KR102503788B1 - Etchant and manufacturing method of display device using the same - Google Patents

Abstract

The present invention relates to an etchant composition. One embodiment of the present invention, based on the total weight of the composition, 8.5% to 10% by weight of an inorganic acid compound, 1% to 10% by weight of a hydrogen sulfate compound, 40% to 60% by weight of an organic acid compound, 1% by weight To 5% by weight of a sulfonic acid compound, 1 to 5% by weight of a chelate compound and the balance of water are disclosed.

Description

Etch composition and method for manufacturing a display device using the same {ETCHANT AND MANUFACTURING METHOD OF DISPLAY DEVICE USING THE SAME}

Embodiments of the present invention relate to an etchant composition and a method for manufacturing a display device using the same.

As the display field for visually expressing various electrical signal information develops, various flat panel display devices having excellent characteristics such as thinning, light weight, and low power consumption are being researched and developed. Among them, the organic light emitting display device is attracting attention as a next-generation display device due to advantages such as a wide viewing angle, fast response speed, and the like, as well as being capable of light weight and thinning.

On the other hand, as the display area of the display device gradually increases, various wires and electrodes included in the display device need to be formed of a material having a specific resistance as low as possible. To this end, various wires and electrodes included in the display device may include silver. However, since the wiring or electrode containing silver has weak bonding strength with the layer or film located above or below the wiring or electrode, the wiring or electrode is laminated with a film containing silver and another conductive film to compensate for this. It can be composed of a multi-layered film.

In addition, various wires and electrodes included in the display device may be formed using a patterning process such as a photolithography method including an etching process. When the wires or electrodes are composed of multilayer films having different properties from each other, a simultaneous etching process may be performed. There is a limit to forming a wire or electrode having characteristics. In addition, since the etchant used to etch conventional wires contains phosphoric acid, damage occurs to other wires in the display device due to phosphoric acid during the etching process, and silver ions are reduced and precipitated through this process, resulting in silver particles Defects may occur in wiring or electrodes due to In addition, in order to prevent the generation of silver particles, the silver-containing film and the other conductive film of the multilayer film may be sequentially etched, but the efficiency of the manufacturing process is significantly reduced.

Embodiments of the present invention relate to an etchant composition capable of simultaneously etching a multilayer film including a silver film without containing phosphoric acid and a method of manufacturing a display device using the same.

One embodiment of the present invention discloses an etchant composition comprising an inorganic acid compound, a hydrogen sulfate compound, a sulfonic acid compound, an organic acid compound, and a residual amount of water, and including 50% to 60% by weight of the organic acid compound based on the total weight of the composition. do.

In this embodiment, the hydrogen sulfate compound may include at least one of ammonium hydrogen sulfate, potassium hydrogen sulfate, and sodium hydrogen sulfate.

In this embodiment, the organic acid compound may include at least one of acetic acid, malic acid, citric acid, tartaric acid, lactic acid, formic acid, succinic acid, and fumaric acid.

In this embodiment, the organic acid compound may include a first organic acid compound and a second organic acid compound that are different from each other.

In this embodiment, the first organic acid compound and the second organic acid compound may each be included in an amount of 20% to 30% by weight based on the total weight of the etchant composition.

In this embodiment, the sulfonic acid compound may include at least one of methanesulfonic acid, p-toluenesulfonic acid, benzenesulfonic acid, and aminomethylsulfonic acid.

In this embodiment, a chelate compound may be further included.

In the present embodiment, the etchant composition contains 8.5% to 10% by weight of the inorganic acid compound, 1% to 10% by weight of the hydrogen sulfate compound, and 1% to 5% by weight of the sulfonic acid compound, based on the total weight of the composition. % by weight, and 1% to 5% by weight of the chelate compound.

One embodiment of the present invention, forming a thin film transistor on a substrate; forming a planarization layer covering the thin film transistor; and forming a first electrode electrically connected to the thin film transistor on the planarization layer, wherein the first electrode is formed by stacking a first conductive layer, a second conductive layer containing silver, and a third conductive layer. has a structure, the first conductive layer and the third conductive layer are transparent or translucent electrode layers, the first conductive layer, the second conductive layer, and the third conductive layer are simultaneously etched by the etchant composition, The etchant composition, based on the total weight of the composition, 8.5% to 10% by weight of an inorganic acid compound, 1% to 10% by weight of a hydrogen sulfate compound, 50% to 60% by weight of an organic acid compound, 1% to 5% by weight Disclosed is a method for manufacturing a display device comprising % of a sulfonic acid compound, 1% to 5% by weight of a chelate compound and the balance of water.

In this embodiment, the hydrogen sulfate compound may include at least one of ammonium hydrogen sulfate, potassium hydrogen sulfate, and sodium hydrogen sulfate.

In this embodiment, the organic acid compound may include at least one of acetic acid, malic acid, citric acid, tartaric acid, lactic acid, formic acid, succinic acid, and fumaric acid.

In this embodiment, the organic acid compound may include a first organic acid compound and a second organic acid compound that are different from each other.

In this embodiment, the first organic acid compound and the second organic acid compound may each be included in an amount of 20% to 30% by weight based on the total weight of the etchant composition.

In this embodiment, the sulfonic acid compound may include at least one of methanesulfonic acid, p-toluenesulfonic acid, benzenesulfonic acid, and aminomethylsulfonic acid.

In this embodiment, the chelate compound may include at least one of citric acid, diethanolamine, DTPA, EDTA, ethylenediamine, IDA, ethanolamine, and malonic acid.

In this embodiment, a portion of the planarization layer is removed to form a divided region, a plurality of wires for applying electrical signals to the thin film transistor are exposed in the divided region, and the first conductive layer and the second conductive layer are exposed. layer and the third conductive layer may be etched by the etchant composition in a state in which the plurality of wires are exposed.

In this embodiment, the wires may be formed in a stacked structure of a first layer containing titanium, a second layer containing aluminum, and a third layer containing titanium.

In this embodiment, an intermediate layer and a second electrode are formed on the first electrode, and a thin film encapsulation layer is formed on the second electrode, and the thin film encapsulation layer is an organic film and an inorganic film having a wider width than the organic film. may contain membranes.

In this embodiment, the divided region may divide the planarization layer into a central portion and an outer portion, and the inorganic layer may be formed to cover the outer portion.

In this embodiment, the second conductive layer may further include an alloying element, and an atomic radius of the alloying element may be equal to or smaller than that of the silver.

Other aspects, features and advantages other than those described above will become apparent from the following drawings, claims and detailed description of the invention.

According to embodiments of the present invention, the etchant does not contain phosphoric acid, and it is possible to prevent silver precipitation during simultaneous etching of a multilayer film including a silver film. Of course, the scope of the present invention is not limited by these effects.

1 to 3 are diagrams illustrating an etching result of a multilayer metal film according to an embodiment.
4 to 6 are diagrams illustrating etching results of a multilayer metal film according to a comparative example.
7 is a plan view schematically illustrating a display device according to an exemplary embodiment of the present invention.
FIG. 8 is a cross-sectional view schematically illustrating an example of the II' cross section of FIG. 7 .
FIG. 9 is a plan view schematically illustrating a voltage line and a planarization layer of the display device of FIG. 7 .
FIG. 10 is a cross-sectional view schematically illustrating an example of a section III-III' of FIG. 9 .
FIG. 11 is a plan view illustrating a phenomenon in which silver particles are re-adsorbed on wires during the etching process of the first electrode of FIG. 9 .

Since the present invention can apply various transformations and have various embodiments, specific embodiments will be illustrated in the drawings and described in detail in the detailed description. Effects and features of the present invention, and methods for achieving them will become clear with reference to the embodiments described later in detail together with the drawings. However, the present invention is not limited to the embodiments disclosed below and may be implemented in various forms.

In the following embodiments, terms such as first and second are used for the purpose of distinguishing one component from another component without limiting meaning.

In the following examples, expressions in the singular number include plural expressions unless the context clearly dictates otherwise.

In the following embodiments, terms such as include or have mean that features or components described in the specification exist, and do not preclude the possibility that one or more other features or components may be added.

In the following embodiments, when a part such as a film, region, component, etc. is said to be on or on another part, not only when it is directly above the other part, but also when another film, region, component, etc. is interposed therebetween. Including if there is

In the drawings, the size of components may be exaggerated or reduced for convenience of explanation. For example, since the size and thickness of each component shown in the drawings are arbitrarily shown for convenience of description, the present invention is not necessarily limited to the illustrated bar.

When an embodiment is otherwise implementable, a specific process sequence may be performed differently from the described sequence. For example, two processes described in succession may be performed substantially simultaneously, or may be performed in an order reverse to the order described.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings, and the same or corresponding components will be given the same reference numerals when described with reference to the drawings.

The etchant composition according to the present invention may be used to etch a single film made of silver (Ag) or a silver alloy, and a multilayer film composed of a single film containing silver and a transparent conductive film. The transparent conductive film includes at least one selected from the group consisting of indium tin oxide (ITO), indium zinc oxide (IZO), indium tin zinc oxide (ITZO), gallium zinc oxide (GZO), and indium gallium zinc oxide (IGZO). can do.

An etchant composition according to an embodiment of the present invention may include an inorganic acid compound, a hydrogen sulfate compound, a sulfonic acid compound, an organic acid compound, and a residual amount of water.

The inorganic acid compound is a main oxidizing agent for silver (Ag), and may be nitric acid (HNO ₃ ), hydrochloric acid (HCl), or the like, and may be used alone or in combination of two or more. The inorganic acid compound may be included in an amount of 8.5% to 10% by weight based on the total weight of the etchant composition. If the content of the inorganic acid compound is greater than 10% by weight, the etching rate is too high and it is difficult to control the etching degree, and the metal film including Ag may be over-etched. On the other hand, if the content of the inorganic acid compound is less than 8.5% by weight, the etching rate may decrease and sufficient etching may not be performed.

The hydrogen sulfate compound is the main etching agent for the transparent conductive film, and the transparent conductive film is not etched unless the etching liquid composition contains the hydrogen sulfate compound. The content of the hydrogen sulfate compound may be 1% to 10% by weight, preferably 2% to 9% by weight. If the hydrogen sulfate compound is greater than 10% by weight, the etching rate of the transparent conductive film is too fast, which may cause erosion defects. there is. The hydrogen sulfate compound may include at least one of ammonium hydrogen sulfate ((NH ₄ )HSO ₄ ), potassium hydrogen sulfate (KHSO ₄ ), and sodium hydrogen sulfate (NaHSO ₄ ).

On the other hand, during the silver process, the inorganic acid compound is decomposed by reaction with silver, and accordingly, the etching performance and etching rate of the silver-containing film may decrease. The organic acid compound is an auxiliary oxidizing agent for the inorganic acid compound, and keeps the etching rate of the silver-containing metal film constant by slowing down the decomposition rate of the inorganic acid.

The content of the organic acid compound may be 50% to 60% by weight, preferably 52% to 58% by weight. If the organic acid compound is greater than 60% by weight, the etching rate of the silver film is too fast, which may cause erosion failure. If the content is less than 50% by weight, the inorganic acid compound has a reduced decomposition inhibitory effect, lowering stability, and may cause silver residue. . Organic acid compounds include acetic acid (CH ₃ CO ₂ H), malic acid (C ₄ H ₆ O ₅ ), citric acid (C ₆ H ₈ O ₇ ), tartaric acid (C ₄ H ₆ O ₆ ), and lactic acid (C ₃ H ₆ O ₃ ), formic acid (CH ₂ O ₂ ), succinic acid (C ₄ H ₆ O ₄ ), and fumaric acid (C ₄ H ₄ O ₄ ).

As an optional embodiment, the organic acid compound may include a first organic acid compound and a second organic acid compound that are different from each other. In this case, the content of the first organic acid compound may be 20% to 30% by weight based on the total weight of the etchant composition, and the content of the third organic acid compound may be 20% to 30% by weight based on the total weight of the etchant composition. For example, the first organic acid compound may be acetic acid and the second organic acid compound may be citric acid, but is not limited thereto.

The sulfonic acid compound slows down the decomposition rate of the inorganic acid, thereby maintaining a constant etching rate of the silver-containing metal film. The content of the sulfonic acid compound may be 1% to 5% by weight, preferably 2% to 5% by weight. If the content of the sulfonic acid compound is greater than 5% by weight, the etching rate of the silver-containing film is too fast, which may cause erosion defects. may occur. Sulfonic acid compounds include methanesulfonic acid (CH ₃ SO ₃ H), p-toluenesulfonic acid (CH ₃ C ₆ H ₄ SO ₃ H), benzenesulfonic acid (C ₆ H ₅ SO ₃ H), and aminomethylsulfonic acid (CH ₅ NO ₃ S ) may include at least one of them.

The etchant composition of the present invention may further include a chelate compound.

The chelating compound is a silver chelating agent, suppresses the reaction of silver ions generated during etching, has an effect of controlling the etching rate, and can increase the number of substrates treated with an etchant. The content of the chelating compound may be 1% to 5% by weight, preferably 2% to 5% by weight. If the content of the chelate compound is less than 1% by weight, a problem may occur in chemical aging, and a tip of the upper transparent conductive film may occur due to a difference in etching rate between the transparent conductive film and the film containing silver. On the other hand, when the content of the chelate compound is greater than 5% by weight, silver residue may be generated due to an excessive decrease in the etching rate of the silver-containing film.

Specific examples of the chelating compound include citric acid (C ₆ H ₈ O ₇ ), diethanolamine (C ₄ H ₁₁ NO ₂ ), DTPA (C ₁₄ H ₂₃ N ₃ O ₁₀ ), EDTA (C ₁₀ H ₁₆ N ₂ O ₈ ), ethylenediamine (C ₂ H ₈ N ₂ ), IDA (C ₄ H ₇ NO ₄ ), ethanolamine (C ₂ H ₇ NO), and malonic acid (C ₃ H ₄ O ₄ ), including at least one of can do.

Hereinafter, the present invention will be described in more detail through examples. However, the following examples are intended to explain the present invention in more detail, and the scope of the present invention is not limited by the following examples. The following examples may be appropriately modified or changed by those skilled in the art within the scope of the present invention.

< etchant Preparation of Composition>

The etchants of Examples 1 to 11 and Comparative Examples 1 to 11 according to the etchant composition as described above were prepared as shown in Table 1 below.

< etchant etching speed, cd Skew( one side ), residue and Precipitation Measurement>

Table 2 below shows the etchant composition prepared according to Table 1 in the state in which a photoresist pattern is formed on a multilayer metal film having a laminated structure of transparent conductive film (ITO) / silver film (Ag) / transparent conductive film (ITO) Shows the result of etching. In addition, FIGS. 1 to 3 are diagrams showing the etching results of the multilayer metal film according to Examples 1 to 11, and FIGS. 4 to 6 show the etching results of the multilayer metal film according to Comparative Examples 1 to 11. it is one degree

In Table 2 below, the etching rate (E / R) of the ITO / Ag / ITO multilayer metal film is an appropriate etching rate when 18 Å / sec to 20 Å / sec, and CD skew (Cut dimension skew, one side) is the photoresist end and It refers to the distance between the ends of ITO/Ag/ITO, and an appropriate range is 0.2 μm to 0.3 μm.

As can be seen from Table 2 and FIGS. 1 to 3, Examples 1 to 11 satisfy the etching rate (E / R) of 18 to 20 Å / sec, and the CD-Skew side is 0.2 μm to It can be seen that it satisfies 0.3 μm, and no residue or precipitation occurs. On the other hand, in Comparative Examples 1, 3, 5, and 7, as a result of each composition of the etchant composition containing less than the amount of the above-described composition, the etching ability was lowered and residue was generated, and all results outside the standard range except for precipitation represents Conversely, Comparative Examples 2, 4, 6, 8, and 9, in which the content of each composition is greater than the amount of the above-described composition, do not satisfy the CD-Skew (one side) standard of 0.2 μm to 0.3 μm due to excessive etching. Able to know. In addition, it can be seen that Comparative Example 9 did not satisfy the aging property due to insufficient content of the chelating agent, and in the case of Comparative Example 10, residue was generated due to the excessive amount of the chelating agent. In the case of Comparative Example 11, it can be seen that the etching rate increases as the phosphorus compound is included, so that the CD-Skew (one side) increases significantly, and reducible precipitation of silver occurs.

< etchant Reliability evaluation according to the increase in the number of processed sheets>

In Table 3, an etching test was performed while increasing the silver ion concentration in the etchant composition of Example 1 of Table 1. Specifically, after reference etching was performed using the etchant of Example 1, silver powder was added to the etchant composition of Example 1 at an amount of 200 ppm after the initial 300 ppm to conduct an etching test. In Table 3 below, ◎ means that the amount of change compared to the reference is within 10%.

According to Table 3, it can be confirmed that the etchant composition according to the present invention does not have a large change in etching rate, CD skew, residue and precipitation even when the silver ion concentration is increased. That is, it can be seen that the etching reliability of the etchant composition is excellent even if the number of etching times increases.

< etchant Reliability evaluation over time >

In Table 4, the etchant composition of Example 1 in Table 1 was subjected to an etching test while increasing the passage of time. Specifically, after a reference etch was performed with the etchant composition of Example 1, a 12-hour unit etch test was added to compare the results of the reference etch. In Table 4 below, ◎ means that the amount of change compared to the reference is within 10%.

As can be seen from Table 4, even when the time elapses, the change in the etching rate, CD skew, residue and precipitation by the etchant composition according to the present invention is not large, indicating that the etchant composition maintains excellent etching reliability. can

7 is a plan view schematically showing a display device according to an embodiment of the present invention, FIG. 8 is a cross-sectional view schematically showing an example of the II' section of FIG. 7, and FIG. 9 is a view of the display device of FIG. A plan view schematically showing a voltage line and a planarization layer, and FIG. 10 is a cross-sectional view schematically showing an example of a section III-III' of FIG. 9 .

Hereinafter, with reference to FIGS. 7 to 10 , the display device 10 and its manufacturing process will be described.

7 to 10, a flat panel display device 10 according to an embodiment of the present invention includes a substrate 101, a display unit 100 positioned on the substrate 101, and a thin film sealing the display unit 100. An encapsulation layer 300 may be included.

The substrate 101 may include various materials. For example, the substrate 101 may be made of a transparent glass material containing SiO ₂ as a main component. However, the substrate 101 is not necessarily limited thereto, and may be formed of a transparent plastic material. Plastic materials include polyethersulphone (PES), polyacrylate (PAR), polyetherimide (PEI), polyethyelenen napthalate (PEN), polyethyeleneterepthalate (PET), polyphenylene sulfide (PPS), polyallylate, polyimide, polycarbonate (PC), cellulose triacetate (TAC), cellulose acetate propionate (CAP), etc. can

On the other hand, in the case of a bottom emission type in which an image is implemented in the direction of the substrate 101, the substrate 101 should be formed of a transparent material. However, in the case of a top emission type in which an image is implemented in a direction opposite to that of the substrate 101, the substrate 101 does not necessarily need to be formed of a transparent material. In this case, the substrate 101 may be formed of metal. When the substrate 101 is formed of metal, the substrate 101 may include iron, chromium, manganese, nickel, titanium, molybdenum, stainless steel (SUS), an Invar alloy, an Inconel alloy, a Kovar alloy, and the like.

The display unit 100 is formed on the substrate 101 . The display unit 100 may include a display area DA that implements an image recognizable by a user and a non-display area NDA outside the display area DA.

A plurality of pixels P may be disposed in the display area DA. The plurality of pixels P may be positioned at intersections of the data line DL and the scan line SL, and the voltage line 200 supplying power to the display element 100b or the like is provided in the non-display area NDA. can be placed. In addition, a pad unit 150 may be disposed in the non-display area NDA to transmit an electrical signal from a power supply device (not shown) or a signal generator (not shown) to the display area DA.

A buffer layer 102 may be formed on the substrate 101 . The buffer layer 102 may provide a flat surface on the top of the substrate 101 and may block foreign matter or moisture penetrating through the substrate 101 . For example, the buffer layer 102 may be made of an inorganic material such as silicon oxide, silicon nitride, silicon oxynitride, aluminum oxide, aluminum nitride, titanium oxide, or titanium nitride, or an organic material such as polyimide, polyester, or acryl. It may contain, and may be formed of a plurality of laminates among the materials exemplified.

A thin film transistor 100a and a display element 100b electrically connected to the thin film transistor 100a may be positioned on the substrate 101 .

The thin film transistor 100a may include an active layer 103 , a gate electrode 105 , a source electrode 107 and a drain electrode 108 . Hereinafter, a case in which the thin film transistor 100a is a top gate type in which an active layer 103, a gate electrode 105, a source electrode 107, and a drain electrode 108 are sequentially formed will be described. However, the present embodiment is not limited thereto, and various types of thin film transistors 100a such as a bottom gate type may be employed.

The active layer 103 may include a semiconductor material such as amorphous silicon or polycrystalline silicon. However, the present embodiment is not limited thereto, and the active layer 103 may contain various materials. As an optional embodiment, the active layer 103 may contain an organic semiconductor material or the like. As another optional embodiment, the active layer 103 may contain an oxide semiconductor material. For example, the active layer 103 is made of metal elements in groups 12, 13, and 14, such as zinc (Zn), indium (In), gallium (Ga), tin (Sn), cadmium (Cd), and germanium (Ge), and combinations thereof. It may contain oxides of selected materials.

A gate insulating layer 104 is formed on the active layer 103 . The gate insulating layer 104 may be formed of a multilayer or single layer of an inorganic material such as silicon oxide and/or silicon nitride. The gate insulating film 104 serves to insulate the active layer 103 and the gate electrode 105 . The gate insulating layer 104 may be formed to extend not only to the display area DA but also to a part of the non-display area.

A gate electrode 105 is formed on top of the gate insulating film 104 . The gate electrode 105 may be connected to a gate line (not shown) for applying an on/off signal to the thin film transistor 100a.

The gate electrode 105 may be made of a low-resistance metal material. For example, the gate electrode 105 may include aluminum (Al), platinum (Pt), palladium (Pd), silver (Ag), magnesium (Mg), gold (Au), nickel (Ni), neodymium (Nd), It can be formed as a single layer or multi-layer with one or more of iridium (Ir), chromium (Cr), lithium (Li), calcium (Ca), molybdenum (Mo), titanium (Ti), tungsten (W), and copper (Cu). can

An interlayer insulating film 106 is formed on the gate electrode 105 . The interlayer insulating film 106 insulates the source electrode 107 and the drain electrode 108 from the gate electrode 105 . The interlayer insulating layer 106 may be formed to extend not only to the display area DA but also to a part of the non-display area.

The interlayer insulating film 106 may be formed of a multi-layered or single-layered film made of an inorganic material. For example, the inorganic material may be a metal oxide or a metal nitride, and specifically, the inorganic material may be silicon oxide (SiO ₂ ), silicon nitride (SiNx), silicon oxynitride (SiON), aluminum oxide (Al ₂ O ₃ ), titanium oxide ( TiO ₂ ), tantalum oxide (Ta ₂ O ₅ ), hafnium oxide (HfO ₂ ), or zinc oxide (ZrO ₂ ).

A source electrode 107 and a drain electrode 108 may be formed on the interlayer insulating layer 106 . The source electrode 107 and the drain electrode 108 are formed to contact the active layer 103 region. The source electrode 107 and the drain electrode 108 are aluminum (Al), platinum (Pt), palladium (Pd), silver (Ag), magnesium (Mg), gold (Au), nickel (Ni), neodymium (Nd) ), iridium (Ir), chromium (Cr), lithium (Li), calcium (Ca), molybdenum (Mo), titanium (Ti), tungsten (W), copper (Cu) in a single layer or multi-layer can be formed For example, the source electrode 107 and the drain electrode 108 may have a three-layer stacked structure of titanium (Ti), aluminum (Al), and titanium (Ti).

A planarization layer 109 is formed on the thin film transistor 100a. The planarization layer 109 eliminates the level difference caused by the thin film transistor 100a and prevents defects from occurring in the display element 100b due to the lower irregularities. The planarization layer 109 may be formed of a single layer or multiple layers of a film made of an organic material. Organic materials include general purpose polymers such as Polymethylmethacrylate (PMMA) and Polystylene (PS), polymer derivatives having phenolic groups, acrylic polymers, imide polymers, arylether polymers, amide polymers, fluorine polymers, and p-xylene polymers. It may include polymers, vinyl alcohol-based polymers, and blends thereof. Also, the planarization layer 109 may be formed of a composite laminate of an inorganic insulating film and an organic insulating film.

The planarization layer 109 may include a partition area V surrounding the display area DA within the non-display area NDA. The partition area V is formed by removing a portion of the planarization layer 109 and can prevent moisture from penetrating into the display area DA along the planarization layer 109 made of an organic material. The planarization layer 109 may be divided into a central portion 109a and an outer portion 109b by the dividing region V, and the central portion 109a may have a larger area than the display area DA.

A display element 100b is formed on the planarization layer 109 . For example, the display element 100b includes a first electrode 111, a second electrode 113 facing the first electrode 111, and an intermediate layer interposed between the first electrode 111 and the second electrode 113. It may be an organic light emitting device having (112).

The first electrode 110 may be formed on the planarization layer 109 and electrically connected to the thin film transistor 100a. The first electrode 110 may have various shapes, for example, it may be patterned and formed into an island shape by a photolithography method.

For example, the first electrode 110 may be a reflective electrode. For example, the first electrode 110 includes a reflective film formed of Ag, Mg, Al, Pt, Pd, Au, Ni, Nd, Ir, Cr, and compounds thereof, and a transparent or translucent electrode layer formed on the reflective film. can do. The transparent or translucent electrode layer is at least one selected from the group consisting of indium tin oxide (ITO), indium zinc oxide (IZO), indium tin zinc oxide (ITZO), gallium zinc oxide (GZO), and indium gallium zinc oxide (IGZO). can be provided.

For example, the first electrode 110 may have a stacked structure of a first conductive layer that is a transparent or translucent electrode layer, a second conductive layer containing silver, and a third conductive layer that is a transparent or translucent electrode layer. In addition, the second conductive layer including silver may further include an alloy element having an atomic radius equal to or smaller than that of silver in order to prevent aggregation of silver. The alloying elements are zinc (Zn), nickel (Ni), cobalt (Co), copper (Cu), gallium (Ga), germanium (Ge), platinum (Pt), antimony (Sb), manganese (Mn), It may include at least one of tungsten (W) and molybdenum (Mo).

The second electrode 113 may be a transparent or translucent electrode, and may be formed of a metal thin film having a small work function including Li, Ca, LiF/Ca, LiF/Al, Al, Ag, Mg, and compounds thereof. . In addition, an auxiliary electrode layer or a bus electrode may be further formed on the metal thin film using a material for forming a transparent electrode such as ITO, IZO, ZnO, or In ₂ O ₃ . Accordingly, the second electrode 113 may transmit light emitted from the organic emission layer included in the intermediate layer 112 . That is, light emitted from the organic light emitting layer may be directly or reflected by the first electrode 110 composed of a reflective electrode and emitted toward the second electrode 113 .

However, the display unit 100 of this embodiment is not limited to the top emission type, and may be a bottom emission type in which light emitted from the organic light emitting layer is emitted toward the substrate 101 side. In this case, the first electrode 110 may be composed of a transparent or translucent electrode, and the second electrode 113 may be composed of a reflective electrode. In addition, the display unit 100 of this embodiment may be a double-sided emission type that emits light in both front and rear directions.

Meanwhile, a pixel defining layer 119 is formed of an insulating material on the first electrode 110 . The pixel defining layer 119 is formed of one or more organic insulating materials selected from the group consisting of polyimide, polyamide, acrylic resin, benzocyclobutene, and phenol resin, and may be formed by a method such as spin coating. The pixel defining layer 119 exposes a predetermined area of the first electrode 110, and the intermediate layer 112 including the organic emission layer is located in the exposed area. That is, the pixel defining layer 119 defines a pixel area of the organic light emitting device.

The organic emission layer included in the intermediate layer 112 may be a low-molecular-weight organic material or a high-molecular organic material, and the intermediate layer 112 includes a hole transport layer (HTL), a hole injection layer (HIL), and an electron transport layer in addition to the organic emission layer. Functional layers such as an electron transport layer (ETL) and an electron injection layer (EIL) may be optionally further included.

Meanwhile, a voltage line 200 and a partition area V dividing the planarization layer 109 into a central portion 109a and an outer portion 109b may be disposed in the non-display area NDA. At least a portion of the voltage line 200 may be disposed in the divided region V. That is, a portion of the voltage line 200 may be exposed in the divided region V.

The voltage line 200 may include a first voltage line 210 and a second voltage line 220 . For example, the first voltage line 210 may be a first power voltage ELVDD line, and the second voltage line 220 may be a second power voltage ELVSS line. The second voltage line 220 may be connected to the second electrode 113 . Although FIG. 8 shows an example in which the second voltage line 220 and the second electrode 113 are connected through the wiring 116, the present invention is not limited to this, and the second voltage line 220 and the second electrode ( 113) is directly accessible.

The first voltage line 210 may include a first main voltage line 212 disposed to correspond to one side of the display area DA and a first connection portion 214 . For example, when the display area DA has a rectangular shape, the first main voltage line 212 may be disposed to correspond to one side of the display area DA. The first voltage line 212 may be parallel to any one side and may have a length greater than or equal to any one side. Any one side corresponding to the first voltage line 212 may be a side adjacent to the pad part 150 .

The first connection portion 214 may protrude from the first main voltage line 212 along the first direction to cross the divided area V. Here, the first direction is a direction from the display area DA toward the pad part 150 , and the first connection part 214 may be connected to the pad part 150 . The first main voltage line 212 may be covered by the central portion 109a, but the first connection portion 214 may be exposed in the divided region V at least until the middle layer 112 is formed.

The second voltage line 220 protrudes along the first direction from the second main voltage line 222 and the second main voltage line 222 surrounding both ends of the first main voltage line 212 and the remaining areas of the display area DA. and may include a second connection portion 224 crossing the divided area V. The second connection portion 224 is connected to the pad portion 150 and may be exposed in the divided region V until at least the process of forming the intermediate layer 112 .

Meanwhile, the voltage line 200 may be formed using the same material as the source electrode 107 and the drain electrode 108 . For example, the voltage line 200 may have a stacked structure of a first layer including titanium (Ti), a second layer including aluminum (Al), and a third layer including titanium (Ti). At this time, since aluminum (Al) has a higher etching rate than titanium (Ti), when the side of the voltage line 200 is exposed in the divided region V, during the process, for example, the first electrode 111 is patterned. During the process, damage may occur to the second layer including aluminum (Al). That is, when the first electrode 111 is etched using a conventional mixed acid etchant containing phosphoric acid, the second layer containing aluminum (Al) is excessively etched, resulting in defects in the third layer containing titanium (Ti). As a result of this occurrence, the step coverage of the voltage line 200 is degraded, and accordingly, damage such as cracks may occur in the thin film encapsulation layer 300 in contact with the voltage line 200 in the divided region V.

In addition, electrons are generated by etching the second layer including aluminum (Al), the generated electrons are combined with silver ions present in the etching solution, and the silver ions are reduced, thereby forming the first connection part 214 or the second connection part Silver particles may be adsorbed on (224). Adsorbed silver particles may be transferred to the first electrode 111 by a cleaning process or the like. Therefore, the first electrode 111 may be defective due to silver particles.

Meanwhile, in the partition area V where the first connection part 214 and the second connection part 224 are exposed, wires for applying electrical signals to the display area DA may also be exposed. The wires may apply electrical signals to the thin film transistor 100a. For example, the wires may connect the pad part 150 and the data line DL, and the wires may also be formed using the same material as the source electrode 107 and the drain electrode 108 . For example, the wires may have a stacked structure of a first layer including titanium (Ti), a second layer including aluminum (Al), and a third layer including titanium (Ti). Therefore, during the process of etching the first electrode 111, the wires exposed in the divided region V by the etching solution are also damaged, and silver particles may be re-adsorbed on the wires.

In order to prevent this, according to the present invention, the etchant composition for etching the first electrode 111 does not contain phosphoric acid, instead of organic acid compound and sulfonic acid compound for etching the second conductive layer containing silver (Ag) By including a hydrogen sulfate compound for etching the transparent or translucent electrode layer, the first to third conductive layers of the first electrode 111 may have excellent etching characteristics and may be etched collectively.

In addition, since the etchant composition according to the present invention does not contain phosphoric acid, during the etching process of the first electrode 111, damage to the wires exposed in the divided region V does not occur, preventing re-adsorption of silver particles. It can be prevented.

FIG. 11 is a plan view illustrating a phenomenon in which silver particles are re-adsorbed on wires during the etching process of the first electrode 111 of FIG. It shows the result of re-adsorption of silver particles on the connected wires. Specifically, FIG. 11 (a) is a result of using a conventional phosphoric acid-containing etchant, and FIG. 11 (b) is a result of using the etchant of Example 1 of Table 1 above.

As can be seen in FIG. 11, when the first electrode 111 is etched using the etchant composition according to the present invention, damage to the wires exposed to the etchant composition is prevented, and thus silver re-adsorption is reduced, resulting in silver Defects of the first electrode due to particles can be prevented.

Referring back to FIG. 8 , a dam portion 109c may be formed in the divided area V. When the organic film 330 of the thin film encapsulation layer 300 for sealing the display unit 100 is formed, the dam part 109c blocks the organic material from flowing toward the edge of the substrate 101, so that the organic film 330 The formation of edge tails can be prevented.

The dam portion 109c may cover the outer surface of the second main voltage line 220 by overlapping and contacting the outer edge of the second main voltage line 220 . In addition, the central portion 109a may cover the inner surface of the second main voltage line 220 by overlapping and contacting the inner edge of the second main voltage line 220 . Therefore, both sides of the second main voltage line 220 may be prevented from being exposed to an etching environment.

The dam portion 109c may be formed of the same material on the same layer as the planarization layer 109 . However, it is not limited thereto, and the dam portion 109c may be composed of two or more layers. For example, when the dam portion 109c has a two-layer structure, the lower layer may be made of the same material as the planarization layer 109 and the upper layer may be made of the same material as the pixel defining layer 119 . In addition, the dam part 109c may be composed of a plurality of two or more. When a plurality of dam parts 109c are formed, the height of the dam parts 109c may increase toward the outer edge of the substrate 101 .

The thin film encapsulation layer 300 can seal the display unit 100 and prevent external oxygen and moisture from penetrating into the display unit 100 . The thin film encapsulation layer 300 may include at least one inorganic layer 310 and 320 and at least one organic layer 330 . 2 shows an example in which the thin film encapsulation layer 300 includes two inorganic films 310 and 320 and one organic film 330 alternately stacked with each other, but the present invention is not limited thereto. don't That is, the thin film encapsulation layer 300 may further include a plurality of additional inorganic encapsulation films and organic encapsulation films alternately disposed, and the number of stacking of the inorganic encapsulation film and the organic encapsulation film is not limited.

The organic layer 330 may include, for example, one or more materials selected from the group consisting of acrylic resin, methacrylic resin, polyisoprene, vinyl resin, epoxy resin, urethane resin, cellulose resin, and perylene resin. .

The inorganic layers 310 and 320 may include, for example, silicon nitride, aluminum nitride, zirconium nitride, titanium nitride, hafnium nitride, tantalum nitride, silicon oxide, aluminum oxide, titanium oxide, tin oxide, cerium oxide, and silicon oxynitride (SiON). It may include one or more materials selected from the group consisting of.

Meanwhile, when the organic film 330 is formed, the dam part 109c blocks the organic material from flowing toward the edge of the substrate 101, so the organic film 330 is positioned inside the dam part 109c. In contrast, the inorganic layers 310 and 320 are larger than the organic layer 330 and may be formed to cover the outer portion 109b. Accordingly, the divided region V is covered by the inorganic films 310 and 320 . In addition, the inorganic layers 310 and 320 may extend outside the outer portion 109b, and the inorganic layers 310 and 320 may contact each other on the outer side of the outer portion 109b.

Although the above has been described with reference to the embodiments shown in the drawings, this is only exemplary, and those skilled in the art will understand that various modifications and equivalent other embodiments are possible therefrom. Therefore, the true technical scope of protection of the present invention should be determined by the technical spirit of the appended claims.

Claims (20)

Including an inorganic acid compound, a hydrogen sulfate compound, a sulfonic acid compound, an organic acid compound and a residual amount of water,
Based on the total weight of the composition, 50% to 60% by weight of the organic acid compound, 8.5% to 10% by weight of the inorganic acid compound, 1% to 10% by weight of the hydrogen sulfate compound, and 1% to 5% by weight of the sulfonic acid compound An etchant composition comprising weight percent. According to claim 1,
The hydrogen sulfate compound is an etchant composition comprising at least one of ammonium hydrogen sulfate, potassium hydrogen sulfate, and sodium hydrogen sulfate. According to claim 1,
The organic acid compound is an etchant composition comprising at least one of acetic acid, malic acid, citric acid, tartaric acid, lactic acid, formic acid, succinic acid, and fumaric acid. According to claim 3,
The organic acid compound is an etchant composition comprising a first organic acid compound and a second organic acid compound that are different from each other. According to claim 4,
The first organic acid compound and the second organic acid compound are each included in 20% to 30% by weight based on the total weight of the etchant composition. According to claim 1,
The sulfonic acid compound is an etchant composition comprising at least one of methanesulfonic acid, p-toluenesulfonic acid, benzenesulfonic acid, and aminomethylsulfonic acid. According to claim 1,
An etchant composition further comprising a chelating compound. According to claim 7,
The etchant composition, based on the total weight of the composition, the etchant composition containing 1% to 5% by weight of the chelate compound. Forming a thin film transistor on a substrate;
forming a planarization layer covering the thin film transistor; and
Forming a first electrode electrically connected to the thin film transistor on the planarization layer; includes,
The first electrode has a laminated structure of a first conductive layer, a second conductive layer containing silver, and a third conductive layer, and the first conductive layer and the third conductive layer are transparent or translucent electrode layers,
The first conductive layer, the second conductive layer, and the third conductive layer are simultaneously etched by the etchant composition,
The etchant composition, based on the total weight of the composition, 8.5% to 10% by weight of an inorganic acid compound, 1% to 10% by weight of a hydrogen sulfate compound, 50% to 60% by weight of an organic acid compound, 1% to 5% by weight A method of manufacturing a display device comprising % of a sulfonic acid compound, 1% to 5% by weight of a chelate compound and the balance of water. According to claim 9,
The method of manufacturing a display device wherein the hydrogen sulfate compound includes at least one of ammonium hydrogen sulfate, potassium hydrogen sulfate, and sodium hydrogen sulfate. According to claim 9,
wherein the organic acid compound includes at least one of acetic acid, malic acid, citric acid, tartaric acid, lactic acid, formic acid, succinic acid, and fumaric acid. According to claim 9,
The organic acid compound is a method of manufacturing a display device comprising a first organic acid compound and a second organic acid compound that are different from each other. According to claim 12,
The first organic acid compound and the second organic acid compound are each included in 20% to 30% by weight based on the total weight of the etchant composition. According to claim 9,
The method of manufacturing a display device, wherein the sulfonic acid compound includes at least one of methanesulfonic acid, p-toluenesulfonic acid, benzenesulfonic acid, and aminomethylsulfonic acid. According to claim 9,
The method of claim 1, wherein the chelate compound includes at least one of citric acid, diethanolamine, DTPA, EDTA, ethylenediamine, IDA, ethanolamine, and malonic acid. According to claim 9,
Part of the planarization layer is removed to form a divided region;
A plurality of wires for applying electrical signals to the thin film transistors are exposed in the divided area;
The first conductive layer, the second conductive layer, and the third conductive layer are etched by the etchant composition in a state in which the plurality of wires are exposed. According to claim 16,
The wirings are formed in a stacked structure of a first layer containing titanium, a second layer containing aluminum, and a third layer containing titanium. According to claim 16,
Forming an intermediate layer and a second electrode on the first electrode,
Forming a thin film encapsulation layer on the second electrode,
The thin film encapsulation layer is a method of manufacturing a display device comprising an organic film and an inorganic film having a wider area than the organic film. According to claim 18,
The division area divides the planarization layer into a central portion and an outer portion,
The inorganic film is a method of manufacturing a display device formed to cover the outer portion. According to claim 9,
The second conductive layer further includes an alloy element, and an atomic radius of the alloy element is equal to or smaller than an atomic radius of the silver.

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