Method for forming carbon layer and substrate processing method using same

Abstract

The present invention provides a method for forming a carbon layer and a substrate processing method using same. The method for forming a carbon layer comprises: a step for supplying a carbon-containing gas onto a first layer containing silicon; a first plasma processing step for supplying an inert gas onto the first layer and forming a first plasma; and a second plasma processing step for supplying an oxygen-containing gas and forming a second plasma after the first plasma processing step.

Description

Method for forming a carbon layer and method for treating a substrate using the same

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

[0002] Carbon layers, such as graphene, are a type of carbon isotope. Carbon atoms are arranged at the vertices of hexagons, forming a two-dimensional planar crystal structure with a hexagonal honeycomb pattern. Carbon layers like graphene possess electrical properties, making them ideal components for a variety of electronic devices.

[0003] Physical exfoliation, chemical vapor deposition, chemical exfoliation, and epitaxial growth methods have been studied as methods for manufacturing carbon layers, but there are still limitations in their efficient manufacturing.

[0004] The present invention has been designed to solve the above-mentioned conventional problems, and the purpose of the present invention is to provide an efficient method for forming a carbon layer.

[0005] In order to achieve the above object, one embodiment of the present invention provides a method for forming a carbon layer, comprising: a step of supplying a carbon-containing gas onto a first layer including silicon; a first plasma treatment step of supplying an inert gas onto the first layer and forming a first plasma; and, after the first plasma treatment step, a second plasma treatment step of supplying an oxygen-containing gas and forming a second plasma.

[0006] A step of forming a silicon oxide layer or a silicon layer on the first layer may be additionally included prior to the step of supplying the carbon-containing gas.

[0007] The step of supplying the carbon-containing gas and the first plasma treatment step can be performed simultaneously.

[0008] The method may further include a step of supplying the carbon-containing gas and a third plasma treatment step of supplying a hydrogen (H2)-containing gas and forming a third plasma after the first plasma treatment step and before the second plasma treatment step.

[0009] The step of supplying the carbon-containing gas, the first plasma treatment step, and the third plasma treatment step can be performed multiple times.

[0010] After the second plasma treatment step, a fourth plasma treatment step of supplying a hydrogen-containing gas and forming a fourth plasma may be additionally included.

[0011] The method further includes a fourth plasma treatment step of supplying a hydrogen-containing gas and forming a fourth plasma after the second plasma treatment step, and the process of performing the second plasma treatment step and the fourth plasma treatment step after performing the step of supplying the carbon-containing gas, the first plasma treatment step, and the third plasma treatment step multiple times can be repeated as one cycle.

[0012] A step of supplying a fluorine-containing etching gas may be additionally included after the second plasma treatment step.

[0013] The second plasma treatment step can be performed after the step of supplying the carbon-containing gas, the first plasma treatment step, and the third plasma treatment step are performed multiple times.

[0014] A fourth plasma treatment step of supplying a hydrogen-containing gas and forming a fourth plasma is further included after the second plasma treatment step, and the step of supplying the carbon-containing gas, the first plasma treatment step, the third plasma treatment step, the second plasma treatment step, and the fourth plasma treatment step are made into one cycle, and the one cycle can be performed multiple times.

[0015] The method further includes a fourth plasma treatment step of supplying a hydrogen-containing gas and forming a fourth plasma after the second plasma treatment step, and the first plasma treatment step, the third plasma treatment step, the second plasma treatment step, and the fourth plasma treatment step can be performed at a temperature of 500°C or less.

[0016] The above inert gas may include at least one of argon (Ar) gas, neon (Ne) gas, helium (he) gas, krypton (Kr) gas, radon (Rn) gas, and xenon (Xe) gas.

[0017] A step of supplying a purge gas or pumping a process gas may be additionally included between the first plasma treatment step and the second plasma treatment step.

[0018] The method may further include a step of supplying a purge gas or pumping a process gas between the first plasma treatment step and the third plasma treatment step, and between the third plasma treatment step and the second plasma treatment step.

[0019] The method may further include a step of supplying a purge gas or pumping a process gas between the first plasma treatment step and the second plasma treatment step, and between the second plasma treatment step and the fourth plasma treatment step.

[0020] The step of supplying the carbon-containing gas, the first plasma treatment step, and the second plasma treatment step can be performed multiple times.

[0021] The present invention also provides a substrate processing method using a substrate processing device including a chamber providing an internal space, a substrate support unit supporting one or more substrates in the internal space, and a gas supply unit supplying gas into the chamber, wherein the method provides a substrate processing method including the above-described carbon layer forming method.

[0022] According to the present invention as described above, a carbon layer can be formed through an atomic layer deposition method, so that the film quality of the carbon layer can be improved, thereby improving the electrical properties of the carbon layer.

[0023] Therefore, the carbon layer can be used as an electrode for solar cells or thin film transistors, and can also be used as a semiconductor layer such as the active layer of a thin film transistor.

[0024] In particular, according to one embodiment of the present invention, by forming oxygen (O2) plasma so that the upper carbon layer can be removed in the form of carbon dioxide (CO2) by combining with oxygen, a carbon layer with excellent physical properties from which defects are removed can be obtained.

[0025] In addition, by forming hydrogen plasma after the process of forming the oxygen (O2) plasma, impurities such as silicon oxide (SiO2) that may be formed on the upper surface of the carbon layer when the constituent material of the substrate, for example, silicon (Si) material, diffuses upward due to the oxygen (O2) plasma can be easily removed, thereby obtaining a carbon layer with excellent physical properties.

[0026] Figure 1 is a schematic process flow diagram of a method for forming a carbon layer according to one embodiment of the present invention.

[0027] Figure 2 is a schematic process flow diagram of a method for forming a carbon layer according to another embodiment of the present invention.

[0028] Figure 3 is a schematic process flow diagram of a method for forming a carbon layer according to another embodiment of the present invention.

[0029] Figure 4 is a schematic process flow diagram of a method for forming a carbon layer according to another embodiment of the present invention.

[0030] Figure 5 is a schematic diagram of a carbon layer forming device according to one embodiment of the present invention.

[0031] FIG. 6 is a schematic diagram of an electronic device according to one embodiment of the present invention to which a carbon layer is applied, and relates to a solar cell according to one embodiment.

[0032] FIG. 7 is a schematic diagram of an electronic device according to another embodiment to which a carbon layer according to the present invention is applied, and relates to a thin film transistor according to another embodiment.

[0033] The advantages and features of the present invention, and the methods for achieving them, will become clearer with reference to the embodiments described in detail below together with the accompanying drawings. However, the present invention is not limited to the embodiments disclosed below, but may be implemented in various different forms. These embodiments are provided solely to ensure that the disclosure of the present invention is complete and to fully inform those skilled in the art of the scope of the invention, and the present invention is defined solely by the scope of the claims.

[0034] The shapes, sizes, ratios, angles, numbers, etc. disclosed in the drawings for explaining embodiments of the present invention are illustrative and are not limited to the matters illustrated in the drawings. Like reference numerals refer to like components throughout the specification. In addition, in describing the present invention, if a detailed description of a related known technology is judged to unnecessarily obscure the gist of the present invention, the detailed description thereof will be omitted. When the terms “includes,” “has,” and “consists of” are used in this specification, other parts may be added unless “only” is used. When a component is expressed in the singular, it includes a case where the plural is included unless there is a specifically explicit description.

[0035] When interpreting a component, it is interpreted as including the error range even if there is no separate explicit description.

[0036] When describing a positional relationship, for example, when the positional relationship between two parts is described as 'on top of', 'upper part of', 'lower part of', 'next to', etc., one or more other parts may be located between the two parts, unless 'right away' or 'directly' is used.

[0037] When describing a temporal relationship, for example, when the temporal continuity is described as 'after', 'following', 'next to', 'before', etc., it can also include cases where it is not continuous, as long as 'right away' or 'directly' is not used.

[0038] While terms like "first" and "second" are used to describe various components, these components are not limited by these terms. These terms are merely used to distinguish one component from another. Therefore, a "first" component referred to below may also be a "second" component within the technical scope of the present invention.

[0039] The features of each of the various embodiments of the present invention can be partially or wholly combined or combined with each other, and various technical connections and operations are possible, and each embodiment can be implemented independently of each other or implemented together in a related relationship.

[0040] Hereinafter, a preferred embodiment of the present invention will be described in detail with reference to the drawings.

[0041] Figure 1 is a schematic process flow diagram of a method for forming a carbon layer according to one embodiment of the present invention.

[0042] A method for forming a carbon layer according to one embodiment of the present invention can be performed using atomic layer deposition (ALD), particularly, plasma atomic layer deposition, and the same applies to other embodiments below.

[0043] First, a substrate is loaded into a chamber and a carbon-containing gas is supplied onto the substrate (S10). Throughout this specification, supplying a gas includes spraying a gas and means performing the process within the chamber.

[0044] The substrate may be formed of a silicon substrate, such as a silicon wafer. Alternatively, the substrate may be formed of a structure in which a silicon layer is formed on a non-semiconductor substrate, such as glass. Alternatively, the substrate may be formed of a structure in which a silicon compound layer, such as silicon oxide or silicon nitride, is formed on the non-semiconductor substrate.

[0045] Accordingly, the carbon layer may be formed on a layer containing silicon, wherein the layer containing silicon may include the silicon wafer, the silicon layer, or the silicon compound layer.

[0046] Throughout this specification, a carbon layer may refer to a layer comprising a carbon element, such as graphene or graphite, and particularly, a layer composed of a single carbon atom. Here, a carbon layer composed of a single carbon atom may include cases in which some other materials are contained due to process limitations.

[0047] Meanwhile, when using the silicon nitride layer as the layer including the silicon, there is a possibility that the carbon layer will not grow well on the silicon nitride layer because the nitrogen (N) atoms in the silicon nitride layer are not easily broken. Therefore, when using the silicon nitride layer, it may be preferable to form a silicon oxide layer or a silicon layer on the silicon nitride layer and then form a carbon layer on the silicon oxide layer or the silicon layer, rather than forming a carbon layer directly on the silicon nitride layer.

[0048] In some cases, a silicon oxide layer or silicon layer may be formed on a silicon compound layer other than a silicon nitride layer or a silicon oxide layer, and a carbon layer may be formed on the silicon oxide layer or silicon layer.

[0049] The above atomic layer deposition method, particularly, the plasma atomic layer deposition method, can be performed within a temperature range that silicon can withstand, for example, at a low temperature range of 500°C or less, or 350°C or less, or 200°C or less.

[0050] The above carbon-containing gas may include hydrocarbon gas.

[0051] The above hydrocarbon gas is a gas that can be expressed as CxHy (wherein x and y are each greater than 0) containing carbon and hydrogen, and examples thereof include methane (CH4) gas, ethane (C2H6) gas, propane (C3H8) gas, and butane (C4H 40) gas, ethylene (C2H4) gas, propene (C3H6) gas, and acetylene (C2H2) gas, but are not necessarily limited thereto.

[0052] Next, a first plasma treatment step is performed to supply an inert gas on the substrate, particularly, on the layer including the silicon, and to form a first plasma (S20).

[0053] The first plasma may utilize an inert gas. The inert gas may include, for example, at least one of argon (Ar) gas, neon (Ne) gas, helium (he) gas, krypton (Kr) gas, radon (Rn) gas, and xenon (Xe) gas. Specifically, the first plasma may be formed of a plasma of an inert gas such as argon (Ar), neon (Ne), helium (he), krypton (Kr), radon (Rn), and xenon (Xe), but is not necessarily limited thereto.

[0054] The above first plasma treatment step (S20) can be performed simultaneously with the carbon-containing gas supply step (S10).

[0055] During the process of performing the above carbon-containing gas supply step (S10) and performing the first plasma treatment step (S20), separate hydrogen gas is not supplied into the chamber. Therefore, by performing the carbon-containing gas supply step (S10) and the first plasma treatment step (S20) without a separate hydrogen gas supply, a first thin film layer can be formed on the substrate, particularly, the layer including the silicon. If the first plasma treatment step (S20) is performed while supplying hydrogen gas, a C-H bond may be generated, and the first thin film layer composed only of carbon (C) may not be formed.

[0056] Next, after the first plasma treatment step (S20), a second plasma treatment step is performed in which an oxygen (O2) containing gas is supplied into the chamber and a second plasma is formed (S30).

[0057] As described above, when the carbon-containing gas supply step (S10) is performed without a separate hydrogen gas supply and the first plasma treatment step (S20) is performed, a first thin film layer made of only carbon is formed on the substrate, particularly on the layer including silicon, and at this time, the first thin film layer may be formed in multiple layers on the layer including silicon.

[0058] The lower first thin film layer in contact with the layer containing silicon has excellent bonding strength with the layer containing silicon, but the upper first thin film layer not in direct contact with the layer containing silicon may have weak bonding strength. Accordingly, the physical properties of the carbon layer ultimately obtained due to the upper first thin film layer may deteriorate. For example, the upper first thin film layer may act as a defective layer.

[0059] Therefore, according to one embodiment of the present invention, by performing a second plasma treatment step (S30) of forming the second plasma with the oxygen (O2) containing gas, the upper first thin film layer is etched or removed. Specifically, when the second plasma is formed with the oxygen (O2) containing gas, the upper first thin film layer can be etched or removed in the form of carbon dioxide (CO2) by combining with oxygen, and thus a carbon layer with excellent physical properties can be ultimately obtained.

[0060] At this time, at least one second thin film layer on the upper side, excluding the first thin film layer of the lower monolayer, is etched or removed by the second plasma treatment step (S30), so that the finally obtained carbon layer may be formed as a single-layer carbon layer, but is not necessarily limited thereto, and the finally obtained carbon layer may be formed as a carbon layer of two or more multilayers.

[0061] The thickness of the carbon layer of the above single layer may be, for example, 3Å or less, or 5Å or less, or 10Å or less, or 15Å or less.

[0062] The thickness of the above-described carbon layer may be, for example, 20 Å or less, or 25 Å or less, or 30 Å or less, or 40 Å or less, or 50 Å or less.

[0063] The above oxygen (O2)-containing gas may be composed of oxygen gas, but is not necessarily limited thereto.

[0064] In the first plasma treatment step (S20), the first RF power for forming the first plasma and the second RF power for forming the second plasma in the second plasma treatment step (S30) may be different. Specifically, the first RF power may be greater than the second RF power.

[0065] Meanwhile, although not specifically shown, a step of supplying a purge gas or a step of pumping the supplied process gas may be performed between the step of supplying the carbon-containing gas (S10) and the first plasma treatment step (S20).

[0066] Additionally, a step of supplying purge gas or a step of pumping the supplied process gas may be performed between the first plasma treatment step (S20) and the second plasma treatment step (S30).

[0067] The step of supplying the carbon-containing gas (S10), the first plasma treatment step (S20), and the second plasma treatment step (S30) can be performed multiple times.

[0068] Figure 2 is a schematic process flow diagram of a method for forming a carbon layer according to another embodiment of the present invention.

[0069] First, a substrate, particularly a substrate having a layer including silicon, is loaded into the chamber, and a carbon-containing gas is supplied onto the substrate (S10).

[0070] This process (S10) is identical to the previously described Fig. 1, so a repeated explanation will be omitted.

[0071] Next, a first plasma treatment step is performed to supply an inert gas onto the substrate, particularly, the layer including the silicon, and form a first plasma (S20).

[0072] This process (S20) is also identical to the previously described Fig. 1, so a repeated explanation will be omitted.

[0073] Next, a third plasma treatment step is performed to supply a hydrogen-containing gas into the chamber and form a third plasma (S25).

[0074] A part of the first thin film layer generated in the aforementioned process (S10, S20) may have a weak bonding strength with the substrate, and when the final carbon layer is manufactured in a state where a multi-layer first thin film layer is formed on the first thin film layer having a weak bonding strength with the substrate, the physical properties of the obtained carbon layer may deteriorate.

[0075] Therefore, in another embodiment of the present invention, a first thin film layer having a weak bonding strength with the substrate can be removed through a third plasma treatment using a hydrogen-containing gas, thereby obtaining a final carbon layer based on a first thin film layer having a strong bonding strength with the substrate.

[0076] The hydrogen-containing gas may be formed of hydrogen gas, but is not necessarily limited thereto. The first RF power for forming the first plasma in the first plasma treatment step (S20) and the third RF power for forming the third plasma in the third plasma treatment step (S25) may be different. Specifically, the first RF power may be greater than the third RF power.

[0077] After the above carbon-containing gas supply step (S10), the first plasma treatment step (S20), and the third plasma treatment step (S25) are repeatedly performed multiple times, a subsequent second plasma treatment step (S30) can be performed.

[0078] Next, a second plasma treatment step is performed to supply oxygen (O2) containing gas into the chamber and form a second plasma (S30).

[0079] This process (S30) is identical to the previously described Fig. 1, so a repeated explanation will be omitted.

[0080] Meanwhile, although not specifically shown, a step of supplying a purge gas or a step of pumping the supplied process gas may be performed between the step of supplying the carbon-containing gas (S10) and the first plasma treatment step (S20).

[0081] Additionally, a step of supplying purge gas or a step of pumping the supplied process gas may be performed between the first plasma treatment step (S20) and the third plasma treatment step (S25).

[0082] Additionally, a step of supplying purge gas or a step of pumping the supplied process gas may be performed between the third plasma treatment step (S25) and the second plasma treatment step (S30).

[0083] Figure 3 is a schematic process flow diagram of a method for forming a carbon layer according to another embodiment of the present invention.

[0084] First, a substrate, particularly a substrate having a layer including silicon, is loaded into the chamber, and a carbon-containing gas is supplied onto the substrate (S10).

[0085] This process (S10) is identical to the aforementioned FIGS. 1 and 2, so a repeated explanation will be omitted.

[0086] Next, a first plasma treatment step is performed to supply an inert gas on the substrate, particularly, on the layer including the silicon, and to form a first plasma (S20).

[0087] This process (S20) is also identical to the previously described Figures 1 and 2, so a repeated explanation will be omitted.

[0088] Next, after the first plasma treatment step (S20), a second plasma treatment step is performed in which an oxygen (O2) containing gas is supplied into the chamber and a second plasma is formed (S30).

[0089] This process (S30) is also identical to the previously described Figures 1 and 2, so a repeated explanation will be omitted.

[0090] Next, the impurity layer generated by the second plasma of the oxygen (O2) containing gas is removed (S40).

[0091] In the second plasma treatment step (S30) described above, when a second plasma of an oxygen (O2)-containing gas is formed, the first thin film layer on the upper layer can be etched or removed in the form of carbon dioxide (CO2) by combining with oxygen. However, at this time, a constituent material of the substrate, for example, a silicon (Si) material, may diffuse upwards by the oxygen (O2) plasma and chemically combine with the oxygen (O2), and accordingly, impurities such as silicon oxide (SiO2) may be generated on the upper surface of the first thin film layer.

[0092] Accordingly, in another embodiment of the present invention, an impurity layer removal step (S40) is additionally performed to remove impurities such as silicon oxide (SiO2) generated on the upper surface of the first thin film layer.

[0093] According to one embodiment, the impurity layer removal step (S40) may include a fourth plasma treatment process of supplying a hydrogen (H2)-containing gas and forming a fourth plasma. When the fourth plasma of the hydrogen (H2)-containing gas is formed, the silicon oxide (SiO2) reacts with hydrogen, breaking the bond between silicon and oxygen to generate Si and H2O, and thus the silicon oxide may be removed.

[0094] At this time, the first RF power for forming the first plasma in the first plasma treatment step (S20) and the fourth RF power for forming the fourth plasma in the fourth plasma treatment step as the impurity layer removal step (S40) may be different. Specifically, the first RF power may be greater than the fourth RF power.

[0095] According to another embodiment, the impurity layer removal step (S40) may include a process of supplying an etching gas. For example, when a fluorine-containing gas such as NF3 is supplied, the silicon oxide (SiO2) may be etched by the fluorine-containing gas, thereby removing the silicon oxide.

[0096] Meanwhile, although not specifically shown, a step of supplying a purge gas or a step of pumping the supplied process gas may be performed between the step of supplying the carbon-containing gas (S10) and the first plasma treatment step (S20).

[0097] Additionally, a step of supplying purge gas or a step of pumping the supplied process gas may be performed between the first plasma treatment step (S20) and the second plasma treatment step (S30).

[0098] Additionally, a step of supplying purge gas or a step of pumping the supplied process gas may be performed between the second plasma treatment step (S30) and the impurity layer removal step (S40).

[0099] Figure 4 is a schematic process flow diagram of a method for forming a carbon layer according to another embodiment of the present invention.

[0100] First, a substrate, particularly a substrate having a layer including silicon, is loaded into the chamber, and a carbon-containing gas is supplied onto the substrate (S10).

[0101] This process (S10) is identical to the aforementioned FIGS. 1, 2, and 3, so a repeated explanation will be omitted.

[0102] Next, a first plasma treatment step is performed to supply an inert gas onto the substrate, particularly, the layer including the silicon, and form a first plasma (S20).

[0103] This process (S20) is also identical to the previously described FIGS. 1, 2, and 3, so a repeated explanation will be omitted.

[0104] Next, a third plasma treatment step is performed to supply a hydrogen-containing gas into the chamber and form a third plasma (S25).

[0105] This process (S20) is identical to the previously described Fig. 2, so a repeated explanation will be omitted.

[0106] Next, a second plasma treatment step is performed to supply oxygen (O2) containing gas into the chamber and form a second plasma (S30).

[0107] This process (S20) is identical to the aforementioned FIGS. 1, 2, and 3, so a repeated explanation will be omitted.

[0108] Next, the impurity layer generated by the second plasma of the oxygen (O2) containing gas is removed (S40).

[0109] This process (S20) is identical to the previously described Fig. 3, so a repeated explanation will be omitted.

[0110] After the carbon-containing gas supply step (S10), the first plasma treatment step (S20) of the inert gas, and the third plasma treatment step (S25) of the hydrogen-containing gas are repeatedly performed multiple times, the second plasma treatment step (S30) of the oxygen-containing gas and the impurity layer removal step (particularly, the fourth plasma treatment of the hydrogen-containing gas) (S40) are performed as one cycle, and by repeating such one cycle, a carbon layer of multiple atomic layers from which defects have been removed can be obtained. In some cases, a carbon layer of a single atomic layer can also be obtained.

[0111] Alternatively, the carbon-containing gas supply step (S10), the first plasma treatment step (S20) of the inert gas, the third plasma treatment step (S25) of the hydrogen-containing gas, the second plasma treatment step (S30) of the oxygen-containing gas, and the impurity layer removal step (particularly, the fourth plasma treatment of the hydrogen-containing gas) (S40) may be performed as one cycle, and such one cycle may be repeatedly performed.

[0112] By repeating this cycle, as the carbon-containing gas is repeatedly supplied, carbon atoms are repeatedly supplied to the first thin film layer constituting the carbon layer, thereby filling the gaps in the first thin film layer, and thus the film quality of the carbon layer ultimately obtained can be further improved.

[0113] Meanwhile, although not specifically shown, a step of supplying a purge gas or a step of pumping the supplied process gas may be performed between the step of supplying the carbon-containing gas (S10) and the first plasma treatment step (S20).

[0114] Additionally, a step of supplying purge gas or a step of pumping the supplied process gas may be performed between the first plasma treatment step (S20) and the third plasma treatment step (S25).

[0115] Additionally, a step of supplying purge gas or a step of pumping the supplied process gas may be performed between the third plasma treatment step (S25) and the second plasma treatment step (S30).

[0116] Additionally, a step of supplying purge gas or a step of pumping the supplied process gas may be performed between the second plasma treatment step (S30) and the impurity layer removal step (S40).

[0117] Figure 5 is a schematic diagram of a carbon layer forming device according to one embodiment of the present invention.

[0118] As can be seen in Fig. 5, a carbon layer forming device (1) according to one embodiment of the present invention comprises a chamber (2), a substrate support unit (3), a gas injection unit (4), a gas storage unit (5), and a power supply unit (6).

[0119] The chamber (2) above provides an internal space, and in particular, provides a processing space (PS) for a carbon layer formation process. Although not specifically illustrated, the chamber (2) may have a structure including an upper dome and a lower dome.

[0120] The chamber (2) may be equipped with an exhaust port (not shown) for exhausting process gases remaining from the processing space (PS). In addition, a heater (not shown) capable of controlling the temperature inside the chamber (2) may be additionally installed in the chamber (2), for example, in the substrate support member (3).

[0121] The above substrate support member (3) can be coupled to the chamber (2) inside the chamber (2).

[0122] The substrate support member (3) supports one or more substrates (10), particularly one or more substrates (10) having a layer including silicon on which the aforementioned carbon layer is formed. The substrate support member (3) can support one or more substrates (10), and thus, carbon layers can be formed on multiple substrates (10) at once.

[0123] The above gas injection unit (4) is positioned inside the chamber (2) opposite the substrate support unit (3) and injects gas toward the substrate support unit (3). For example, the gas injection unit (4) may be positioned above the substrate support unit (3) and inject process gas downward toward the substrate support unit (3). The processing space (PS) is provided between the gas injection unit (4) and the substrate support unit (3).

[0124] The above gas injection unit (4) can be coupled to a chamber lid (not shown). The chamber lid can be coupled to the chamber (2) so as to cover the upper portion of the chamber (2).

[0125] The above gas injection unit (4) can be connected to the gas storage unit (5). Accordingly, the gas injection unit (4) can receive process gas from the gas storage unit (5) and inject the supplied process gas toward the substrate support unit (3).

[0126] The above gas injection unit (4) can be connected to a power supply unit (6). Accordingly, plasma can be generated inside the chamber (2) using plasma power supplied from the power supply unit (6).

[0127] The above gas injection unit (4) may include a first gas injection unit (4a) and a second gas injection unit (4b).

[0128] 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) via a pipe or hose, and the other side of the first gas injection unit (4a) can be connected to the processing space (PS). Accordingly, the first gas supplied from the gas storage unit (5) can move along the first gas path of the first gas injection unit (4a) and then be injected into the processing space (PS).

[0129] The above 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).

[0130] The above second gas injection unit (4b) is for injecting a second gas. The second gas and the first gas may be different gases.

[0131] The first gas and the second gas may include at least one of a carbon-containing gas, an inert gas, an oxygen-containing gas, and a hydrogen-containing gas.

[0132] One side of the second gas injection unit (4b) is connected to the gas storage unit (5) via a pipe or hose, and the other side of the second gas injection unit (4b) can be connected to the processing space (PS). Accordingly, the second gas supplied from the gas storage unit (5) can move along the second gas path of the second gas injection unit (4b) and then be injected into the processing space (PS).

[0133] The above 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).

[0134] 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).

[0135] 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).

[0136] The first gas injection unit (4a) and the second gas injection unit (4b) can inject gas toward different areas in the processing space (PS).

[0137] 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.

[0138] 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.

[0139] 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.

[0140] FIG. 6 is a schematic diagram of an electronic device according to one embodiment of the present invention to which a carbon layer is applied, and relates to a solar cell according to one embodiment.

[0141] As can be seen in FIG. 6, 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).

[0142] 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).

[0143] The above substrate (510) may be made of a transparent material such as glass or plastic, but is not necessarily limited thereto.

[0144] The first electrode (520) may be formed using a deposition process such as atomic layer deposition (ALD). The first electrode (520) may be formed of the carbon layer described above.

[0145] The above first conductive charge transport layer (530) may be formed as a hole transport layer or an electron transport layer.

[0146] 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.

[0147] 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.

[0148] 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.

[0149] 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).

[0150] 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).

[0151] 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.

[0152] 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.

[0153] In the above ABX3, the B is composed of the divalent cation.

[0154] In the above ABX3, X is composed of at least one halogen compound.

[0155] The above amine series compound may be selected from the group consisting of methylamine, ethylamine, and phenethylamine.

[0156] The above amidine series compound may be composed of formamidine.

[0157] 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.

[0158] Specifically, the organometallic compound containing the divalent cation is represented by the following chemical formula 1:

[0159] Chemical Formula 1

[0160]

[0161] (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.

[0162] It can be composed of a compound expressed as .

[0163] 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.

[0164] The above hydrogen halide can be selected from the group consisting of HI, HBr, Hf, and HCl.

[0165] 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.

[0166] 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.

[0167] 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.

[0168] In the above CABX3, the C may be composed of at least one alkali metal.

[0169] 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.

[0170] In the above CABX3, the B is composed of the divalent cation, and the X is composed of at least one halogen compound.

[0171] 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.

[0172] The above alkali metal series compound has the following chemical formula 2:

[0173] Chemical Formula 2

[0174]

[0175] (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)

[0176] It can be composed of a compound expressed as .

[0177] 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.

[0178] The above second conductive charge transport layer (550) may be formed as an electron transport layer or a hole transport layer.

[0179] 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.

[0180] 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.

[0181] 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).

[0182] 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.

[0183] The above second metal (570) can be patterned into a predetermined shape so that sunlight can enter the inside of the cell.

[0184] The above second electrode (570) can be formed by patterning the above-described carbon layer.

[0185] Although not specifically illustrated, a solar cell according to an embodiment of the present invention in which a carbon layer is applied as an electrode may include, but is not limited to, a III-V solar cell and a tandem solar cell.

[0186] Meanwhile, the aforementioned graphene can also be used as a semiconductor layer, such as an active layer of a thin film transistor. Fig. 7 is a schematic cross-sectional view of a thin film transistor according to another embodiment of the present invention to which a carbon layer is applied.

[0187] As can be seen in Fig. 7, a gate electrode (220) is formed on a substrate (S), a gate insulating film (210) is formed on the gate electrode (220), an active layer (230) made of the aforementioned carbon layer is formed on the gate insulating film (210), and a source electrode (240) and a drain electrode (250) are formed on the active layer (230) to form a thin film transistor (200) having a bottom gate structure. Alternatively, a thin film transistor having a top gate structure may be formed by forming an active layer (230) made of the aforementioned carbon layer on a substrate (S), forming a gate insulating film (210) on the active layer (230), forming a gate electrode (220) on the gate insulating film (210), forming an interlayer insulating film on the gate electrode (220), and forming a source electrode (240) and a drain electrode (250) electrically connected to the gate electrode (220) on the interlayer insulating film.

[0188] 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 (220), the source electrode (240) and the drain electrode (250) may be formed of the above-described carbon layer.

[0189] 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 supplying a carbon-containing gas onto a first layer containing silicon; A first plasma treatment step of supplying an inert gas on the first layer and forming a first plasma; and A method for forming a carbon layer, comprising, after the first plasma treatment step, a second plasma treatment step of supplying an oxygen-containing gas and forming a second plasma.

2. In paragraph 1, A method for forming a carbon layer, further comprising a step of forming a silicon oxide layer or a silicon layer on the first layer prior to the step of supplying the carbon-containing gas.

3. In paragraph 1, A method for forming a carbon layer, characterized in that the step of supplying the carbon-containing gas and the first plasma treatment step are performed simultaneously.

4. In paragraph 3, A method for forming a carbon layer, comprising: a step of supplying the carbon-containing gas; and a third plasma treatment step of supplying a hydrogen (H2)-containing gas and forming a third plasma after the first plasma treatment step and before the second plasma treatment step.

5. In paragraph 4, A method for forming a carbon layer, characterized in that the step of supplying the carbon-containing gas, the first plasma treatment step, and the third plasma treatment step are performed multiple times.

6. In paragraph 1, A method for forming a carbon layer further comprising a fourth plasma treatment step of supplying a hydrogen-containing gas and forming a fourth plasma after the second plasma treatment step.

7. In paragraph 5, It further includes a fourth plasma treatment step of supplying a hydrogen-containing gas and forming a fourth plasma after the second plasma treatment step, A method for forming a carbon layer, characterized in that the process of performing the step of supplying the carbon-containing gas, the first plasma treatment step, and the third plasma treatment step multiple times, and then performing the second plasma treatment step and the fourth plasma treatment step is performed as one cycle, and the one cycle is repeatedly performed.

8. In paragraph 1, A method for forming a carbon layer, comprising an additional step of supplying a fluorine-containing etching gas after the second plasma treatment step.

9. In paragraph 5, A method for forming a carbon layer, characterized in that the second plasma treatment step is performed after the step of supplying the carbon-containing gas, the first plasma treatment step, and the third plasma treatment step are performed multiple times.

10. In paragraph 4, It further includes a fourth plasma treatment step of supplying a hydrogen-containing gas and forming a fourth plasma after the second plasma treatment step, A method for forming a carbon layer, characterized in that the step of supplying the carbon-containing gas, the first plasma treatment step, the third plasma treatment step, the second plasma treatment step, and the fourth plasma treatment step are performed as one cycle, and the one cycle is performed multiple times.

11. In paragraph 4, It further includes a fourth plasma treatment step of supplying a hydrogen-containing gas and forming a fourth plasma after the second plasma treatment step, A method for forming a carbon layer, characterized in that the first plasma treatment step, the third plasma treatment step, the second plasma treatment step, and the fourth plasma treatment step are performed at a temperature of 500°C or less.

12. In paragraph 1, A method for forming a carbon layer, characterized in that the inert gas comprises at least one of argon (Ar) gas, neon (Ne) gas, helium (he) gas, krypton (Kr) gas, radon (Rn) gas, and xenon (Xe) gas.

13. In paragraph 1, A method for forming a carbon layer, characterized in that it further comprises a step of supplying a purge gas or pumping a process gas between the first plasma treatment step and the second plasma treatment step.

14. In paragraph 4, A method for forming a carbon layer, characterized in that it further comprises a step of supplying a purge gas or pumping a process gas between the first plasma treatment step and the third plasma treatment step, and between the third plasma treatment step and the second plasma treatment step.

15. In paragraph 6, A method for forming a carbon layer, characterized in that it further comprises a step of supplying a purge gas or pumping a process gas between the first plasma treatment step and the second plasma treatment step, and between the second plasma treatment step and the fourth plasma treatment step.

16. In paragraph 1, A method for forming a carbon layer, characterized in that the step of supplying the carbon-containing gas, the first plasma treatment step, and the second plasma treatment step are performed multiple times.

17. A substrate processing method using a substrate processing device including a chamber providing an internal space, a substrate support unit supporting one or more substrates in the internal space, and a gas supply unit supplying gas into the chamber, The above method is a substrate treatment method including a carbon layer forming method according to any one of claims 1 to 16 described above.

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