Etching liquid composition and oxide semiconductor device

Abstract

Disclosed is an etching liquid composition and an oxide semiconductor device. The etching liquid composition includes one or more of an amine compound and an amino acid compound, hydrogen peroxide, a chelating agent, an etchant, an inhibitor, and water. The etching liquid composition has good etching performance for copper-based metals and molybdenum-based metals and reduces damage to an oxide semiconductor layer.

Description

Technical Field

[0001] The present application relates to the field of display technology, and in particular to an etching solution composition and an oxide semiconductor device. Background Art

[0002] A display panel generally includes a substrate and a laminated structure of a copper-based metal and a molybdenum-based metal disposed on the substrate. To effectively etch this metal laminate, an etching solution generally contains fluorine.

[0003] However, for oxide semiconductor thin-film transistors, when a stacked structure of copper-based metals and molybdenum-based metals is used as the source and drain electrodes, the oxide semiconductor located below the source and drain electrodes will also be corroded by the fluorine-containing etching solution due to its own etching characteristics, causing damage to the oxide semiconductor, such as IGZO (Indium Gallium Zinc Oxide), thereby affecting the performance of the device.

[0004] Furthermore, to improve the carrier mobility and ensure the stability of oxide semiconductor thin-film transistors, oxide semiconductors with increased gallium or zinc content are being used. The increased gallium or zinc content makes the oxide semiconductor more susceptible to corrosion, exacerbating the damage problem of the oxide semiconductor layer.

[0005] Therefore, there is a need for an etching solution that can effectively etch copper-based metals and molybdenum-based metals while causing minimal damage to the oxide semiconductor layer. Summary of the Invention

[0006] The embodiments of the present application provide an etching solution composition that has good etching performance on copper-based metals and molybdenum-based metals and reduces damage to the oxide semiconductor layer.

[0007] An embodiment of the present application provides an etching solution composition, which includes one or more of an amine compound and an amino acid compound, hydrogen peroxide, a chelating agent, an etching agent, an inhibitor, and water.

[0008] Optionally, in some embodiments of the present application, the amine compound includes one or more of hexamethylenetetramine, 1-methyl-2,3,4,5,6,7-hexaminoindole, 1,2,3,4,5,6-hexaminohexane and 2-ethylhexylamine, and the amino acid compound includes one or more of arginine, histidine, lysine, aspartic acid and glutamic acid.

[0009] Optionally, in some embodiments of the present application, based on the total weight of the etching solution composition being 100%, the total weight of the amine compound and the amino acid compound is 0.01 to 1%.

[0010] Optionally, in some embodiments of the present application, based on the total weight of the etching solution composition being 100%, the total weight of the amine compound and the amino acid compound is 0.3-0.6%.

[0011] Optionally, in some embodiments of the present application, based on the total weight of the etching solution composition being 100%, the weight of the amine compound is 0.25-0.35%, and the weight of the amino acid compound is 0.1-0.2%.

[0012] Optionally, in some embodiments of the present application, the chelating agent includes one or more of iminodisuccinic acid, iminodiacetic acid, aminotriacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, aminotrimethylenephosphonic acid, 1-hydroxyethylenediphosphonic acid, ethylenediaminetetramethylenephosphonic acid and diethylenetriaminepentamethylenephosphonic acid;

[0013] The etchant includes one or more of ammonium sulfate, ammonium bisulfate, potassium sulfate, potassium bisulfate, sodium sulfate and sodium bisulfate;

[0014] The inhibitor includes one or more of 3-amino-1,2,3-triazole, 3-amino-1,2,4-triazole, 4-amino-1,2,3-triazole, 4-amino-1,2,4-triazole, 5-methyltetrazole, 5-aminotetrazole, imidazole and pyrazole.

[0015] Optionally, in some embodiments of the present application, based on the total weight of the etching solution composition as 100%, the weight of the hydrogen peroxide is 18-23%, the weight of the chelating agent is 2-3%, the weight of the etchant is 1-3%, and the weight of the inhibitor is 0.05%-0.5%.

[0016] Optionally, in some embodiments of the present application, based on the total weight of the etching solution composition as 100%, the etching solution composition includes 0.25-0.35% amine compound, 0.1-0.2% amino acid compound, 21-23% hydrogen peroxide, 2.5% iminodisuccinic acid, 1.8-2.0% ammonium bisulfate, 0.05-0.1% pyrazole and water.

[0017] Optionally, in some embodiments of the present application, the amine compound includes hexamethylenetetramine, and the amino acid compound includes one or both of lysine and aspartic acid.

[0018] Correspondingly, an embodiment of the present application also provides an oxide semiconductor device, which includes an oxide semiconductor layer and a source and a drain arranged on the oxide semiconductor layer, wherein the source and the drain include a stacked structure of a copper-based metal and a molybdenum-based metal, and the source and the drain are etched using the etching solution composition described in the above embodiment.

[0019] The etching solution composition provided in the embodiments of the present application includes one or more of an amine compound and an amino acid compound, hydrogen peroxide, a chelating agent, an etching agent, an inhibitor, and water. It has good etching performance for copper-based metals and platinum-based metals. The added amine compound and / or amino acid compound can combine with the oxygen element in the oxide semiconductor and adsorb on the surface of the oxide semiconductor layer, thereby protecting the oxide semiconductor layer and reducing damage to the oxide semiconductor layer caused by the etching solution composition. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] In order to more clearly illustrate the technical solutions in the embodiments of the present application, the following briefly introduces the drawings required for use in the description of the embodiments. Obviously, the drawings described below are only some embodiments of the present application. For those skilled in the art, other drawings can be obtained based on these drawings without creative work.

[0021] Figure 1 This is a scanning electron microscope cross-sectional observation image of a test piece (IGZO indium:gallium:zinc molar ratio is 1:3:6) etched by the etching solution composition provided in Example 1 of the present application.

[0022] Figure 2 This is a top-view scanning electron microscope image of a test piece (IGZO indium:gallium:zinc molar ratio of 1:3:6) etched with the etching solution composition provided in Example 1 of the present application.

[0023] Figure 3 This is a scanning electron microscope cross-sectional observation image of a test piece (IGZO indium: gallium: zinc molar ratio is 1:3:6) etched by the etching solution composition provided in Comparative Example 1 of the present application.

[0024] Figure 4 This is a top-view scanning electron microscope image of a test piece etched with the etching solution composition provided in Comparative Example 1 of the present application (IGZO indium:gallium:zinc molar ratio is 1:3:6). DETAILED DESCRIPTION

[0025] The following will be combined with the drawings in the embodiments of the present application to clearly and completely describe the technical solutions in the embodiments of the present application. Obviously, the described embodiments are only part of the embodiments of the present application, not all of the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without making creative work are within the scope of protection of this application. In addition, it should be understood that the specific implementation methods described here are only used to illustrate and explain the present application and are not used to limit the present application. It should be noted that the description order of the following embodiments is not intended to limit the preferred order of the embodiments. In this application, unless otherwise specified, the directional words used, such as "upper" and "lower", generally refer to the upper and lower parts of the device in actual use or working state, specifically the drawing direction in the accompanying drawings; while "inside" and "outside" refer to the outline of the device. In this application, "reaction" can be a chemical reaction or a physical reaction.

[0026] The present application provides an etching solution composition and an oxide semiconductor device. The etching solution composition includes one or more of an amine compound and an amino acid compound, hydrogen peroxide, a chelating agent, an etching agent, an inhibitor, and water.

[0027] The etching solution composition provided in the present application has good etching performance for copper-based metals and molybdenum-based metals. At the same time, the added amine compounds and / or amino acid compounds can combine with the oxygen element in the oxide semiconductor and adsorb on the surface of the oxide semiconductor layer, thereby protecting the oxide semiconductor layer and reducing damage to the oxide semiconductor layer caused by the etching solution composition.

[0028] The following details:

[0029] The present application provides an etching solution composition, which includes one or more of an amine compound and an amino acid compound, hydrogen peroxide, a chelating agent, an etching agent, an inhibitor, and water.

[0030] In one embodiment, the amine compound includes one or more of hexamethylenetetramine, 1-methylindole-2,3,4,5,6,7-hexamine, 1,2,3,4,5,6-hexane-1,2,3,4,5,6-hexamine, and 2-ethylhexyamine. The amino acid compound includes one or more of arginine, histidine, lysine, aspartic acid, and glutamic acid. These compounds can combine with oxygen in the oxide semiconductor and adsorb on the surface of the oxide semiconductor layer, thereby protecting the oxide semiconductor layer and reducing damage to the oxide semiconductor layer caused by the etching solution composition.

[0031] In one embodiment, the total weight of the amine compound and the amino acid compound is 0.01-1%, based on the total weight of the etching solution composition being 100%. Specifically, the total weight of the amine compound and the amino acid compound can be 0.01%, 0.05%, 0.1%, 0.3%, 0.5%, 0.7%, or 1%, based on the total weight of the etching solution composition being 100%. In this embodiment, setting the total weight of the amine compound and the amino acid compound in the etching solution composition to 0.01-1% can reduce damage to the oxide semiconductor layer without affecting the etching performance of the etching solution composition on copper-based metals and molybdenum-based metals.

[0032] In one embodiment, the total weight of the amine compound and the amino acid compound is 0.3-0.6% based on the total weight of the etching solution composition as 100%. Specifically, the total weight of the amine compound and the amino acid compound can be 0.3%, 0.35%, 0.4%, 0.45%, 0.5%, 0.55% or 0.6%, etc., based on the total weight of the etching solution composition as 100%. In this embodiment, the total weight of the amine compound and the amino acid compound in the etching solution composition is set to 0.3-0.6%,

[0033] In one embodiment, based on the total weight of the etching solution composition as 100%, the weight of the amine compound is 0.25-0.35%, and the weight of the amino acid compound is 0.1-0.2%. Specifically, based on the total weight of the etching solution composition as 100%, the weight of the amine compound can be 0.25%, 0.28%, 0.3%, 0.32%, or 0.35%, and the weight of the amino acid compound can be 0.1%, 0.13%, 0.15%, 0.17%, or 0.2%. It should be noted that since the amine compound has a larger molecular weight and the amino acid compound has a smaller molecular weight, the use of the two can produce a synergistic effect. The larger molecular weight amine compound can be adsorbed on a large area of ​​the oxide semiconductor layer surface, and the smaller molecular weight amino acid compound can adsorb the remaining unbound areas, thereby further enhancing the protective effect on the oxide semiconductor layer. In this embodiment, the weight of the amine compound is set to 0.25-0.35%, and the weight of the amino acid compound is set to 0.1-0.2%. This ensures that the etching solution composition has good etching efficiency for copper-based metals and molybdenum-based metals, while improving the protection effect on the oxide semiconductor layer and further reducing damage to the oxide semiconductor layer, especially the oxide semiconductor layer with increased gallium zinc content.

[0034] In one embodiment, the chelating agent includes one or more of iminodisuccinic acid, iminodiacetic acid, nitrilotriacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, aminotris(methylenephosphonic acid), (1-hydroxyethane-diyl)bis(phosphonic acid), ethylenediaminetetra(methylenephosphonic acid), and diethylenetriaminepenta(methylenephosphonicacid). These compounds can inhibit the decomposition of hydrogen peroxide and passivate metal ions generated during the etching process, thereby improving the stability of the etching solution composition.

[0035] The etchant includes one or more of ammonium sulfate, ammonium bisulfate, potassium sulfate, potassium bisulfate, sodium sulfate and sodium bisulfate, and is used to improve the etching speed to achieve the effect of improving process efficiency.

[0036] The inhibitor includes one or more of 3-amino-1,2,3-triazole, 3-amino-1,2,4-triazole, 4-amino-1,2,3-triazole, 4-amino-1,2,4-triazole, 5-methyltetrazole, 5-aminotetrazole, imidazole and pyrazole, which can be combined with the surface of the metal trace to inhibit corrosion caused by the etching solution composition, reduce the critical dimension bias of the metal trace, and improve process accuracy.

[0037] In one embodiment, based on the total weight of the etching solution composition as 100%, the weight of hydrogen peroxide is 18-23%, the weight of the chelating agent is 2-3%, the weight of the etchant is 1-3%, and the weight of the inhibitor is 0.05%-0.5%. Specifically, based on the total weight of the etching solution composition as 100%, the weight of hydrogen peroxide can be 18%, 20%, 21%, or 23%, etc., the weight of the chelating agent can be 2%, 2.2%, 2.5%, 2.8%, or 3%, etc., the weight of the etchant can be 1%, 1.5%, 2%, 2.5%, or 3%, etc., and the weight of the inhibitor can be 0.05%, 0.1%, 0.25%, 0.35%, or 0.5%, etc. In this embodiment, the weight of hydrogen peroxide in the etching solution composition is set to 18-23%, the weight of the chelating agent is set to 2-3%, the weight of the etching agent is set to 1-3%, and the weight of the inhibitor is set to 0.05%-0.5%. This allows the etching solution composition to maintain an appropriate etching rate for copper-based metals and molybdenum-based metals, and while maintaining etching efficiency, inhibits corrosion of metal traces, ensures the stability of the etching solution composition, and provides the etching solution composition with excellent and stable etching performance.

[0038] In one embodiment, the pH value of the etching solution composition is in the range of 4 to 7. Specifically, the pH value of the etching solution composition can be in the range of 4 to 6, or 4 to 5. When using a hydrogen peroxide-based etching solution, the lower the pH, the better the etching effect on copper-based metals, and the higher the pH, the better the etching effect on molybdenum-based metals. In addition, when the pH is high, the stability of hydrogen peroxide will decrease. Therefore, in this embodiment, the pH value of the etching solution composition is in the range of 4 to 5, which can ensure the etching efficiency of the etching solution composition for copper-based metals and molybdenum-based metals and the stability of the etching performance of the etching solution composition. Optionally, the pH of the etching solution composition can be controlled within a specific range by adding a pH adjuster. The pH adjuster can include one or more of metal hydroxides and ammonium hydroxide functional groups. The amount of the pH adjuster added can be adjusted according to actual conditions, and this application does not limit this.

[0039] In one embodiment, the etching solution composition further includes a stabilizer. The stabilizer may include a polyol compound, such as polyethylene glycol. In this embodiment, the addition of the stabilizer to the etching solution composition can increase the viscosity of the etching solution composition, thereby improving the stability of the etching solution composition. Specifically, based on the total weight of the etching solution composition as 100%, the weight of the stabilizer can be 0.5-3%. The amount of the stabilizer added can be adjusted according to actual conditions and is not limited in this application.

[0040] Accordingly, the embodiment of the present application also provides an oxide semiconductor device, the oxide semiconductor device includes an oxide semiconductor layer and a source and a drain arranged on the oxide semiconductor layer, the source and the drain include a stacked structure of copper-based metals and molybdenum-based metals, and the source and the drain are etched using the etching solution composition described in the above embodiment. It should be noted that the present application does not limit the specific structure of the oxide semiconductor device, which can be an etch stop layer (ESL) structure or a back channel etch (BCE) structure. It is understandable that since the source and drain of the oxide semiconductor device are etched using the etching solution composition described in the above embodiment, the damage to the oxide semiconductor layer under the source and drain after etching is reduced, thereby improving the yield and performance of the oxide semiconductor device.

[0041] It should be noted that copper-based metals include copper (Cu) and alloys containing copper, and molybdenum-based metals include molybdenum (Mo) and alloys containing molybdenum. In some embodiments of the present application, the laminated structure of the copper-based metal and the molybdenum-based metal may be a copper-based metal in the lower layer and a molybdenum-based metal in the upper layer, or a molybdenum-based metal in the lower layer and a copper-based metal in the upper layer, or a multilayer structure including the copper-based metal and the molybdenum-based metal. The specific configuration of the laminated structure of the copper-based metal and the molybdenum-based metal can be selected according to actual conditions and is not limited in this application.

[0042] Hereinafter, the etching solution composition and the oxide semiconductor device of the present application will be described through specific examples.

[0043] Example 1

[0044] The etching solution composition is prepared in the following ratio: based on the total weight of the etching solution composition as 100%, 0.25% hexamethylenetetramine, 0.1% lysine, 23% hydrogen peroxide, 2.5% iminodisuccinic acid, 0.1% pyrazole, 2.0% ammonium hydrogen sulfate, 1% polyethylene glycol, and the balance is water.

[0045] The difference between Examples 2 to 8 and Comparative Example 1 and Example 1 is that the components of the etching solution composition are changed (the total weight of the etching solution composition is 100%, and the balance is water), as shown in Table 1 below.

[0046] Table 1: Etching solution composition ratios of Examples and Comparative Examples

[0047]

[0048]

[0049] The etching performance of the etching solution composition was evaluated as follows:

[0050] Test piece preparation: An organic insulating film was formed on a glass substrate; a layer of IGZO with varying molar ratios of indium, gallium, and zinc (including 1:1:1, 1:2:3, and 1:3:6) was formed on the organic insulating film; a three-layer metal structure (150 / 2600 / 300mm thick) of molybdenum-titanium alloy (MoTi), copper (Cu), and molybdenum-titanium alloy (MoTi) was formed on the IGZO layer; after patterning using a photoresist process, the sample was cut into 4×3cm test pieces using a diamond knife.

[0051] Etching: 1 kg of the etching solution composition provided in the above examples and comparative examples was added to a beaker and heated in a water bath. When the temperature reached 33°C, a test piece was placed in the beaker for etching. The etching time was based on the final point detection (when the copper-molybdenum laminate outside the photoresist layer was completely etched). Each test piece was etched for 300 seconds.

[0052] Observation: The etched specimens were cleaned and dried, and the damage on the cross section and surface of the IGZO layer of the specimens was observed using a scanning electron microscope.

[0053] The etching performance of each etching solution composition is shown in Table 2 below.

[0054] Table 2

[0055]

[0056]

[0057] As shown in Table 2, the etching solutions provided in Examples 1 to 5 contain moderate levels of hydrogen peroxide and etchant, and contain amine compounds such as hexamethylenetetramine and amino acids such as lysine and aspartic acid. Therefore, they are able to maintain a good etching rate for copper and molybdenum metals, are suitable for conventional production processes, and protect the IGZO layer while minimizing damage to the IGZO layer. Furthermore, when the molar ratio of indium:gallium:zinc in the IGZO increases from 1:1:1 to 1:2:3 and 1:3:6, the etching solutions provided in Examples 1 to 5 can still effectively protect the IGZO layer.

[0058] Specifically, taking the etching solution composition provided in Example 1 as an example, please refer toFigure 1 and Figure 2 , Figure 1 and Figure 2 The following are scanning electron microscope cross-sectional observations and top-down observations of a test piece etched with the etching solution composition provided in Example 1 (IGZO indium: gallium: zinc molar ratio of 1:3:6). In the cross-sectional observation, it can be observed that the thickness of the IGZO layer under the photoresist that has not been exposed to the etching solution is comparable to the thickness of the IGZO layer etched by the etching solution outside the photoresist; in the top-down observation, it can be observed that the surface of the IGZO layer is relatively flat. The above results all indicate that the IGZO layer is not significantly damaged, indicating that the etching solution composition exhibits excellent etching performance and does not cause significant damage to the IGZO layer.

[0059] Please also refer to Figure 3 and Figure 4 , Figure 3 and Figure 4 The following are scanning electron microscopy cross-sectional and top-down images of a test piece (IGZO indium:gallium:zinc molar ratio of 1:3:6) etched with the etching solution composition provided in Comparative Example 1. In the cross-sectional image, it can be observed that the thickness of the IGZO layer below the photoresist, which has not been exposed to the etching solution, is greater than the thickness of the IGZO layer outside the photoresist that has been etched by the etching solution. In the top-down image, it can be observed that the surface of the IGZO layer is relatively rough, indicating that the IGZO layer is not effectively protected and has been damaged by the etching solution.

[0060] In summary, the etching solution composition provided in the embodiments of the present application has good etching performance for copper-based metals and molybdenum-based metals, while significantly reducing the damage of the etching solution composition to the oxide semiconductor layer with increased gallium-zinc content.

[0061] The above is a detailed introduction to an etching solution composition and an oxide semiconductor device provided in the embodiments of the present application. Specific examples are used herein to illustrate the principles and implementation methods of the present application. The description of the above embodiments is only used to help understand the method and core ideas of the present application. At the same time, for those skilled in the art, based on the ideas of the present application, there may be changes in the specific implementation methods and application scopes. In summary, the content of this specification should not be understood as limiting the present application.

Claims

1. An etching solution composition, characterized in that Based on the total weight of the etching solution composition as 100%, the etching solution composition includes 0.25-0.35% of an amine compound, 0.1-0.2% of an amino acid compound, 21-23% of hydrogen peroxide, 2.5% of iminodisuccinic acid, 1.8-2.0% of ammonium bisulfate, 0.05-0.1% of pyrazole, and the balance of water; The amine compound includes hexamethylenetetramine, and the amino acid compound includes one or both of lysine and aspartic acid.

2. An oxide semiconductor device, characterized in that: The oxide semiconductor device includes an oxide semiconductor layer and a source electrode and a drain electrode disposed on the oxide semiconductor layer. The source electrode and the drain electrode include a stacked structure of a copper-based metal and a molybdenum-based metal. The source electrode and the drain electrode are etched using the etching solution composition according to claim 1.

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