a second plate (330) having a plurality of openings (332) that are electrically insulated from the first plate (310, 320), spaced apart from the first plate (310, 320), and arranged in an alternating manner with the first gas injection hole (312) and the second gas injection hole (322). Here, the first gas injection hole (312) is connected to a first gas flow path, and the second gas injection hole (322) is connected to a second gas flow path.

[0162] The first plate (310, 320) can act as a first electrode for generating plasma in a reaction space, and therefore, the first plate (310, 320) can be referred to as a first electrode.

[0163] The above first plate (310, 320) may include an upper frame (310) and a lower frame (320).

[0164] The upper frame (310) can be detachably attached to the lower surface of the lead (12), and at the same time, a portion of the upper surface thereof, for example, a central portion of the upper surface thereof, can be spaced apart from the lower surface of the lead (12) by a predetermined distance. Accordingly, the first gas provided from the first gas providing unit (110) can diffuse in the space between the upper surface of the upper frame (310) and the lower surface of the lead (12).

[0165] The lower frame (320) is installed at a certain distance from the lower surface of the upper frame (310). Accordingly, the second gas provided from the second gas providing unit (120) can diffuse in the space between the upper surface of the lower frame (320) and the lower surface of the upper frame (310).

[0166] The upper frame (310) and the lower frame (320) can be connected by a first sealing member (350) that seals their outer surfaces, thereby sealing their internal space. The first sealing member (350) may be formed of an insulating material for electrically insulating the upper frame (310) and the lower frame (320) from each other, or conversely, may be formed of a conductive material for electrically connecting the upper frame (310) and the lower frame (320) to each other.

[0167] The first gas path may be formed so that the first gas provided from the first gas providing unit (110) diffuses in the space between the lower surface of the lid (12) and the upper frame (310), penetrates the upper frame (310) and the lower frame (320), and is supplied into the chamber (10). At this time, the first gas injection hole (312) may be formed in the first gas path, and specifically, may be formed so as to penetrate the upper frame (310) and the lower frame (320) while being isolated from the space between the upper surface of the lower frame (320) and the lower surface of the upper frame (310).

[0168] The second gas path may be formed so that the second gas provided from the second gas supply unit (120) diffuses in the space between the lower surface of the upper frame (310) and the upper surface of the lower frame (320) and is supplied into the chamber (10) by penetrating the lower frame (320). At this time, the second gas injection hole (322) may be formed in the second gas path, and specifically, may be formed by penetrating the lower frame (320) while communicating with the space between the upper surface of the lower frame (320) and the lower surface of the upper frame (310).

[0169] Accordingly, the first gas path and the second gas path may not be connected to each other, and the first gas and the second gas may be separately supplied from the gas supply device through the first plate (310, 320) to the lower side of the first plate (310, 320).

[0170] The second plate (330) can act as a second electrode for generating plasma in the reaction space, and therefore, the second plate (330) can be referred to as a second electrode.

[0171] The second plate (330) is insulated from the first plate (310, 320) and can be installed spaced apart from the lower side of the first plate (310, 320). That is, the second plate (330) is insulated from the lower frame (320) and can be installed spaced apart from the lower side of the lower frame (320).

[0172] The second plate (330) is installed at a predetermined distance (D1) from the lower surface of the lower frame (320). Accordingly, the first gas and the second gas supplied downward through the first plate (310, 320) can diffuse in the space between the upper surface of the second plate (330) and the lower surface of the lower frame (320). The lower frame (320) and the second plate (330) may be configured to have an outer circumferential surface sealed by a second sealing member (360). At this time, the second sealing member (360) may be formed of an insulating material for electrically insulating the lower frame (320) and the second plate (330) from each other.

[0173] At this time, the second plate (330) may be installed spaced apart from the lower side of the lower frame (320) by a distance such that the plasma sheath region that may be formed on the lower surface of the lower frame (320) and the plasma sheath region that may be formed on the upper surface of the second plate (330) overlap. Here, the plasma sheath region refers to a dark field region where positive (+) ions are densely packed between the plasma and the surface of the structure, so that energy exchange occurs, but plasma is hardly formed.

[0174] If the plasma sheath region that can be formed on the lower surface of the lower frame (320) and the plasma sheath region that can be formed on the upper surface of the second plate (330) do not overlap, plasma can be formed between the plasma sheath regions, but in another embodiment of the present invention, the lower frame (320) and the second plate (330) are spaced apart from each other by a distance such that the plasma sheath region that can be formed on the lower surface of the lower frame (320) and the plasma sheath region that can be formed on the upper surface of the second plate (330) overlap each other, thereby preventing plasma from being generated between the lower surface of the lower frame (320) and the upper surface of the second plate (330).

[0175] Meanwhile, since the first gas and the second gas supplied downward through the first plate (310, 320) need to diffuse in the space between the lower surface of the lower frame (320) and the upper surface of the second plate (330), the lower surface of the lower frame (320) and the upper surface of the second plate (330) must be spaced apart at a distance that allows the gas to flow smoothly. Accordingly, the second plate (330) may be spaced apart from the lower frame (320) by a distance of 3 mm or less, for example, 1 to 3 mm. If the second plate (330) is spaced apart from the lower frame (320) by less than 1 mm, gas cannot flow smoothly in the space between the lower surface of the lower frame (320) and the upper surface of the second plate (330), and if it is spaced apart by more than 3 mm, plasma is generated in the space between the lower surface of the lower frame (320) and the upper surface of the second plate (330), causing particles, which leads to process defects.

[0176] In addition, the second plate (330) has a plurality of openings (332) that are arranged alternately with the first gas injection holes (312) and the second gas injection holes (322). That is, as illustrated in FIG. 10, the second plate (330) is formed with a plurality of openings (332) that do not overlap with any of the first gas injection holes (312) and the second gas injection holes (322) in a plan view. Such a plurality of openings (332) may be formed so as to be arranged between the first gas injection holes (312) and the second gas injection holes (322) in a plan view. In addition, the plurality of openings (332) may be formed so as to be arranged at a central position between the first gas injection holes (312) and the second gas injection holes (322).

[0177] If at least some of the plurality of openings (332) are arranged to overlap with the first gas injection hole (312) or the second gas injection hole (322), most of the gas supplied from the first gas injection hole (312) or the second gas injection hole (322) will pass through the openings (332) arranged to overlap with the first gas injection hole (312) or the second gas injection hole (322) and be injected, respectively. However, some of the gas may not be injected through the openings (332), but may flow into the space between the lower surface of the lower frame (320) and the upper surface of the second plate (330), and may stagnate in the space. Such stagnant gas may impede the smooth flow of gas and may cause particle formation. Accordingly, in the present invention, a plurality of openings (332) may be formed in the second plate (330) so as to be arranged alternately with the first gas injection hole (312) and the second gas injection hole (322).

[0178] The above opening (332) may include a first opening (333) formed close to the lower frame (320) of the first plate, as illustrated in FIG. 11, and a second opening (335) connected to the first opening (333) and having a larger diameter than the first opening (333).

[0179] The above opening (332) may include a first opening (333) having a predetermined length (H1) and a predetermined diameter (D2) from the upper surface of the second plate (330) and a second opening (335) having a predetermined length (H2) and a predetermined diameter (D3) from the lower surface of the second plate (330). At this time, the first opening (333) serves as an inlet for gas, and gas diffused in the space between the lower surface of the lower frame (320) and the upper surface of the second plate (330) flows in through the first opening (333). On the other hand, the second opening (335) serves as an outlet for gas, and gas flowing in through the first opening (333) is sprayed to the lower side of the second plate (330) through the second opening (335).

[0180] The first opening (333) is arranged to be staggered with respect to the first gas injection hole (312) and the second gas injection hole (322), and the second opening (335) may be formed to have a diameter larger than that of the first opening (333) and to extend downward from the first opening (333). Meanwhile, the second opening (335) may include a connecting portion (335a) formed to have an increased diameter at a connection portion with the first opening (333).

[0181] The first opening (333) guides the gas diffused between the lower surface of the lower frame (320) and the upper surface of the second plate (330) to the second opening (335) underneath. The first opening (333) has a diameter (D2) selected to uniformly guide the gas diffused between the lower surface of the lower frame (320) and the upper surface of the second plate (330) to each of the second openings (335). At this time, the first opening (333) may have a diameter (D2) capable of forming a plasma sheath region inside. For this purpose, the first opening (333) may have a diameter (D2) of 0.5 to 1.0 mm. If the diameter (D2) of the first opening (333) is formed to be less than 0.5 mm, gas cannot flow smoothly through the first opening (333), and it becomes difficult to remove particles that may exist within the first opening (333) during cleaning. On the other hand, if the diameter (D2) of the first opening (333) is formed to exceed 1.0 mm, plasma may be generated within the first opening (333), which may cause clogging by particles. The first opening (333) may extend from the upper surface of the second plate (330) and may be formed to be shorter than the length of the second opening (335).

[0182] The second opening (335) is formed by being connected to the lower side of the first opening (333). The second opening (335) generates plasma in the interior of the second plate (330), i.e., in a roughly cylindrical space. That is, the second opening (335) provides a large surface area to promote plasma ionization of the gas flowing into the second opening (335), thereby generating high-density plasma.

[0183] Meanwhile, the second opening (335) may include a connecting portion (335a) formed to have an increasing diameter at a connection portion with the first opening (333). The connecting portion (335a) serves to smoothly transfer gas supplied through the first opening (333) from the upper side of the second opening (335) to the second opening (335). The connecting portion (335a) may have a shape in which the cross-section gradually increases from one end connected to the first opening (333) to the other end, whereby the gas supplied through the first opening (333) can be guided through the connecting portion (335a) without stagnation and smoothly transferred to the second opening (335). However, the connecting portion (335a) is not an essential component, and if the connecting portion (335a) is omitted, a cylindrical second opening (335) can be directly connected to the lower side of the first opening (333).

[0184] The power supply device (400) may be connected to the gas supply unit (300) to supply power to the gas supply unit (300) to generate plasma within the chamber (10). That is, the power supply device (400) may supply RF power to generate plasma within the chamber (10).

[0185] The power supply (400) can be connected to the second plate (330) to supply RF power only to the second plate (330), and in this case, the first plate (310, 320) can be grounded. At this time, the first plate (310, 320) and the second plate (330) can be insulated by a second sealing member (360) formed of an insulating material. In this way, when the power supply (400) supplies RF power to the second plate (330) and the first plate (310, 320) is grounded, the first plate (310, 320) and the second plate (330) each form electrodes for generating capacitively coupled plasma (CCP). In addition, the substrate support (22) is also grounded, so that capacitively coupled plasma can be generated between the second plate (330) and the support (22). Alternatively, the power supply (400) may be configured to supply RF power to each of the first plate (310, 320) and the second plate (330).

[0186] By using the graphene layer forming device of the present invention, a graphene layer can be formed on a substrate (S) by atomic layer deposition (ALD) by supplying a first gas through a first gas supply port and supplying a second gas through a second gas supply port.

[0187] FIG. 12 is a schematic diagram of an electronic device according to one embodiment to which a graphene layer according to the present invention is applied, and relates to a solar cell according to one embodiment.

[0188] As can be seen in FIG. 12, a solar cell according to one embodiment of the present invention comprises a substrate (510), a first electrode (520), a first conductive charge transfer layer (530), a photoelectric conversion layer (540), a second conductive charge transfer layer (550), a transparent conductive layer (560), and a second electrode (570).

[0189] A solar cell according to one embodiment of the present invention can be manufactured through a process of forming a first electrode (520) on a substrate (510), forming a first conductive charge transfer layer (530) on the first electrode (520), forming a photoelectric conversion layer (540) on the first conductive charge transfer layer (530), forming a second conductive charge transfer layer (550) on the photoelectric conversion layer (540), forming a transparent conductive layer (560) on the second conductive charge transfer layer (550), and forming a second electrode (570) on the transparent conductive layer (560).

[0190] The above substrate (510) may be made of a transparent material such as glass or plastic, but is not necessarily limited thereto.

[0191] The first electrode (520) may be formed by a deposition process such as atomic layer deposition (ALD). The first electrode (520) may be formed of the graphene layer described above.

[0192] The above first conductive charge transport layer (530) may be formed as a hole transport layer or an electron transport layer.

[0193] The above hole transport layer can be formed by including various P-type organic materials known in the art, such as Spiro-MeO-TAD, Spiro-TTB, polyaniline, polypyrrolidone, poly-3,4-ethylenedioxythiophene-polystyrenesulfonate (PEDOT-PSS), or poly-[bis(4-phenyl)(2,4,6-trimethylphenyl)amine](PTAA), Poly(3-hexylthiophene-2,5-diyl) (P3HT), various P-type metal oxides known in the art, such as Ni oxide, Mo oxide or V oxide, W oxide, Cu oxide, and various other P-type organic or inorganic materials known in the art.

[0194] The electron transport layer may be formed by including an N-type organic material such as BCP (Bathocuproine), C60, or PCBM (Phenyl-C61-butyric acid methyl ester), various N-type metal oxides known in the art such as ZnO, c-TiO2 / mp-TiO2, SnO2, or IZO, and various other N-type organic or inorganic materials known in the art.

[0195] The above first conductive charge transport layer (530) may be composed of a plurality of hole transport layers or a plurality of electron transport layers.

[0196] The above first conductive charge transfer layer (530) can be formed by a deposition process such as CVD (Chemical Vapor Deposition) or ALD (Atomic Layer Deposition).

[0197] The above photoelectric conversion layer (540) is made of a perovskite compound of ABX3 and can be formed by a deposition process such as CVD (Chemical Vapor Deposition) or ALD (Atomic Layer Deposition).

[0198] The above perovskite compound can be obtained through a process of forming a compound of ABX3 by depositing at least one compound selected from an amine series compound and an amidine series compound, an organometallic compound containing a divalent cation, and at least one hydrogen halide through a CVD (Chemical Vapor Deposition) or ALD (Atomic Layer Deposition) process.

[0199] In the above ABX3, the A may be formed of a monovalent organic cation of the amine series compound, may be formed of a monovalent organic cation of the amidine series compound, or may be formed by including a monovalent organic cation of the amine series compound and a monovalent organic cation of the amidine series compound. The A may be formed of a structure in which the monovalent organic cation of the amine series compound is included in an x ​​ratio and the monovalent organic cation of the amidine series compound is included in a y ratio. At this time, x and y are each greater than 0, and x+y=1.

[0200] In the above ABX3, the B is composed of the divalent cation.

[0201] In the above ABX3, X is composed of at least one halogen compound.

[0202] The above amine series compound may be selected from the group consisting of methylamine, ethylamine, and phenethylamine.

[0203] The above amidine series compound may be composed of formamidine.

[0204] The organometallic compound containing the above divalent cation may contain a metal selected from the group consisting of Pb, Sn, Ge, Sb, Bi, and Ba.

[0205] Specifically, the organometallic compound containing the divalent cation is represented by the following chemical formula 1:

[0206] Chemical Formula 1

[0207]

[0208] (R in the above chemical formula 1 1 Inland R 12 are each independently composed of hydrogen or an alkyl group, and X is selected from the group consisting of Pb, Sn, Ge, Sb, Bi, and Ba.

[0209] It can be composed of a compound expressed as .

[0210] Alternatively, the organometallic compound containing the above divalent cation is Pb(CH3)4, Pb(C2H5)4, Pb(SCN)2, (C2H5)3PbOCH2C(CH3)3, Pb(C 11 H 19 O2)2, Pb((CH3)3C-COCHCO-C(CH3)3)2, Pb((C6H5)2PCH2P(C6H5)2)2, Pb(N(CH3)2C(CH3)2OH)2, and C 12 H 28 It can be selected from the group consisting of N2O2Pb.

[0211] The above hydrogen halide can be selected from the group consisting of HI, HBr, Hf, and HCl.

[0212] The above amine series compound, the amidine series compound, the organometallic compound containing the divalent cation, and the hydrogen halide are made of substances that vaporize at a temperature in the range of room temperature to 200°C, and preferably, are made of substances that vaporize at a temperature in the range of 50°C to 150°C. Accordingly, the process for manufacturing the ABX3 compound can be performed at a temperature of 200°C or lower, preferably 150°C or lower, through a chemical vapor deposition (CVD) process or an atomic layer deposition (ALD), so that organic substances in the final ABX3 compound can be prevented from being decomposed during the CVD or ALD process. Meanwhile, it is also possible to apply plasma when performing the CVD or ALD process.

[0213] According to another embodiment of the present invention, the perovskite compound can be obtained through a process of depositing and forming a compound of CABX3 by reacting at least one compound selected from an amine series compound and an amidine series compound, at least one alkali metal series compound, an organometallic compound containing a divalent cation, and a hydrogen halide through a CVD (Chemical Vapor Deposition) or ALD (Atomic Layer Deposition) process.

[0214] In the above CABX3, the A may be formed of a monovalent organic cation of the amine series compound, may be formed of a monovalent organic cation of the amidine series compound, or may be formed by including a monovalent organic cation of the amine series compound and a monovalent organic cation of the amidine series compound.

[0215] In the above CABX3, the C may be composed of at least one alkali metal.

[0216] The above CA may be formed into a structure in which the monovalent organic cation of the amine series compound is included in an x ​​ratio, the monovalent organic cation of the amidine series compound is included in a y ratio, and the monovalent cation of the alkali metal is included in a z ratio. At this time, x, y, and z are each greater than 0, and x+y+z=1.

[0217] In the above CABX3, the B is composed of the divalent cation, and the X is composed of at least one halogen compound.

[0218] The above amine series compound, the above amidine series compound, the above organometallic compound containing the divalent cation, and the above hydrogen halide are the same as those described above, so a repeated description will be omitted.

[0219] The above alkali metal series compound has the following chemical formula 2:

[0220] Chemical Formula 2

[0221]

[0222] (R in the above chemical formula 2 1 Inland R 6 are each independently composed of hydrogen or an alkyl group, and Y is an alkali metal)

[0223] It can be composed of a compound expressed as .

[0224] According to another embodiment of the present invention, the instability of monovalent organic cations that are vulnerable to moisture, heat, and plasma can be compensated for by adding at least one alkali metal series compound to the reactant.

[0225] The above second conductive charge transport layer (550) may be formed as an electron transport layer or a hole transport layer.

[0226] When the first conductive charge transport layer (530) is formed as a hole transport layer, the second conductive charge transport layer (550) is formed as an electron transport layer, and when the first conductive charge transport layer (530) is formed as an electron transport layer, the second conductive charge transport layer (550) is formed as a hole transport layer.

[0227] The above second conductive charge transport layer (550) may be composed of a plurality of electron transport layers or a plurality of hole transport layers.

[0228] The above second conductive charge transfer layer (550) can be formed by a deposition process such as CVD (Chemical Vapor Deposition) or ALD (Atomic Layer Deposition).

[0229] The transparent conductive layer (560) may be formed of, but is not necessarily limited to, ITO or IZO. The transparent conductive layer (560) may be formed by a deposition process such as ALD. The transparent conductive layer (60) may be omitted.

[0230] The above second metal (570) can be patterned into a predetermined shape so that sunlight can enter the inside of the cell.

[0231] The above second electrode (570) can be formed by patterning the above-described graphene layer.

[0232] FIG. 13 is a schematic diagram of an electronic device according to another embodiment to which a graphene layer according to the present invention is applied, and relates to a solar cell according to another embodiment.

[0233] As can be seen in FIG. 13, a solar cell according to another embodiment of the present invention comprises a crystalline solar cell (600), a buffer layer (700), a perovskite solar cell (500), a first electrode (520), and a second electrode (570).

[0234] A solar cell according to another embodiment of the present invention can be manufactured through a process of forming the buffer layer (700) on the crystalline solar cell (600), forming the perovskite solar cell (500) on the buffer layer (700), forming the first electrode (520) on the lower surface of the crystalline solar cell (600), and forming the second electrode (570) on the upper surface of the perovskite solar cell (500).

[0235] The above crystalline solar cell (600) can be formed through a process of forming a rough structure by etching one side and the other side of a semiconductor substrate (610) such as a wafer, doping a predetermined dopant on one side of the semiconductor substrate (610) to form a first semiconductor layer (620), and doping a predetermined dopant on the other side of the semiconductor substrate (610) to form a second semiconductor layer (630).

[0236] As one side and the other side of the semiconductor substrate (610) are formed with a rough structure, the first semiconductor layer (620) and the second semiconductor layer (630) are formed in a shape corresponding to the rough structure.

[0237] Meanwhile, it is not necessarily limited thereto, and one of the one side and the other side of the semiconductor substrate (610) may be formed with a rough structure and the other side may be formed as a plane. In some cases, both the one side and the other side of the semiconductor substrate (610) may be formed as a plane.

[0238] The semiconductor substrate (610) may be formed of a P-type or N-type wafer, the first semiconductor layer (620) may be doped with a dopant having a different polarity from that of the semiconductor substrate (610), and the second semiconductor layer (630) may be doped with a dopant having the same polarity as that of the semiconductor substrate (610). For example, the semiconductor substrate (610) may be formed of a P-type wafer, the first semiconductor layer (620) may be doped with an N-type dopant, and the second semiconductor layer (630) may be doped with a P-type dopant to form a P+ layer.

[0239] The buffer layer (700) is formed on the first semiconductor layer (620). As the first semiconductor layer (620) is formed in a rough structure, the buffer layer (700) is formed in a shape corresponding to the rough structure.

[0240] The above buffer layer (700) is provided between the crystalline solar cell (600) and the perovskite solar cell (500), so that the solar cell according to one embodiment of the present invention forms a tandem solar cell structure through tunnel junction.

[0241] The buffer layer (700) is preferably made of a material that allows long-wavelength light passing through the perovskite solar cell (500) to be incident on the crystalline solar cell (600) without loss. For example, the buffer layer (700) may be made of a transparent conductive oxide, a carbonaceous conductive material, a metallic material, or a conductive polymer, and in some cases, the material may be doped with an n-type or p-type dopant.

[0242] The perovskite solar cell (500) may include a first conductive charge transfer layer (530) provided on the buffer layer (700), a photoelectric conversion layer (540) provided on the first conductive charge transfer layer (530), a second conductive charge transfer layer (550) provided on the photoelectric conversion layer (540), and a transparent conductive layer (560) provided on the second conductive charge transfer layer (550).

[0243] The first conductive charge transfer layer (530), the photoelectric conversion layer (540), the second conductive charge transfer layer (550), and the transparent conductive layer (560) are the same as those in the above-described embodiment, so a repeated description will be omitted.

[0244] The first electrode (520) formed on the lower surface of the above-described crystalline solar cell (600) and the second electrode (570) formed on the upper surface of the above-described perovskite solar cell (500) can be configured to allow sunlight or its reflected light to be incident into the interior of the solar cell by being patterned in a predetermined shape.

[0245] At least one of the first electrode (520) and the second electrode (570) may be formed of the above-described graphene layer.

[0246] Although not shown, a passivation layer with a rough structure can be additionally formed on the second electrode (570). At this time, a portion of the passivation layer is etched so that the second electrode (570) can be exposed.

[0247] By forming the above passivation layer into a rough structure, the amount of light incident on the perovskite solar cell can be increased.

[0248] The passivation layer may be formed of polydimethylsiloxane, and when the polydimethylsiloxane is formed on the perovskite solar cell, a micropyramid-shaped irregular structure may be obtained. The passivation layer may be formed of various materials, such as SiO, SiON, SiN, Al2O3, or MgF.

[0249] FIG. 14 is a schematic diagram of an electronic device according to another embodiment to which a graphene layer according to the present invention is applied, and relates to a solar cell according to another embodiment.

[0250] As can be seen in Fig. 14, a solar cell according to another embodiment of the present invention comprises a semiconductor substrate (810), a first electrode (820), a first semiconductor layer (830), a buffer layer (840), a second semiconductor layer (850), and a second electrode (860). The first semiconductor layer (830) and the second semiconductor layer (850) can function as a photoelectric conversion layer.

[0251] A solar cell according to another embodiment of the present invention can be manufactured through a process of forming the first semiconductor layer (830) on the semiconductor substrate (810), forming the buffer layer (840) on the first semiconductor layer (830), forming the second semiconductor layer (850) on the buffer layer (840), forming the first electrode (820) on the lower surface of the semiconductor substrate (810), and forming the second electrode (860) on the upper surface of the second semiconductor layer (850).

[0252] The above semiconductor substrate (810) may be made of an N-type or P-type semiconductor.

[0253] The first semiconductor layer (830) includes a first type III-V group semiconductor layer (831) and a second type III-V group semiconductor layer (832). The first type III-V group semiconductor layer (831) may be formed to have the same polarity as the semiconductor substrate (810), and the second type III-V group semiconductor layer (832) may be formed to have a different polarity from the semiconductor substrate (810).

[0254] For example, the first type III-V group semiconductor layer (831) may be formed of at least one layer of N-type GaAs, N-type InGaAs, and N-type InGaP, and the second type III-V group semiconductor layer (832) may be formed of at least one layer of P-type GaAs, P-type InGaAs, and P-type AlGaAs.

[0255] The first type III-V group semiconductor layer (831) and the second type III-V group semiconductor layer (832) can be formed by an ALD process or a CVD process, respectively. For example, the first type III-V group semiconductor layer (831) and the second type III-V group semiconductor layer (832) can be formed by an ALD process including a step of injecting one or more gases containing a Group III element and a step of injecting one or more gases containing a Group V element, respectively. Alternatively, the first type III-V group semiconductor layer (831) and the second type III-V group semiconductor layer (832) can be formed by a CVD process including a step of injecting one or more gases containing a Group III element and one or more gases containing a Group V element together, respectively.

[0256] The group 3 element may include at least one element selected from gallium (Ga), indium (In), aluminum (Al), and boron (B), and the group 5 element may include at least one element selected from arsenic (As), phosphorus (P), and antimony (Sb).

[0257] The above buffer layer (840) may be formed of a III-V group semiconductor layer, but is not necessarily limited thereto. The above buffer layer (840) may be formed by an ALD or CVD process.

[0258] The second semiconductor layer (850) includes a first type III-V group semiconductor layer (851) and a second type III-V group semiconductor layer (852). The second semiconductor layer (850) may have a different light absorption wavelength from that of the first semiconductor layer (830).

[0259] The first type III-V group semiconductor layer (851) may be formed to have the same polarity as the semiconductor substrate (810), and the second type III-V group semiconductor layer (852) may be formed to have a polarity different from the semiconductor substrate (810).

[0260] For example, the first type III-V group semiconductor layer (851) may be formed of at least one layer of N-type GaAs, N-type InGaAs, and N-type InGaP, and the second type III-V group semiconductor layer (852) may be formed of at least one layer of P-type GaAs, P-type InGaAs, and P-type AlGaAs.

[0261] The above-mentioned first type III-V group semiconductor layer (851) and the above-mentioned second type III-V group semiconductor layer (852) can be formed by an ALD process or a CVD process, respectively.

[0262] At least one of the first electrode (820) and the second electrode (860) may be formed of the above-described graphene layer.

[0263] Meanwhile, although not specifically illustrated, the aforementioned graphene layer may also be used as a semiconductor layer, such as an active layer of a thin film transistor. For example, a bottom-gate structure thin film transistor may be formed by forming a gate electrode on a substrate, forming a gate insulating film on the gate electrode, forming an active layer made of the aforementioned graphene layer on the gate insulating film, and forming a source electrode and a drain electrode on the active layer. Alternatively, a top-gate structure thin film transistor may be formed by forming an active layer made of the aforementioned graphene layer on a substrate, forming a gate insulating film on the active layer, forming a gate electrode on the gate insulating film, forming an interlayer insulating film on the gate electrode, and forming a source electrode and a drain electrode electrically connected to the gate electrode on the interlayer insulating film.

[0264] In the thin film transistor of the above bottom gate structure and the thin film transistor of the above top gate structure, at least one of the gate electrode, the source electrode, and the drain electrode may be formed of the above-described graphene layer.

[0265] Although the embodiments of the present invention have been described in more detail with reference to the attached drawings, the present invention is not necessarily limited to these embodiments, and various modifications may be implemented without departing from the technical spirit of the present invention. Therefore, the embodiments disclosed in the present invention are not intended to limit the technical spirit of the present invention, but to explain it, and the scope of the technical spirit of the present invention is not limited by these embodiments. Therefore, it should be understood that the embodiments described above are illustrative in all aspects and not restrictive. The protection scope of the present invention should be interpreted by the claims, and all technical ideas within a scope equivalent thereto should be interpreted as being included in the scope of the rights of the present invention.

Claims

1. A step of spraying hydrocarbon gas on a substrate and forming a first plasma; and comprising a step of forming a second plasma on the substrate, A method for forming a graphene layer, characterized in that the step of injecting the hydrocarbon gas and forming the first plasma is performed without supplying hydrogen gas.

2. In paragraph 1, A method for forming a graphene layer, characterized in that the process of injecting the hydrocarbon gas and the process of forming the first plasma are performed simultaneously.

3. In paragraph 1, A method for forming a graphene layer, characterized in that the step of forming the second plasma includes a process of removing hydrocarbon gas remaining on the substrate.

4. In paragraph 1, A method for forming a graphene layer, characterized in that the step of forming the second plasma is performed while supplying hydrogen gas onto the substrate.

5. In paragraph 4, A method for forming a graphene layer, characterized in that the step of forming the second plasma while supplying the hydrogen gas includes a process of removing carbon remaining on the substrate by combining it with the hydrogen gas.

6. In paragraph 1, A method for forming a graphene layer, characterized in that the step of forming the second plasma comprises a process of stopping the injection of the hydrocarbon gas and continuously performing the formation of the first plasma.

7. In paragraph 1, A method for forming a graphene layer, characterized in that the RF power of the first plasma is greater than the RF power of the second plasma.

8. In paragraph 1, A method for forming a graphene layer, characterized in that at least one of the first plasma and the second plasma is composed of Ar plasma.

9. In paragraph 1, The above hydrocarbon gas is injected through a plurality of first injection holes of the first gas injection unit, The gas for forming the first plasma is injected through a plurality of second injection holes of the second gas injection unit, The hydrocarbon gas is supplied to the plurality of first injection holes through the first gas path, and the gas for forming the first plasma is supplied to the plurality of second injection holes through the second gas path. A method for forming a graphene layer, characterized in that the first gas path and the second gas path are provided independently of each other.

10. In paragraph 9, It further includes a plurality of third injection holes connected to the plurality of first injection holes or the plurality of second injection holes, A method for forming a graphene layer, characterized in that the hydrocarbon gas is injected through the first injection hole and the third injection hole, or the gas for forming the first plasma is injected through the second injection hole and the third injection hole.

11. In paragraph 10, It includes a first electrode and a second electrode to which RF power is applied so as to have different potentials, A method for forming a graphene layer, wherein the third injection hole is provided by a space between the first electrode and the second electrode, and plasma is formed within the plurality of third injection holes.

12. In paragraph 9, A method for forming a graphene layer, comprising: a first plate having a plurality of first injection holes and second injection holes; and a second plate having a plurality of openings spaced apart from the first plate and arranged in an alternating manner with the first injection holes and the second injection holes, wherein the openings include a first opening formed on the side of the first plate and a second opening connected to the first opening and having a larger diameter than the first opening and a longer length than the first opening.

13. In paragraph 12, A method for forming a graphene layer, wherein the second opening includes a connecting portion connected to the first opening, and the connecting portion has a diameter that increases from one end connected to the first opening to the other end.

14. A method for forming a graphene layer in a chamber including an upper dome and a lower dome, The method comprises the steps of injecting hydrocarbon gas into the chamber and forming a first plasma; and comprising a step of forming a second plasma within the chamber; A method for forming a graphene layer, characterized in that the step of injecting the hydrocarbon gas and forming the first plasma is performed without supplying hydrogen gas.

15. In paragraph 14, The above hydrocarbon gas is injected from the first gas injection unit provided in the chamber, The gas for forming the first plasma is injected from a second gas injection unit provided in the chamber, A method for forming a graphene layer, wherein the gas for forming the second plasma is injected from the second gas injection unit.

16. In paragraph 15, The first gas injection unit includes a first gas path, and the second gas injection unit includes a second gas path. A method for forming a graphene layer, wherein the first gas path and the second gas path are separated from each other.

17. Process for forming a semiconductor layer on a substrate; and It comprises a process of forming an electrode on the above substrate, A method for manufacturing an electronic device, wherein at least one of the processes for forming the semiconductor layer and the process for forming the electrode comprises a graphene layer forming method according to any one of claims 1 to 16 described above.

18. In paragraph 17, The electronic device comprises a solar cell including a first electrode, a photoelectric conversion layer, and a second electrode, A method for manufacturing an electronic device, comprising a process for forming at least one electrode among the first electrode and the second electrode, including a method for forming a graphene layer according to any one of claims 1 to 16 described above.

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