Plasma etching method and method of manufacturing display device

Abstract

A plasma etching method and a method of manufacturing a display device are provided. The plasma etching method reduces redeposition of by-products generated in a process of etching a copper layer. The plasma etching method includes performing a substrate placement operation including placing a substrate on a mounting portion in a chamber of a plasma etching apparatus, the substrate including a conductive layer including copper; performing a first preliminary etching operation including supplying a first etching gas containing a chlorine element into the chamber and applying a first bias voltage to a lower electrode disposed below the substrate; and performing a first etching operation including supplying a second etching gas containing a hydrogen element into the chamber and applying a second bias voltage to the lower electrode, where the first bias voltage is smaller than the second bias voltage.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims priority to and all benefits derived from Korean Patent Application No. 10-2023-0132462, filed on October 5, 2023, the contents of which are incorporated herein by reference in their entirety. Technical Field

[0003] One or more embodiments relate to a plasma etching method and a method of manufacturing a display device, and more particularly, to a plasma etching method capable of reducing redeposition of byproducts generated in an etching process for a copper layer and a method of manufacturing a display device by using the plasma etching method. Background Art

[0004] There is an increasing demand for display devices capable of displaying high-resolution images. In some cases, configuring some display devices to display high-resolution images may include reducing the pixel size of the display device and reducing the size of pixel circuits corresponding to the pixels, respectively. In some cases, configuring such a display device may also include reducing the width of electrodes and / or lines included in the pixel circuits, and therefore, it is desirable to be able to use copper having high conductivity to form electrodes and lines.

[0005] Some methods may use a wet etching process to form electrodes and lines using copper, but in some cases, wet etching may not be effective in supporting precise control of electrode and line features (e.g., width, etc.). Some other methods may include forming electrodes and lines using copper in a plasma etching process. Summary of the invention

[0006] In some plasma etching processes according to the related art, when byproducts generated in the process of etching the copper layer are discharged to the outside of the chamber in a gaseous state, the byproducts lose energy due to contact with the inner surface of the chamber, etc. Therefore, the byproducts may be re-deposited on the inner surface of the chamber in a solid state.

[0007] One or more embodiments include a plasma etching method capable of reducing redeposition of byproducts generated in a process of etching a copper layer and a method of manufacturing a display device. However, the purpose of the description is an example and does not limit the scope of the present disclosure.

[0008] Additional aspects will be set forth in part in the detailed description which follows and, in part, will be obvious from the description, or may be learned by practice of the presented embodiments of the disclosure.

[0009] According to one or more embodiments, a plasma etching method includes: performing a substrate arrangement operation, the substrate arrangement operation including arranging a substrate on a mounting portion in a chamber of a plasma etching device, the substrate including a conductive layer including copper; performing a first preliminary etching operation, the first preliminary etching operation including supplying a first etching gas including a chlorine element into the chamber and applying a first bias voltage to a lower electrode arranged below the substrate; and performing a first etching operation, the first etching operation including supplying a second etching gas including a hydrogen element into the chamber and applying a second bias voltage to the lower electrode, wherein the first bias voltage is less than the second bias voltage.

[0010] The conductive layer may include: a first portion on which a mask is arranged; and a second portion on which the mask is not arranged, the first preliminary etching operation may also include forming a conversion portion by converting copper contained in the second portion into copper chloride, and the first etching operation may also include removing the conversion portion.

[0011] The first preliminary etching operation may further include converting the copper contained in the second portion into copper chloride through a reaction corresponding to at least one of the following reaction formulas:

[0012] Reaction 1: Cu(S)+1 / 2Cl 2 (g) →CuCl(s);

[0013] Reaction 2: CuCl(s)+1 / 2Cl 2 (g) →CuCl 2 (s);

[0014] Reaction 3: Cu(S)+Cl 2 (g) →CuCl 2 (g); and

[0015] Reaction 4: 3Cu(S)+3 / 2Cl 2 (g) →Cu 3 Cl 3 (g).

[0016] The first etching operation may further include removing the converted portion by a reaction corresponding to at least one of the following reaction formulas:

[0017] Reaction 5: 3CuCl 2 (s)+3H(g)→Cu 3 Cl 3 (g) + 3HCl (g);

[0018] Reaction 6: CuCl 2 (s)+3H(g)→CuH(g)+2HCl(g);

[0019] Reaction 7: CuCl(s)+2H(g)→CuH(g)+HCl(g); and

[0020] Reaction 8: 3CuCl 2 (s)+3 / 2H 2 (g) →Cu 3 Cl 3 (g) + 3HCl (g).

[0021] The first etching operation may further include stopping applying the second bias voltage to the lower electrode in response to a temperature of the mounting portion being greater than 10°C.

[0022] The first etching operation may further include stopping supplying a second etching gas including a hydrogen element into the chamber in response to a temperature of the mounting portion being greater than 10°C.

[0023] The plasma etching method may also include: performing a second preliminary etching operation, the second preliminary etching operation including supplying a first etching gas containing a chlorine element into a chamber and applying a first bias voltage to a lower electrode arranged below the substrate; and performing a second etching operation, the second etching operation including supplying a second etching gas containing a hydrogen element into the chamber and applying a second bias voltage to the lower electrode.

[0024] The conductive layer may include a first portion on which a mask is arranged; and a second portion on which no mask is arranged, the second portion may include a first sub-portion adjacent to a surface of the second portion and a second sub-portion other than the first sub-portion, the first preliminary etching operation may also include forming a first conversion sub-portion by converting copper contained in the first sub-portion into copper chloride, and the first etching operation may also include removing the first conversion sub-portion.

[0025] The second preliminary etching operation may further include forming a second converted sub-portion by converting copper included in the second sub-portion into copper chloride, and the second etching operation may further include removing the second converted sub-portion.

[0026] The thickness of the first sub-portion may be from about or greater to less than about

[0027] According to one or more embodiments, a method for manufacturing a display device includes: performing a substrate arrangement operation, the substrate arrangement operation including arranging a substrate on a mounting portion in a chamber of a plasma etching device, the substrate including a conductive layer including copper; performing a first preliminary etching operation, the first preliminary etching operation including supplying a first etching gas including a chlorine element into the chamber and applying a first bias voltage to a lower electrode arranged below the substrate; and performing a first etching operation, the first etching operation including supplying a second etching gas including a hydrogen element into the chamber and applying a second bias voltage to the lower electrode, wherein the first bias voltage is less than the second bias voltage.

[0028] The conductive layer may include: a first portion on which a mask is arranged; and a second portion on which the mask is not arranged, the first preliminary etching operation may also include forming a conversion portion by converting copper contained in the second portion into copper chloride, and the first etching operation may also include removing the conversion portion.

[0029] The first preliminary etching operation may further include converting the copper contained in the second portion into copper chloride through a reaction corresponding to at least one of the following reaction formulas:

[0030] Reaction 1: Cu(S)+1 / 2Cl 2 (g) →CuCl(s);

[0031] Reaction 2: CuCl(s)+1 / 2Cl 2 (g) →CuCl 2 (s);

[0032] Reaction 3: Cu(S)+Cl 2 (g) →CuCl 2 (g); and

[0033] Reaction 4: 3Cu(S)+3 / 2Cl 2 (g) →Cu 3 Cl 3 (g).

[0034] The first etching operation may further include removing the converted portion by a reaction corresponding to at least one of the following reaction formulas:

[0035] Reaction 5: 3CuCl 2 (s)+3H(g)→Cu 3 Cl 3 (g) + 3HCl (g);

[0036] Reaction 6: CuCl 2 (s)+3H(g)→CuH(g)+2HCl(g);

[0037] Reaction 7: CuCl(s)+2H(g)→CuH(g)+HCl(g); and

[0038] Reaction 8: 3CuCl 2 (s)+3 / 2H 2 (g) →Cu 3 Cl 3 (g) + 3HCl (g).

[0039] The first portion may correspond to the gate electrode.

[0040] The first portion may correspond to at least one of the source electrode and the drain electrode.

[0041] The first etching operation may further include stopping applying the second bias voltage to the lower electrode in response to a temperature of the mounting portion being greater than 10°C.

[0042] The first etching operation may further include stopping supplying a second etching gas including a hydrogen element into the chamber in response to a temperature of the mounting portion being greater than 10°C.

[0043] The method may also include: performing a second preliminary etching operation, the second preliminary etching operation including supplying a first etching gas containing a chlorine element into a chamber and applying a first bias voltage to a lower electrode arranged below the substrate; and performing a second etching operation, the second etching operation including supplying a second etching gas containing a hydrogen element into the chamber and applying a second bias voltage to the lower electrode.

[0044] The conductive layer may include: a first portion on which a mask is arranged; and a second portion on which no mask is arranged, the second portion may include a first sub-portion adjacent to a surface of the second portion and a second sub-portion other than the first sub-portion, the first preliminary etching operation may also include forming a first conversion sub-portion by converting copper contained in the first sub-portion into copper chloride, the first etching operation may also include removing the first conversion sub-portion, the second preliminary etching operation may also include forming a second conversion sub-portion by converting copper contained in the second sub-portion into copper chloride, and the second etching operation may also include removing the second conversion sub-portion.

[0045] The thickness of the first sub-portion may be from about or greater to less than about BRIEF DESCRIPTION OF THE DRAWINGS

[0046] The above and other aspects, features and advantages of certain embodiments of the present disclosure will become more apparent from the following description taken in conjunction with the accompanying drawings, in which:

[0047] Figure 1is a block diagram of an example of a plasma etching apparatus using a plasma etching method according to an embodiment;

[0048] Figure 2 is a flow chart of a plasma etching method according to an embodiment;

[0049] Figures 3 to 5 Is used to describe Figure 2 A view of a plasma etching method;

[0050] Figure 6 is a flow chart of a plasma etching method according to an embodiment;

[0051] Figures 7 to 11 Is used to describe Figure 6 A view of a plasma etching method; and

[0052] Fig.12 is a schematic cross-sectional view of a display device manufactured according to an embodiment. DETAILED DESCRIPTION

[0053] Reference will now be made in detail to embodiments, examples of which are illustrated in the accompanying drawings, wherein similar reference numerals refer to similar elements throughout. In this regard, the present embodiments may have different forms and should not be construed as being limited to the description set forth herein. Therefore, embodiments are described herein only by reference to the figures to explain the aspects of this description. As used herein, the term "and / or" includes any and all combinations of one or more of the relevant listed items. Throughout this disclosure, the expression "at least one of a, b, and c" means only a, only b, only c, both a and b, both a and c, both b and c, all of a, b, and c, or variations thereof.

[0054] Although the present disclosure can have various modifications and alternative forms, the embodiments supported by the present disclosure are shown in the accompanying drawings by way of example and will be described in detail herein. By referring to the embodiments described in detail below and the accompanying drawings, the effects and characteristics of the present disclosure and the methods for achieving them will become apparent. However, the present disclosure is not limited to the embodiments disclosed below and can be implemented in various forms.

[0055] It will be understood that although the terms "first", "second", etc. may be used herein to describe various components, these components should not be limited by these terms. These components are used to distinguish one component from another component and are not limited thereto.

[0056] As used herein, the singular expressions “a”, “an” and “the” are intended to include the plural forms as well, unless the context clearly indicates otherwise.

[0057] It will also be understood that the terms “comprises” and / or “comprising” as used herein specify the presence of stated features or components, but do not exclude the presence or addition of one or more other features or components.

[0058] In the present disclosure, the expression "A and / or B" may indicate A, B, or A and B. In addition, the expression "at least one of A and B" may indicate A, B, or A and B.

[0059] In the present disclosure, when an element such as a layer, film, region, plate, etc. is referred to as being “on” another element, the reference may indicate not only a case where the element is “directly on” the other element but also a case where another element is located between the element and the other element.

[0060] In the present disclosure, it will be understood that when an element, region or layer is referred to as being connected to another element, region or layer, the element, region or layer can be directly and / or indirectly connected to the other element, region or layer. For example, it will be understood that in the present disclosure, when an element, region or layer is referred to as being in contact with or electrically connected to another element, region or layer, the element, region or layer can be directly and / or indirectly in contact with or electrically connected to another element, region or layer.

[0061] In the present disclosure, the x-axis, y-axis, and z-axis may not be limited to the three axes of the rectangular coordinate system and may be interpreted in a broader sense. For example, the x-axis, y-axis, and z-axis may be perpendicular to each other, or may represent different directions that are not perpendicular to each other.

[0062] In the present disclosure, when a specific embodiment can be implemented in different ways, the specific process order can be performed differently from the described order. For example, two processes described in succession can be performed substantially simultaneously or in the reverse order of the described order.

[0063] In the present disclosure, the expression "in a plan view" means when an object is viewed downward. That is, for example,

[0064] In the present disclosure, “in a plan view” may mean “when an object is observed in a direction perpendicular to a substrate”.

[0065] The terms "about" or "approximately" as used herein include the stated value, and include an appropriate range of deviations for the particular value as determined by one of ordinary skill in the art, taking into account the errors associated with the measurements and the measurements of a particular quantity. For example, the term "about" can mean within one or more standard deviations, or within ±30%, 20%, 10%, 5% of the stated value.

[0066] As used herein, the term "substantially the same" means approximately or actually the same (eg, within a threshold difference amount).

[0067] Hereinafter, embodiments of the present disclosure will be described in detail with reference to the accompanying drawings. In the description with reference to the accompanying drawings, the same reference numerals are assigned to the same or substantially the same components, and the description will not be repeated. For ease of explanation, the elements in the accompanying drawings may have an enlarged or reduced size. For example, for ease of explanation, the size and thickness of the elements in the accompanying drawings are randomly indicated, and therefore, the present disclosure is not necessarily limited to the illustrations of the accompanying drawings.

[0068] Figure 1 2 is a block diagram of an example of a plasma etching apparatus 1 using a plasma etching method according to an embodiment. The plasma etching method according to an embodiment may be performed by the plasma etching apparatus 1 .

[0069] refer to Figure 1 The plasma etching apparatus 1 may include a chamber 10, a mounting portion 20, a lower electrode 30, an upper electrode 40, a power supply portion 50, a gas supply portion 60, and a controller 70. The plasma etching apparatus 1 may further include a cooling portion 80.

[0070] The plasma etching device 1 may be, for example, an inductively coupled plasma (ICP) etching device. However, the embodiments of the present disclosure are not limited thereto. For example, the plasma etching device 1 may be a capacitively coupled plasma (CCP) etching device or a microwave plasma etching device.

[0071] A space may be formed inside the chamber 10, and a portion of the space may be open. In some aspects, a gate valve (not shown) may be formed in the open portion of the chamber 10. In this case, for example, according to the operation of the gate valve, the open portion of the chamber 10 may be opened or closed. Therefore, relative to the substrate, the chamber 10 can provide a space separated from the outside. That is, for example, the chamber 10 can provide a closed space so that a plasma etching process is performed on the substrate. The chamber 10 may generally have a square column shape. However, embodiments of the present disclosure are not limited thereto. For example, the chamber 10 may have a cylindrical shape. The chamber 10 may include a lower wall, an upper wall, and a side wall defining a space formed inside the chamber 10, as described herein.

[0072] The substrate may include a display substrate, a semiconductor substrate, a glass substrate, etc. A copper layer to be etched to form an electrode and / or a line may be formed on the substrate, and a mask may be formed or arranged on the copper layer. The mask may define a portion of the copper layer that is to be etched. The mask may include a hard mask containing a metal, silicon oxide, etc., and may be formed of a photoresist. In addition to the copper layer, one or more patterned or non-patterned layers may be formed or arranged on the substrate. One or more patterned or non-patterned layers may be suitable for a specific device (for example, a display device DA formed in association with one or more plasma etching methods described herein (see Fig.12 )) of any layer.

[0073] The mounting portion 20 may support a substrate. For example, a substrate may be mounted on the mounting portion 20. In some aspects, the mounting portion 20 may be formed as a plate fixed in the chamber 10. Alternatively, the mounting portion 20 may be formed as a shuttle on which the substrate is mounted and can move linearly in the chamber 10. The mounting portion 20 may include an electrostatic chuck (not shown) that can be controlled to fix the substrate to the mounting portion 20. The electrostatic chuck may fix the substrate to the mounting portion 20 by using an electrostatic adsorption force.

[0074] The lower electrode 30 may be disposed under and / or in the mounting portion 20 . Figure 1 The lower electrode 30 is illustrated as being arranged below the mounting portion 20 as a separate element separated from the mounting portion 20. However, the embodiments of the present disclosure are not limited thereto. For example, the mounting portion 20 may have an element corresponding to the lower electrode 30 inside the mounting portion 20. In this case, for example, the plasma etching apparatus 1 may not include the lower electrode 30 as a separate element separated from the mounting portion 20. That is, for example, the lower electrode 30 may be arranged below the substrate.

[0075] The mounting portion 20 may include a circulation channel (not shown) for cooling inside the mounting portion 20. The circulation channel may be connected to the cooling portion 80, and thus, the temperature of the mounting portion 20 may be controlled by the cooling portion 80. For example, the cooling portion 80 may supply a refrigerant to the mounting portion 20 in a circulation manner so that the plasma etching apparatus 1 may maintain or obtain a preset temperature at the mounting portion 20.

[0076] The upper electrode 40 may be arranged on the chamber 10. The upper electrode 40 may be a high frequency (RF) antenna. The antenna may have a flat coil shape. For example, the upper electrode 40 may include an inner coil 40a and an outer coil 40b. The inner coil 40a and the outer coil 40b may have a spiral shape or a concentric circle shape. The inner coil 40a and the outer coil 40b may generate an inductively coupled plasma in the inner space of the chamber 10. In some aspects, two coils are described as an example, but it is understood that the number and arrangement of the coils of the upper electrode 40 described herein and other characteristics are not limited thereto.

[0077] Although not shown, a dielectric window having a disk shape may be disposed between the upper electrode 40 and the chamber 10. The dielectric window may include a dielectric material. For example, the dielectric window may include Al 2 O 3 The dielectric window can transmit power from the upper electrode 40 (antenna) into the chamber 10.

[0078] The power supply part 50 may supply bias power and source power to the lower electrode 30 and the upper electrode 40, respectively. For example, the power supply part 50 may apply source power to the upper electrode 40 in association with forming plasma in the chamber 10. The power supply part 50 may apply bias power to the lower electrode 30.

[0079] The gas supply part 60 may supply gas into the chamber 10 and may exhaust gas from the chamber 10. For example, the gas supply part 60 may include a gas supply pipe, a flow controller, and a gas supply source. The gas supply part 60 may supply various gases into the chamber 10 and exhaust various gases from the chamber 10 through the upper part and / or the side surface of the chamber 10. The gas supply part 60 may provide different gases into the chamber 10 at a desired ratio. In detail, the gas supply part 60 may store a plurality of gases and may supply the gases into the chamber 10 through the gas supply pipe. The flow controller may control the flow rate of the gas supply introduced into the chamber 10 through the gas supply pipe. The gas supply part 60 may supply gases used in different processes into the chamber 10. For example, the gas supply part 60 may supply gases used in the preliminary etching process and gases used in the etching process into the chamber 10. According to an embodiment, the gas may include an inert gas.

[0080] The controller 70 may control general functions associated with performing features of the plasma etching apparatus 1. For example, the controller 70 may be connected to the power supply portion 50 and may control the operation of the power supply portion 50. The controller 70 may include a microcomputer and various interfaces, and may control the operation of the power supply portion 50 according to a program and recipe information stored in an external memory or an embedded memory. For example, the controller 70 may execute a program in association with controlling the operation of the power supply portion 50.

[0081] In detail, the controller 70 may control the application of source power to the upper electrode 40. For example, the controller 70 may apply source power to the upper electrode 40 so that the electromagnetic field induced by the upper electrode 40 is applied to the gas injected into the chamber 10, and the application of the electromagnetic field to the gas may cause plasma to be generated. In some aspects, the controller 70 may control the application of bias power to the lower electrode 30. For example, the controller 70 applies bias power to the lower electrode 30 so that the surface of the substrate has a desired voltage and ion energy distribution, and a desired ion flux and etching rate are obtained.

[0082] Figure 1 The plasma etching apparatus 1 including some elements related to the present embodiment is illustrated, but is not limited thereto. Therefore, it is obvious to a person skilled in the art that, in addition to Figure 1 In addition to the components shown in the figure, the plasma etching apparatus 1 may also include other components and other general components that support various aspects of the plasma etching apparatus 1. For example, the plasma etching apparatus 1 may include or may be connected to a control unit configured to control or operate Figure 1 Alternatively, the controller 70 of the plasma etching apparatus 1 may control Figure 1 , other elements except the power supply part 50 shown in the figure. For example, the controller 70 of the plasma etching apparatus 1 may control the operation of the mounting part 20, the gas supply part 60 and / or the cooling part 80. That is, for example, the illustrated plasma etching apparatus 1 is an example, and various modifications may be made as recognized by those skilled in the art.

[0083] Figure 2 is a flow chart of a plasma etching method according to an embodiment. Figures 3 to 5 Is used to describe Figure 2 FIG. 4 is a view of a plasma etching method.

[0084] refer to Figure 2 , the plasma etching method according to the embodiment may include a substrate arrangement operation S10, a first preliminary etching operation S20, and a first etching operation S30. For example, the plasma etching method may include performing the substrate arrangement operation S10, the first preliminary etching operation S20, and the first etching operation S30.

[0085] refer to Figure 3 In the substrate arrangement operation S10, the plasma etching method may include arranging a substrate S on which a conductive layer CON including copper may be formed on the mounting portion 20 in the chamber 10 of the plasma etching apparatus 1. The substrate S may include a display substrate, a semiconductor substrate, a glass substrate, etc. The plasma etching method may include forming the conductive layer CON on the substrate S.

[0086] For example, the conductive layer CON may be formed on the substrate S by sputtering. That is, for example, the plasma etching method may include depositing the conductive layer CON on the substrate S. In other words, the plasma etching method may include arranging the conductive layer CON on the substrate S. The conductive layer CON may include copper. For example, the conductive layer CON may include a copper layer. That is, for example, the conductive layer CON may include a thin layer of copper.

[0087] The plasma etching method may include etching the conductive layer CON to form an electrode and / or a line. To this end, the plasma etching method may include arranging a mask M on the conductive layer CON. The mask M may include a hard mask including a metal, silicon oxide, etc., and may be formed of a photoresist. The mask M may define a portion of the conductive layer CON to be etched.

[0088] In other words, the conductive layer CON may include a first portion CON1 and a second portion CON2. The first portion CON1 may be a portion that is not etched, and the second portion CON2 may be a portion to be etched. That is, for example, the mask M may be arranged on the first portion CON1, and the mask M may not be arranged on the second portion CON2. In other words, the mask M may be arranged so that the mask M is on the first portion CON1 but not on the second portion CON2. The plasma etching method may include forming or arranging one or more patterned or non-patterned layers between the substrate S and the conductive layer CON. The one or more patterned or non-patterned layers may be any layer suitable for a specific device (e.g., a display device DA formed in association with one or more plasma etching methods described herein).

[0089] refer to Figure 4 In the first preliminary etching operation S20, the plasma etching method may include supplying a first etching gas containing chlorine gas into the chamber 10. In the present disclosure, chlorine gas refers to a gas containing chlorine molecules Cl 2 The chlorine gas contains the chlorine element, and therefore, the “first etching gas containing chlorine gas” described herein may be the “first etching gas containing the chlorine element”.

[0090] A portion of the chlorine gas of the first etching gas may form chlorine plasma through the upper electrode 40. Therefore, copper contained in a portion of the conductive layer CON may be converted into copper chloride. For example, the plasma etching method may include converting copper of the second portion CON2 on which the mask M is not disposed into copper chloride, such as CuCl, CuCl 2 or Cu 3 Cl 3 Thus, a CuCl and / or CuCl 2That is, for example, the plasma etching method may include forming the second converted portion CON2' by converting copper of the second portion CON2 into copper chloride.

[0091] In detail, a portion of the chlorine gas of the first etching gas may form chlorine plasma through the upper electrode 40, and the chlorine plasma may include chlorine positive ions and chlorine free radicals. Another portion of the chlorine gas of the first etching gas may be adjacent to the surface of the second portion CON2 or may be absorbed by the surface of the second portion CON2. The chlorine gas adjacent to the surface of the second portion CON2 or absorbed by the surface of the second portion CON2 may react with the copper of the second portion CON2, and the chlorine positive ions and chlorine free radicals may increase the rate of the reaction. That is, for example, the first preliminary etching operation S20 may be a reactive ion etching process. Therefore, for example, the plasma etching method may include converting the copper of the second portion CON2 into copper chloride.

[0092] Generally, the plasma etching method may include reacting copper with chlorine molecules Cl by using one or more of the reaction equations 1 to 4 described herein. 2 The reaction converts copper into copper chloride.

[0093] Reaction 1: Cu(S)+1 / 2Cl 2 (g) →CuCl(s).

[0094] Reaction 2: CuCl(s)+1 / 2Cl 2 (g) →CuCl 2 (s).

[0095] Reaction 3: Cu(S)+Cl 2 (g) →CuCl 2 (g).

[0096] Reaction 4: 3Cu(S)+3 / 2Cl 2 (g) →Cu 3 Cl 3 (g).

[0097] The CuCl produced in reaction 1 and the CuCl produced in reaction 2 2 It can be in solid state, and the CuCl produced in reaction formula 3 2 and Cu generated in reaction 4 3 Cl 3 It can be in gaseous state. The CuCl produced in reaction formula 3 2 and Cu generated in reaction 4 3 Cl 3Therefore, as the reaction proceeds, the copper in the second part CON2 can be converted into CuCl produced in reaction formula 1 and CuCl produced in reaction formula 2. 2 That is, for example, the copper of the second portion CON2 may be converted into copper chloride. Thus, a copper chloride containing CuCl and / or CuCl may be formed. 2 The second conversion part CON2'.

[0098] The plasma etching method may include applying a first bias power in the first preliminary etching operation S20. In detail, in the first preliminary etching operation S20, the plasma etching method may include applying a first bias power to the lower electrode 30. The first bias power applied to the lower electrode 30 in the first preliminary etching operation S20 may be less than the second bias power applied to the lower electrode 30 in the second etching operation S50 to be described herein. The effect achieved by the first bias power being less than the second bias power will be described later herein.

[0099] According to another embodiment, the first etching gas may further include hydrogen. In this case, for example, the hydrogen may be included in the first etching gas in an amount of 10 volume percent (%) or less relative to the total volume of the first etching gas. In an example in which the first etching gas includes hydrogen in an amount greater than 10 volume percent (%) relative to the total volume of the first etching gas, the amount of chlorine included in the first etching gas may be greatly reduced, and thus, the copper of the second portion CON2 and the chlorine molecules Cl 2 The rate of the reaction may be reduced.

[0100] refer to Figure 5 In the first etching operation S30, the plasma etching method may include supplying a second etching gas containing hydrogen gas into the chamber 10. In the present disclosure, hydrogen gas refers to a gas containing hydrogen molecules H 2Gas. Hydrogen gas contains hydrogen element, and therefore, the "second etching gas containing hydrogen gas" described herein may be a "second etching gas containing hydrogen element". In the case of a general plasma etching process, the amount of gas in the chamber 10 may be controlled by simultaneously supplying gas into the chamber 10 and exhausting gas from the chamber 10. Therefore, the plasma etching method may be implemented without providing an additional operation of purging the first etching gas between the first preliminary etching operation S20 and the first etching operation S30. That is, for example, the plasma etching method may include supplying a second etching gas containing hydrogen gas into the chamber 10, and simultaneously exhausting a first etching gas containing chlorine gas from the chamber 10. Therefore, for example, in the first etching operation S30, the plasma etching method may include filling the chamber 10 with a second etching gas containing hydrogen gas. However, embodiments of the present disclosure are not limited thereto, and the plasma etching method may include performing an additional operation of exhausting (purging) the first etching gas between the first preliminary etching operation S20 and the first etching operation S30.

[0101] A portion of the hydrogen gas of the second etching gas may form hydrogen plasma through the upper electrode 40. Therefore, a portion of the conductive layer CON in which copper is converted into copper chloride in the first preliminary etching operation S20 may be removed. For example, the plasma etching method may include removing the second portion CON2 in which copper is converted into copper chloride in the first preliminary etching operation S20. That is, for example, the plasma etching method may include removing CuCl and / or CuCl converted from the copper of the second portion CON2 in the first preliminary etching operation S20. 2 The second conversion part CON2' is formed.

[0102] In detail, a portion of the hydrogen gas of the second etching gas may form hydrogen plasma through the upper electrode 40, and the hydrogen plasma may include hydrogen positive ions and hydrogen radicals. Another portion of the hydrogen gas of the second etching gas may be adjacent to the surface of the second conversion portion CON2' or may be absorbed by the surface of the second conversion portion CON2'. The hydrogen gas adjacent to the surface of the second conversion portion CON2' or absorbed by the surface of the second conversion portion CON2' may react with CuCl and / or CuCl in the second conversion portion CON2'. 2 The first etching operation S30 may be a reactive ion etching process.

[0103] Generally, the plasma etching method may include using one or more of the reaction formulas 5 to 8 described herein to make CuCl or CuCl 2 With hydrogen molecule H 2 or single molecule hydrogen H reaction to remove CuCl or CuCl 2 .

[0104] Reaction 5: 3CuCl 2 (s)+3H(g)→Cu 3 Cl 3 (g) + 3HCl (g).

[0105] Reaction 6: CuCl 2 (s)+3H(g)→CuH(g)+2HCl(g).

[0106] Reaction equation 7: CuCl(s)+2H(g)→CuH(g)+HCl(g).

[0107] Reaction 8: 3CuCl 2 (s)+3 / 2H 2 (g) →Cu 3 Cl 3 (g) + 3HCl (g).

[0108] The Cu generated in reaction equations 5 and 8 3 Cl 3 and HCl may be in a gaseous state, and the CuH and HCl produced in reaction formula 6 and reaction formula 7 may be in a gaseous state. The plasma etching method may include: 3 Cl 3 and HCl are exhausted to the outside of the chamber 10 in a gaseous state. Therefore, the cupric chloride of the second conversion portion CON2' may be removed. That is, for example, the plasma etching method may include etching the conductive layer CON based on the pattern of the mask M. In other words, the second portion CON2 may be removed, and the first portion CON1 may remain.

[0109] When hydrogen plasma is formed, hydrogen molecules H 2 The dissociation rate of the hydrogen molecules H in the cavity 10 may not be high enough (for example, the dissociation rate may be lower than a threshold value). 2 The amount of H may be significantly greater than the amount of single molecule hydrogen H present in the chamber 10, and the reaction of reaction formula 8 may be mainly performed in the chamber 10. However, the reaction of reaction formula 8 may be an endothermic reaction, and in some embodiments, the plasma etching method may include increasing the rate of the reaction of reaction formula 8 according to the additional energy supply.

[0110] For the additional energy supply, the plasma etching method may include applying a second bias power in the first etching operation S30, wherein the second bias power is greater than the first bias power applied in the first preliminary etching operation S20. That is, for example, the plasma etching method may include applying a second bias power to the lower electrode 30 in the first etching operation S30, and the second bias power may be greater than the first bias power. In other words, the first bias power may be less than the second bias power.

[0111] That is, for example, the plasma etching method may include: while supplying a first etching gas mainly containing chlorine gas into the chamber 10, applying a relatively reduced bias power (first bias power) to the lower electrode 30. The plasma etching method may include: while supplying a second etching gas mainly containing hydrogen gas into the chamber 10, applying a relatively increased bias power (second bias power) to the lower electrode 30. In an example, the first bias power may be 25% or less of the source power, and the second bias power may be 50% or more of the source power. That is, for example, when the source power is 2000W, the first bias power may be 500W or less, and the second bias power may be 1000W or more.

[0112] Generally, for plasma etching of a copper layer, a mixed gas mainly containing a halogen-based gas (such as fluorine or chlorine gas, for example) may be used. The mixed gas may also contain hydrogen, nitrogen, helium, argon, etc. suitable for plasma etching. In an example in which a mixed gas containing chlorine is used to plasma etch a copper layer, the chlorine may react with copper to form a byproduct in the form of cupric chloride, for example, CuCl, CuCl 2 or Cu 3 Cl 3 .

[0113] CuCl and CuCl in byproducts 2 In solid state, CuCl and CuCl at normal pressure 2 The boiling point of may be approximately 1000° C. While the plasma etching process is performed, the pressure in the chamber 10 is 10 -2 Support up to 10 -4 Under the support, CuCl and CuCl 2 The boiling point of CuCl can be 250°C or higher. 2 Can be converted into CuH and Cu which can evaporate at room temperature 3 Cl 3 , and can be discharged to the outside of the chamber 10.

[0114] When plasma etches a copper layer, it may be necessary to apply a bias power in order to increase the etching rate. However, when a high bias power is applied, chlorine particles with high energy (e.g., chlorine cations, chlorine radicals, or chlorine molecules Cl)2 ) can be increased. In the example where chlorine particles with high energy react with copper, the generated CuCl and CuCl 2 However, even when CuCl or CuCl 2 During evaporation, the evaporated CuCl or CuCl 2 The evaporated CuCl or CuCl may contact the inner surface of the chamber 10 or the like while being discharged to the outside of the chamber 10 and may lose energy, so that the evaporated CuCl or CuCl 2 It can be redeposited on the inner surface of the chamber 10 in a solid state.

[0115] As the described redeposition continues, the exhaust conditions that maintain the low pressure in chamber 10 may be changed, and when redeposition is excessive (e.g., evaporated CuCl or CuCl redeposited in the solid state) 2 The amount exceeds the threshold), the redeposited CuCl or CuCl 2 The tube (eg, the gas supply tube) included in the gas supply portion 60 may be blocked. For example, the tube may be formed by redeposited CuCl or CuCl 2 In addition, in some cases, the byproducts redeposited on the substrate S may contaminate the substrate S and thus may degrade the quality of the product or reduce the yield of the product. In some other ways, the redeposited CuCl and CuCl are removed. 2 The chamber 10 of the plasma etching apparatus 1 may be heated to 250° C. or higher. Therefore, it may be difficult to effectively remove the redeposited CuCl and CuCl by other methods. 2 .

[0116] However, referring to the embodiments described herein, the plasma etching method may include supplying a first etching gas containing chlorine gas into the chamber 10 in the first preliminary etching operation S20, and may also include supplying a second etching gas containing hydrogen gas into the chamber 10 in the first etching operation S30. In the first preliminary etching operation S20, the plasma etching method may include applying a first bias power to the lower electrode, wherein the first bias power is less than the second bias power applied in the first etching operation S30. Therefore, for example, by using the first bias power at a lower power level as described herein, chlorine particles with high energy (e.g., particles with energy higher than a threshold energy value), such as chlorine cations, chlorine radicals, or chlorine molecules Cl, may not exist. 2 For example, or the number of chlorine particles having high energy may be small (eg, below a threshold amount).

[0117] Thus, for example, when chlorine particles react with copper, the CuCl and CuCl produced from the reaction 2 It may not evaporate. The CuCl and CuCl produced therein2 In some cases where evaporation does occur, the extent of evaporation can be minimized. Thus, the process for etching a copper layer described herein supports the reduction of redeposition of byproducts generated by etching. That is, for example, according to the present embodiment described herein, in which CuCl and CuCl are generated 2 Applying a relatively reduced bias voltage to the lower electrode 30 in the process can minimize the CuCl and CuCl 2 The degree of evaporation is increased and the redeposition of by-products is reduced.

[0118] According to another embodiment, the second etching gas may further include a gas different from hydrogen. For example, the second etching gas may further include helium or argon, which may not react with copper. Therefore, for example, the plasma etching method may include appropriately adjusting the flow rate of the second etching gas.

[0119] According to another embodiment, the second etching gas may further include chlorine. In this case, for example, the chlorine may be included in the second etching gas in an amount of 25 volume percent (%) or less relative to the total volume of the second etching gas. In an example in which the second etching gas includes chlorine in an amount greater than 25 volume percent (%) relative to the total volume of the second etching gas, the newly generated CuCl and CuCl 2 can be evaporated and redeposited. That is, for example, when CuCl and CuCl 2 When it is removed by reacting with hydrogen, the copper exposed to the outside can react with chlorine molecules Cl 2 reaction, and the CuCl and CuCl produced by the reaction 2 Can be evaporated and redeposited.

[0120] Figures 2 to 5 It is illustrated that the copper of the entire second portion CON2 may be converted into copper chloride in the first preliminary etching operation S20, and the entire second portion CON2 may be removed in the first etching operation S30. However, embodiments of the present disclosure are not limited thereto. For example, when the thickness of the conductive layer CON is sufficiently large (e.g., higher than a threshold thickness value), the copper of a portion of the second portion CON2 may be converted into copper chloride in the first preliminary etching operation S20, and a portion of the second portion CON2 may be removed in the first etching operation S30. In this case, for example, the plasma etching method may include repeatedly performing a preliminary etching operation and an etching operation. That is, for example, the plasma etching method may include repeatedly performing a cycle including a preliminary etching operation and an etching operation. In an example, the plasma etching method may include performing the cycle multiple times until one or more target criteria (e.g., a target amount of removal of a portion of the second portion CON2, a target amount of removal of copper chloride, etc.) are met.

[0121] Figure 6is a flow chart of a plasma etching method according to an embodiment. Figures 7 to 11 Is used to describe Figure 6 FIG. 4 is a view of a plasma etching method.

[0122] Figure 6 The plasma etching method includes the following steps: Figure 2 Aspects of the plasma etching method are described herein, and repeated descriptions of similar elements are omitted for brevity. Figure 6 Plasma etching method and Figure 2 The modified embodiment of the plasma etching method corresponds to the embodiment of the present invention, and therefore, the following description is based on Figure 6 Plasma etching method and Figure 2 Hereinafter, for the sake of convenience, the plasma etching method described in this article will not be described. Figures 1 to 5 The aspects described are the same as those described above.

[0123] refer to Figure 6 , the plasma etching method according to the embodiment may include a substrate arrangement operation S10, a first preliminary etching operation S20, a first etching operation S30, a second preliminary etching operation S40, and a second etching operation S50. For example, the plasma etching method may include performing a substrate arrangement operation S10, a first preliminary etching operation S20, a first etching operation S30, a second preliminary etching operation S40, and a second etching operation S50.

[0124] refer to Figure 7 , in a substrate arrangement operation S10, the plasma etching method may include arranging a substrate S on which a conductive layer CON including copper may be formed on a mounting portion 20 in a chamber 10 of a plasma etching apparatus 1. The conductive portion CON may include a first portion CON1 and a second portion CON2. The first portion CON1 may be a portion that is not etched, and the second portion CON2 may be a portion to be etched. That is, for example, a mask M may be arranged on the first portion CON1, and the mask M may not be arranged on the second portion CON2. In other words, the mask M may be arranged so that the mask M is on the first portion CON1, but not on the second portion CON2.

[0125] The second portion CON2 may include a 2-1 portion CON21 (also referred to herein as a first sub-portion of the second portion CON2) and a 2-2 portion CON22 (also referred to herein as a second sub-portion of the second portion CON2). The 2-1 portion CON21 may be a portion of the second portion CON2 in the direction of the mask M, and the 2-2 portion CON22 may be a portion of the second portion CON2 in the direction opposite to the mask M. That is, for example, the 2-1 portion CON21 may be a portion of the second portion CON2 in the direction opposite to the substrate S, and the 2-2 portion CON22 may be a portion of the second portion CON2 in the direction of the substrate S. In other words, the 2-1 portion CON21 may be a portion of the second portion CON2 adjacent to the surface of the second portion CON2, and the 2-2 portion CON22 may be a different portion of the second portion CON2. For example, the 2-2 portion CON22 may be a portion of the second portion CON2 other than the 2-1 portion CON21.

[0126] refer to Figure 8 In the first preliminary etching operation S20, the plasma etching method may include supplying a first etching gas containing chlorine gas into the chamber 10. A portion of the chlorine gas of the first etching gas may form chlorine plasma through the upper electrode 40. Therefore, copper contained in a portion of the conductive layer CON may be converted into copper chloride. For example, copper in a portion of the second portion CON2 on which the mask M is not disposed may be converted into copper chloride, for example, CuCl, CuCl 2 or Cu 3 Cl 3 Therefore, a CuCl and / or CuCl 2 That is, for example, the 2-1 conversion portion CON21' can be formed by converting copper of the 2-1 portion CON21 into copper chloride.

[0127] In detail, in the first preliminary etching operation S20, copper of a portion of the second portion CON2, which portion is adjacent to the surface of the second portion CON2, may be converted into copper chloride. That is, for example, in the first preliminary etching operation S20, copper of the 2-1 portion CON21 may be converted into copper chloride. In other words, in the first preliminary etching operation S20, the surface of the second portion CON2 may be filled with copper chloride. That is, for example, copper on the surface of the second portion CON2 may be converted into CuCl and / or CuCl in a solid state. 2 , and therefore, the surface of the second portion CON2 may be filled with CuCl and / or CuCl 2 .

[0128] The technology described herein may include appropriately adjusting the thickness of the 2-1st conversion portion CON21' according to the process efficiency and the degree of by-product generation during the process. In some embodiments, the thickness of the 2-1st conversion portion CON21' may be from or greater to less than In other words, the thickness of the 2-1st conversion portion CON21' can be to within the range.

[0129] For example, if the thickness of the 2-1st conversion portion CON21' is less than Then, the number of preliminary etching operations and the number of etching operations associated with removing the entire second portion CON2 may be excessively increased (e.g., above a threshold value). In some cases, a portion of the chlorine gas supplied in the etching operation may remain in the preliminary etching operation, and CuCl and / or CuCl may be newly generated in the preliminary etching operation due to the chlorine gas. 2 Therefore, when the number of preliminary etching operations and the number of etching operations excessively increase, CuCl and / or CuCl newly generated in the preliminary etching operations and the etching operations 2 The amount can be increased. In which the thickness of the 2-1 conversion portion CON21 'is In larger examples, the duration associated with converting copper to copper chloride may be excessively increased (eg, above a threshold duration).

[0130] refer to Fig. 9 In the first etching operation S30, the plasma etching method may include supplying a second etching gas containing hydrogen into the chamber 10. A portion of the hydrogen gas of the second etching gas may form hydrogen plasma through the upper electrode 40. Therefore, a portion of the conductive layer CON in which copper is converted into copper chloride in the first preliminary etching operation S20 may be removed by the hydrogen plasma. For example, the 2-1 portion CON21 in which copper is converted into copper chloride in the first preliminary etching operation S20 may be removed. That is, for example, the first etching operation S30 may remove the copper in the second portion CON21 converted into CuCl and / or CuCl in the first preliminary etching operation S20. 2 The formed 2-1 conversion part CON21'.

[0131] In some embodiments, the plasma etching method may include ending the first etching operation S30 when the temperature of the mounting portion 20 is greater than 10° C. In detail, when the temperature of the mounting portion 20 is greater than 10° C., the plasma etching method may include stopping the first etching operation S30, and may further include applying a second bias voltage to the lower electrode 30. At the same time, the process may include stopping the first etching operation S30, and may further include continuing to supply a second etching gas containing hydrogen into the chamber 10.

[0132] As described herein, a portion of the chlorine gas supplied in the etching operation may remain in the preliminary etching operation, and CuCl and / or CuCl may be newly generated in the preliminary etching operation due to the chlorine gas. 2 CuCl and CuCl 2 The plasma etching device 1 is a non-volatile material at room temperature, and the pressure in the chamber 10 is from 10 -2 Support up to 10 -4 Under the support, CuCl and CuCl 2 It can be evaporated when heat of 250° C. or higher is applied thereto.

[0133] However, due to the additional energy supply according to the second bias voltage applied in the first etching operation S30, the temperature of the substrate S may rise. Therefore, for example, even without the additional heat supply, CuCl and / or CuCl 2 Therefore, in order to prevent the newly generated CuCl and / or CuCl 2 In order to prevent evaporation and redeposition of the substrate S, the technology described herein includes suppressing the temperature increase in the substrate S. For example, the technology described herein may include controlling the temperature of the substrate S by controlling the temperature of the mounting portion 20. In detail, the substrate S may be arranged on the mounting portion 20, and therefore, the temperature of the substrate S may be the same as or similar to the temperature of the mounting portion 20. Therefore, the technology described herein may include controlling the temperature of the substrate S by controlling the temperature of the mounting portion 20.

[0134] However, the electron thermal energy or ion bombardment energy in the plasma exhibits a distribution, and therefore, the substrate S may be locally heated to a sufficient temperature to evaporate CuCl and CuCl by particles having higher energy. 2 For example, in an example in which the temperature of the mounting portion 20 is sufficiently lowered to, for example, 10° C. or lower, the temperature of the entire portion of the substrate S may be lower than that of CuCl and CuCl. 2 Therefore, the plasma etching method may include interrupting the application of the second bias voltage when the temperature of the mounting portion 20 is greater than 10° C., which may prevent the newly generated CuCl and / or CuCl 2 That is, the plasma etching method may include stopping the application of the second bias voltage based on the temperature of the mounting portion 20 (eg, when the temperature of the mounting portion 20 is greater than 10° C.).

[0135] refer to Fig.10In the second preliminary etching operation S40, the plasma etching method may include supplying a first etching gas containing chlorine gas into the chamber 10. As in the first preliminary etching operation S20, a portion of the chlorine gas of the first etching gas may form chlorine plasma through the upper electrode 40. Therefore, copper contained in a portion of the conductive layer CON may be converted into copper chloride. For example, copper of the 2-2 portion CON22 on which the mask M is not disposed may be converted into copper chloride, such as CuCl, CuCl 2 or Cu 3 Cl 3 Thus, a CuCl and / or CuCl 2 That is, for example, the 2-2 conversion portion CON22' can be formed by converting copper of the 2-2 portion CON22 into copper chloride.

[0136] In detail, as the 2-1 portion CON21 is removed in the first etching operation S30, the 2-2 portion CON22 may be adjacent to the surface of the second portion CON2. Therefore, the copper of the 2-2 portion CON22 adjacent to the surface of the second portion CON2 may be converted into copper chloride. In other words, in the second preliminary etching operation S40, the surface of the second portion CON2 may be filled with copper chloride. That is, for example, the copper of the surface of the second portion CON2 may be converted into CuCl and / or CuCl in a solid state. 2 , and the surface of the second portion CON2 may be filled with CuCl and / or CuCl 2 .

[0137] refer to Fig.11 In the second etching operation S50, the plasma etching method may include supplying a second etching gas containing hydrogen into the chamber 10. As in the first etching operation S30, a portion of the hydrogen of the second etching gas may form hydrogen plasma through the upper electrode 40. Therefore, in the second etching operation S50, a portion of the conductive layer CON in which copper is converted into copper chloride in the second preliminary etching operation S40 may be removed. For example, in the second etching operation S50, a 2-2 portion CON22 in which copper is converted into copper chloride in the second preliminary etching operation S40 may be removed. That is, for example, in the second etching operation S50, copper in the 2-2 portion CON22 converted into CuCl and / or CuCl in the second preliminary etching operation S40 may be removed. 2 The formed 2-2 conversion part CON22'.

[0138] Figure 6It is illustrated that the plasma etching method according to the embodiment includes two preliminary etching operations and two etching operations. However, the embodiments of the present disclosure are not limited thereto. For example, the embodiments of the present disclosure support changing the preliminary etching operation and the etching operation of the plasma etching method based on the thickness of the copper layer to be etched and the number of times the etching operation is performed. The plasma etching method described in this article may include repeatedly and alternately performing preliminary etching operations and etching operations. That is, for example, the plasma etching method may include repeatedly performing a cycle including a preliminary etching operation and an etching operation. In an example, the plasma etching method may include performing the cycle multiple times until one or more target criteria are met (e.g., achieving target etching, removing a target amount of copper chloride, etc.). For example, for a cycle including a preliminary etching operation and an etching operation, the plasma etching method may include performing the cycle three, four, five or more times.

[0139] In the description of the flowchart in this article, the operations may be performed in an order different from the order shown, or may be performed in a different order or at a different time. Certain operations may also be omitted from the flowchart, one or more operations may be repeated, or other operations may be added to the flowchart.

[0140] Embodiments of the present disclosure support one or more processes (methods, flow charts) that are supported by the features and embodiments described herein. Descriptions of elements that are "arrangeable," "depositable," "formable," etc. include processes (methods, flow charts) and techniques according to example aspects described herein.

[0141] Hereinafter, a display device as one of various electronic devices and electronic components that can be manufactured according to an embodiment of the method described herein will be described. The method described herein can be used to manufacture a display device, such as an organic light emitting display device as an example.

[0142] Fig.12 1 is a schematic cross-sectional view of a display device DA manufactured according to an embodiment. As those skilled in the art will appreciate, the display device DA may include various other elements in addition to the illustrated elements.

[0143] refer to Fig.12 , the display device DA may include a substrate S. The display device DA may include transistors and emission devices formed of various layers formed on the substrate S. In detail, the display device DA may include a substrate S, a pixel circuit layer 200 , a display element layer 300 , and an encapsulation layer 400 .

[0144] The substrate S may include glass, metal, or a polymer resin. The substrate S may have a flexible or bendable property. In this case, for example, the substrate S may include a polymer resin, such as polyethersulfone, polyacrylate, polyetherimide, polyethylene naphthalate, polyethylene terephthalate, polyphenylene sulfide, polyarylate, polyimide, polycarbonate, or cellulose acetate propionate. However, embodiments of the present disclosure support various modifications of the substrate S. For example, the substrate S may have a multilayer structure including a barrier layer and two layers containing a polymer resin described herein. The barrier layer may be between the two layers and may include an inorganic material (such as a silicon oxide (SiO X ), silicon nitride (SiN X ), silicon oxynitride (SiO X N Y ) etc. as an example).

[0145] The pixel circuit layer 200 may be arranged on the substrate S. The pixel circuit layer 200 may include a transistor TFT, an inorganic insulating layer IIL, and an organic insulating layer OIL. The transistor TFT may include a semiconductor layer Act, a gate electrode GE, a source electrode SE, and a drain electrode DE. The inorganic insulating layer IIL may include a gate insulating layer IIL1, a first interlayer insulating layer IIL2, and a second interlayer insulating layer IIL3.

[0146] The semiconductor layer Act may be arranged on the substrate S. The semiconductor layer Act may include polycrystalline silicon. Alternatively, the semiconductor layer Act may include amorphous silicon, an oxide semiconductor, or an organic semiconductor. According to an embodiment, the semiconductor layer Act may include a channel region, a source region, and a drain region, wherein the source region and the drain region are respectively arranged at different sides of the channel region.

[0147] The gate insulating layer IIL1 may be disposed on the semiconductor layer Act and the substrate S. The gate insulating layer IIL1 may include an inorganic insulating material such as SiO X 、SiN X 、SiO X N Y 、Al 2 O 3 、TiO 2 、 2 O 5 , HfO 2 or ZnO x For example, ZnO x Can include ZnO and / or ZnO 2 .

[0148] The gate electrode GE may be arranged on the gate insulating layer IIL1. That is, for example, the gate insulating layer IIL1 may be arranged between the semiconductor layer Act and the gate electrode GE, and thus may provide insulating properties between the semiconductor layer Act and the gate electrode GE. The gate electrode GE may overlap with the channel region of the semiconductor layer Act. The gate electrode GE may include a low-resistance metal material. According to an embodiment, the gate electrode GE may include a conductive material including Mo, Al, Cu, Ti, etc., and may have a single-layer or multi-layer structure including a conductive material. According to an embodiment, the gate electrode GE may have a multi-layer structure of Ti / Cu.

[0149] That is, for example, the gate electrode GE may be formed by stacking a conductive material including Mo, Al, Cu, Ti, etc. on the substrate S and patterning the stacked conductive material. In detail, when copper is used as the gate electrode GE, a copper layer may be formed on the substrate S, for example, by sputtering, etc. That is, for example, a copper layer may be deposited on the substrate S. Then, a mask may be formed or arranged on the copper layer, and the copper layer may be etched using a plasma etching method according to an embodiment described herein to form the gate electrode GE, which is a patterned copper layer. That is, for example, according to the embodiment described herein with reference to Figures 1 to 11 The first portion CON1 of the described embodiment may correspond to the gate electrode GE.

[0150] When etching the copper layer, the temperature of the mounting portion 20 on which the substrate S is mounted may be maintained or lowered so that the temperature is 10° C. or lower, and thus the temperature of the substrate S may be lowered. In addition, hydrogen contained in the gas provided in the etching operation may react with CuCl 2 An endothermic reaction occurs, and thus the temperature of the substrate S may be reduced. Therefore, in the case where the substrate S is a plastic substrate, the substrate S may not be damaged while the copper layer is plasma etched. In some cases, even if the substrate S is damaged by plasma etching of the copper layer, the extent of the damage may be minimized.

[0151] The first interlayer insulating layer IIL2 may be disposed on the gate electrode GE and the gate insulating layer IIL1. The first interlayer insulating layer IIL2 may include an inorganic insulating material such as SiO X 、SiN X 、SiO X N Y 、Al 2 O 3 、TiO 2 、 2 O 5 , HfO 2 or ZnO x For example.

[0152] The source electrode SE and the drain electrode DE may be arranged on the first interlayer insulating layer IIL2. Each of the source electrode SE and the drain electrode DE may be connected to the semiconductor layer Act through a contact hole formed in the gate insulating layer IIL1 and the first interlayer insulating layer IIL2. At least one of the source electrode SE and the drain electrode DE may include a conductive material including Mo, Al, Cu, Ti, etc., and may have a single-layer or multi-layer structure including the conductive material. According to an embodiment, at least one of the source electrode SE and the drain electrode DE may have a multi-layer structure of Ti / Cu / Ti. In an example in which copper is used as at least one of the source electrode SE and the drain electrode DE, at least one of the source electrode SE and the drain electrode DE may be formed by etching the copper layer using the same method as when copper is used as the gate electrode GE. That is, for example, according to reference 1 in this article Figures 1 to 11 The first portion CON1 of the described embodiment may correspond to at least one of the source electrode SE and the drain electrode DE. Therefore, the same description on these aspects is omitted.

[0153] The second interlayer insulating layer IIL3 may be disposed on the source electrode SE, the drain electrode DE, and the first interlayer insulating layer IIL2. The second interlayer insulating layer IIL3 may include an inorganic insulating material such as SiO X 、SiN X 、SiO X N Y 、Al 2 O 3 、TiO 2 、 2 O 5 , HfO 2 or ZnO x For example.

[0154] The organic insulating layer OIL may be disposed on the second interlayer insulating layer IIL3. The organic insulating layer OIL may generally planarize the upper portion of the pixel circuit layer 200. The organic insulating layer OIL may include, for example, an organic material such as acrylic acid, benzocyclobutene (BCB), or hexamethyldisiloxane (HMDSO). Fig.12 The example of illustrative embodiments illustrates that the organic insulating layer OIL includes a single layer, but the embodiments of the present disclosure are not limited thereto, and the organic insulating layer OIL may include a plurality of layers. Therefore, the embodiments of the present disclosure support modifying the organic insulating layer OIL in various ways.

[0155] The display element layer 300 may be arranged on the pixel circuit layer 200. The display element layer 300 may include a display element 310 and a pixel defining layer 320. The display element 310 may be electrically connected to the transistor TFT. The display element 310 may include an organic light emitting diode having a pixel electrode 311, an opposing electrode 313, and an intermediate layer 312 arranged between the pixel electrode 311 and the opposing electrode 313. The intermediate layer 312 may include an emission layer. The description that the display element 310 is electrically connected to the transistor TFT may be understood as the pixel electrode 311 of the organic light emitting diode being electrically connected to the transistor TFT.

[0156] The pixel electrode 311 may contact any one of the source electrode SE and the drain electrode DE through a contact hole formed in the second interlayer insulating layer IIL3 and the organic insulating layer OIL, so that the pixel electrode 311 is electrically connected to the transistor TFT. The pixel electrode 311 may include a conductive oxide such as indium tin oxide (ITO), IZO, zinc oxide (ZnO), indium oxide (In 2 O 3 ), indium gallium oxide (IGO) or aluminum zinc oxide (AZO) as examples. According to another embodiment, the pixel electrode 311 may include a reflective layer including Ag, Mg, Al, Pt, Pd, Au, Ni, Nd, Ir, Cr or a compound of any one of Ag, Mg, Al, Pt, Pd, Au, Ni, Nd, Ir and Cr. According to another embodiment, the pixel electrode 311 may also include a reflective layer including ITO, IZO, ZnO or In above / below the reflective layer described herein. 2 O 3 layer.

[0157] The pixel defining layer 320 may cover the edge of the pixel electrode 311. The pixel defining layer 320 may have a pixel opening portion, and the pixel opening portion may overlap the pixel electrode 311. The pixel opening portion may define an emission area of ​​light emitted from the display element 310. The pixel defining layer 320 may include an organic insulating material and / or an inorganic insulating material. According to some embodiments, the pixel defining layer 320 may include a light blocking material.

[0158] The intermediate layer 312 may be arranged on the pixel electrode 311 and the pixel defining layer 320. The intermediate layer 312 may include a low molecular weight material or a high molecular weight material. In the example where the intermediate layer 312 includes a low molecular weight material, the intermediate layer 312 may have a stacked structure including a hole injection layer (HIL), a hole transport layer (HTL), an emission layer (EML), an electron transport layer (ETL), an electron injection layer (EIL), and any one or combination of other suitable elements for the intermediate layer 312 according to the exemplary aspects of the present disclosure, and the intermediate layer 312 may be formed by using a vacuum deposition method. In the example where the intermediate layer 312 includes a high molecular weight material, the intermediate layer 312 may have a structure including HTL and EML. In some aspects, the HTL may include poly (3,4-ethylenedioxythiophene) (PEDOT), and the EML may include polystyrene (PPV)-based and polyfluorene-based high molecular weight materials.

[0159] The intermediate layer 312 may be formed by a screen printing method, an inkjet printing method, a laser induced thermal imaging method (LITI), etc. However, the intermediate layer 312 is not necessarily limited to the examples described herein, and may have various structures. In some aspects, the intermediate layer 312 may include a layer integrally formed as a single body throughout the plurality of pixel electrodes 311, or may include a layer patterned to correspond to the plurality of pixel electrodes 311, respectively.

[0160] The counter electrode 313 may be disposed on the intermediate layer 312 and the pixel defining layer 320. The counter electrode 313 may be integrally formed as a single body throughout the plurality of organic light emitting diodes and may correspond to the plurality of pixel electrodes 311. The counter electrode 313 may include a substrate including ITO, In 2 O 3 The counter electrode 313 may include a transmissive conductive layer of Mg or IZO, or may include a transflective layer including a metal such as Al or Ag. For example, the counter electrode 313 may include a transflective layer including Mg or Ag.

[0161] In some cases, the display element 310 may be damaged by external moisture or oxygen. The display device DA may include an encapsulation layer 400 that covers the display element 310 and protects the display element 310 from being exposed to external moisture or oxygen. Fig.12 , the encapsulation layer 400 may include a first inorganic encapsulation layer 410 , an organic encapsulation layer 420 , and a second inorganic encapsulation layer 430 .

[0162] The first inorganic encapsulation layer 410 may cover the counter electrode 313 and may include SiO X 、SiN X and / or SiO X N YHowever, according to one or more implementations supported by aspects of the present disclosure, the display device DA may include one or more other layers, such as a capping layer disposed between the first inorganic encapsulation layer 410 and the counter electrode 313. The first inorganic encapsulation layer 410 may be formed along the structure below the first inorganic encapsulation layer 410 (e.g., the capping layer, the counter electrode 313, and other structures described herein), and therefore, reference Fig.12 , the first inorganic encapsulation layer 410 may have a non-flat upper surface.

[0163] The organic encapsulation layer 420 may cover the first inorganic encapsulation layer 410. In some embodiments, unlike the first inorganic encapsulation layer 410, the organic encapsulation layer 420 may have a substantially flat upper surface. The organic encapsulation layer 420 may include one or more materials selected from the group consisting of polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polyimide, polyethylene sulfonate, polyoxymethylene, polyarylate, and hexamethyldisiloxane. The second inorganic encapsulation layer 430 may cover the organic encapsulation layer 420 and may include SiO X 、SiN X and / or SiO X N Y .

[0164] according to Fig.12 In aspects of the multi-layer structure illustrated in FIG, the encapsulation layer 400 includes a first inorganic encapsulation layer 410, an organic encapsulation layer 420, and a second inorganic encapsulation layer 430. In some aspects, for a case where a crack occurs in the encapsulation layer 400 due to the multi-layer structure, the crack may not be connected between the first inorganic encapsulation layer 410 and the organic encapsulation layer 420 or between the organic encapsulation layer 420 and the second inorganic encapsulation layer 430. Therefore, aspects of the display device DA may prevent or minimize the formation of a path caused by the crack, thereby preventing or minimizing any penetration of external moisture or oxygen into the display device DA.

[0165] According to the embodiments as described herein, a plasma etching method and a method of manufacturing a display device capable of reducing redeposition of byproducts generated in a process of etching a copper layer can be realized. However, the scope of the present disclosure is not limited to the effects described herein.

[0166] It should be understood that the embodiments described herein should be considered in a descriptive sense, rather than for limiting purposes. The description of features or aspects within each embodiment should generally be considered to be applicable to other similar features or aspects in other embodiments. Although one or more embodiments have been described with reference to the figures, it will be understood by those of ordinary skill in the art that various changes may be made in form and detail without departing from the scope and spirit as defined in the appended claims.

Claims

1. A plasma etching method, comprising: performing a substrate placement operation, the substrate placement operation comprising placing a substrate on a mounting portion in a chamber of a plasma etching apparatus, the substrate comprising a conductive layer including copper; performing a first preliminary etching operation, the first preliminary etching operation comprising supplying a first etching gas containing a chlorine element into the chamber and applying a first bias voltage to a lower electrode disposed below the substrate; as well as performing a first etching operation, the first etching operation including supplying a second etching gas containing hydrogen element into the chamber and applying a second bias voltage to the lower electrode, Wherein, the first bias voltage is smaller than the second bias voltage.

2. The plasma etching method according to claim 1, wherein: The conductive layer includes: a first portion, on which a mask is arranged; and a second portion, on which the mask is not arranged, The first preliminary etching operation further includes forming a converted portion by converting copper contained in the second portion into copper chloride, and The first etching operation also includes removing the converted portion.

3. The plasma etching method according to claim 2, wherein: The first preliminary etching operation further includes converting the copper contained in the second portion into the copper chloride by a reaction corresponding to at least one of the following reaction formulas: Reaction 1: Cu(s)+1 / 2Cl2(g)→CuCl(s); Reaction 2: CuCl(s)+1 / 2Cl2(g)→CuCl2(s); Reaction 3: Cu(s)+Cl2(g)→CuCl2(g); and Reaction equation 4: 3Cu(s)+3 / 2Cl2(g)→Cu3Cl3(g).

4. The plasma etching method according to claim 2, wherein: The first etching operation further comprises removing the converted portion by a reaction corresponding to at least one of the following reaction formulas: Reaction equation 5: 3CuCl2(s)+3H(g)→Cu3Cl3(g)+3HCl(g); Reaction 6: CuCl2(s)+3H(g)→CuH(g)+2HCl(g); Reaction 7: CuCl(s)+2H(g)→CuH(g)+HCl(g); and Reaction equation 8: 3CuCl2(s)+3 / 2H2(g)→Cu3Cl3(g)+3HCl(g).

5. The plasma etching method according to claim 1, wherein: The first etching operation further includes stopping applying the second bias voltage to the lower electrode in response to a temperature of the mounting portion being greater than 10°C.

6. The plasma etching method according to claim 1, wherein: The first etching operation further includes stopping supplying the second etching gas containing the hydrogen element into the chamber in response to a temperature of the mounting portion being greater than 10°C.

7. The plasma etching method according to claim 1, further comprising: performing a second preliminary etching operation, the second preliminary etching operation comprising supplying the first etching gas containing the chlorine element into the chamber and applying the first bias voltage to the lower electrode disposed below the substrate; as well as A second etching operation is performed, the second etching operation including supplying the second etching gas containing the hydrogen element into the chamber and applying the second bias voltage to the lower electrode.

8. The plasma etching method according to claim 7, wherein: The conductive layer includes: a first portion, on which a mask is arranged; and a second portion, on which the mask is not arranged, The second portion includes a first sub-portion adjacent to a surface of the second portion and a second sub-portion other than the first sub-portion, The first preliminary etching operation further includes forming a first converted sub-portion by converting copper contained in the first sub-portion into copper chloride, The first etching operation also includes removing the first conversion sub-portion, The second preliminary etching operation further includes forming a second converted sub-portion by converting copper contained in the second sub-portion into copper chloride, and The second etching operation further includes removing the second conversion sub-portion.

9. The plasma etching method according to claim 8, wherein: The thickness of the first sub-portion is from or greater to less than 10. A method for manufacturing a display device, the method comprising: performing a substrate placement operation, the substrate placement operation comprising placing a substrate on a mounting portion in a chamber of a plasma etching apparatus, the substrate comprising a conductive layer including copper; performing a first preliminary etching operation, the first preliminary etching operation comprising supplying a first etching gas containing a chlorine element into the chamber and applying a first bias voltage to a lower electrode disposed below the substrate; as well as performing a first etching operation, the first etching operation including supplying a second etching gas containing hydrogen element into the chamber and applying a second bias voltage to the lower electrode, Wherein, the first bias voltage is smaller than the second bias voltage.

11. The method for manufacturing a display device according to claim 10, wherein: The conductive layer includes: a first portion, on which a mask is arranged; and a second portion, on which the mask is not arranged, The first preliminary etching operation further includes forming a converted portion by converting copper contained in the second portion into copper chloride, and The first etching operation also includes removing the converted portion.

12. The method for manufacturing a display device according to claim 11, wherein: The first preliminary etching operation further includes converting the copper contained in the second portion into the copper chloride by a reaction corresponding to at least one of the following reaction formulas: Reaction 1: Cu(s)+1 / 2Cl2(g)→CuCl(s); Reaction 2: CuCl(s)+1 / 2Cl2(g)→CuCl2(s); Reaction 3: Cu(s)+Cl2(g)→CuCl2(g); and Reaction equation 4: 3Cu(s)+3 / 2Cl2(g)→Cu3Cl3(g).

13. The method for manufacturing a display device according to claim 11, wherein: The first etching operation further comprises removing the converted portion by a reaction corresponding to at least one of the following reaction formulas: Reaction equation 5: 3CuCl2(s)+3H(g)→Cu3Cl3(g)+3HCl(g); Reaction 6: CuCl2(s)+3H(g)→CuH(g)+2HCl(g); Reaction 7: CuCl(s)+2H(g)→CuH(g)+HCl(g); and Reaction equation 8: 3CuCl2(s)+3 / 2H2(g)→Cu3Cl3(g)+3HCl(g).

14. The method for manufacturing a display device according to claim 11, wherein: The first portion corresponds to the gate electrode.

15. The method for manufacturing a display device according to claim 11, wherein: The first portion corresponds to at least one of a source electrode and a drain electrode.

16. The method for manufacturing a display device according to claim 10, wherein: The first etching operation further includes stopping applying the second bias voltage to the lower electrode in response to a temperature of the mounting portion being greater than 10°C.

17. The method for manufacturing a display device according to claim 10, wherein: The first etching operation further includes stopping supplying the second etching gas containing the hydrogen element into the chamber in response to a temperature of the mounting portion being greater than 10°C.

18. The method for manufacturing a display device according to claim 10, further comprising: performing a second preliminary etching operation, the second preliminary etching operation comprising supplying the first etching gas containing the chlorine element into the chamber and applying the first bias voltage to the lower electrode disposed below the substrate; as well as A second etching operation is performed, the second etching operation including supplying the second etching gas containing the hydrogen element into the chamber and applying the second bias voltage to the lower electrode.

19. The method for manufacturing a display device according to claim 18, wherein: The conductive layer includes: a first portion, on which a mask is arranged; and a second portion, on which the mask is not arranged, The second portion includes a first sub-portion adjacent to a surface of the second portion and a second sub-portion other than the first sub-portion, The first preliminary etching operation further includes forming a first converted sub-portion by converting copper contained in the first sub-portion into copper chloride, The first etching operation also includes removing the first conversion sub-portion, The second preliminary etching operation further includes forming a second converted sub-portion by converting copper contained in the second sub-portion into copper chloride, and The second etching operation further includes removing the second conversion sub-portion.

20. The method for manufacturing a display device according to claim 19, wherein: The thickness of the first sub-portion is from or greater to less than

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