Compatible display panel aluminum etching liquid and preparation method and application thereof
By using a combination of fluoride -containing compounds and organic amine in the etching solution, the existing etching solution is difficult to compatible with the problems of Moalmo and Tialti metal membrane layers, and the stable controllable etching rate and shape of MO, Al, and TI are realized Optimization of appearance.
Patent Information
- Application Number
- CN202411435318.2
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-10-15
- Publication Date
- 2025-01-28
AI Technical Summary
The existing etching liquid is difficult to compatible with the MoAlMo and TiAlTi metal film layers, resulting in morphological defects and etching rate difficult to control.
A combination of fluoride -containing compounds and organic amine is used to leave the F ion by reacting the TI etching rate by reacting to the organic amine reaction, and adsorbing through oxygen atoms and nitrogen atoms and MOs and AL to prevent point erosion.
The stable and controllable etching rate of MO, Al, and TI is achieved, avoiding appearance defects, and also etching Moalmo and Tialti metal layers.
Smart Images
Figure CN119372649A_ABST
Abstract
Description
Technical Field
[0001] The invention relates to etching liquid technology, and in particular to a compatible display panel aluminum etching liquid, and a preparation method and application thereof. Background Art
[0002] Traditional MoAlMo etching solutions mostly use a phosphoric acid-nitric acid-acetic acid system, which is widely used in the manufacturing processes of liquid crystal displays (TFT-LCD), light-emitting diodes (LEDs), and organic light-emitting diodes (OLEDs). In the manufacturing process of the above-mentioned different components, etching solutions with different component contents are required due to the different structural compositions and thicknesses of the film layers. For example, in the display panel manufacturing process, etching solutions made of TiAlTi materials are required, and traditional etching solutions made of TiAlTi materials are mostly mixed acid systems containing F.
[0003] For MoAlMo materials, traditional phosphoric acid-nitric acid-acetic acid etching solutions are usually used for etching. Due to the chemical activity and electrochemical effect of metal Mo itself, the corrosion rate of Mo is often 2 to 5 times that of metal Al. If a mixed acid system etching solution containing F is used to etch MoAlMo, the corrosion rate of Mo will increase further, and pitting is very likely to occur due to the presence of F ions, causing serious morphological defects. Therefore, it is difficult for current etching solutions to be compatible with multiple metal film layers at the same time, especially when the etched metal contains molybdenum, titanium, and aluminum metals, it is difficult to simultaneously control the etching rates of Mo, Al, and Ti, resulting in morphological defects. Summary of the invention
[0004] The purpose of the present invention is to propose a compatible display panel aluminum etching solution, in view of the problem that the current etching solution is not compatible with MoAlMo and TiAlTi and easily causes morphological defects. The etching solution has a stable and controllable etching rate for Mo, Al and Ti materials, does not damage the insulating layer and the photoresist, and has very good application prospects and large-scale industrial promotion potential in the field of display panel manufacturing.
[0005] It should be noted that, in the present invention, unless otherwise specified, the specific meaning of "including" in relation to composition limitations and descriptions includes both open-ended "including", "comprising", etc. and similar meanings, as well as closed-ended "composed of", "composed of", etc. and similar meanings.
[0006] To achieve the above object, the technical solution adopted by the present invention is: a compatible display panel aluminum etching solution, comprising the following components in weight proportion:
[0007]
[0008] Furthermore, the inorganic acid comprises component A and component B, wherein component A is one or more of phosphoric acid, sulfuric acid, carbonic acid and perchloric acid, and component B is nitric acid.
[0009] Furthermore, the inorganic acid comprises component A and component B in a mass ratio of preferably 10-30:1-5.
[0010] Furthermore, the inorganic acid comprises component A and component B in a mass ratio of more preferably 20:1.
[0011] Furthermore, the inorganic acid is phosphoric acid and nitric acid.
[0012] Furthermore, the inorganic acid is phosphoric acid and nitric acid in a mass ratio of preferably 10-30:1-5.
[0013] Furthermore, the inorganic acid is phosphoric acid and nitric acid in a mass ratio of more preferably 20:1.
[0014] Furthermore, the inorganic acid is 22-30 parts.
[0015] The inorganic acid of the present invention adopts a composite acid, for example, a combination of phosphoric acid and nitric acid. Phosphoric acid, as a stable polybasic inorganic weak acid, can provide a basic hydrogen ion concentration for chemical reactions, and its ionization products dihydrogen phosphate and hydrogen phosphate can also exist as buffer components to maintain the hydrogen ion concentration; nitric acid, as an oxidizing strong acid, mainly provides oxidizing properties for the etching process to ensure that the etching process can proceed. If the phosphoric acid content is too high / low, it will affect the initial hydrogen ion concentration, resulting in an overly fast / slow etching reaction; if the nitric acid content is too high / low, it will cause a violent / weakened metal oxidation process, affecting the rate of reaction between metal oxides and hydrogen ions, and the "content" here refers to a mass ratio relationship exceeding a limit.
[0016] Furthermore, the organic acid comprises component C and component D, wherein component C is one or more of formic acid, acetic acid, propionic acid and lactic acid; and component D is one or more of 2-aminoethanesulfonic acid, p-aminobenzenesulfonic acid and aminonaphthalenesulfonic acid.
[0017] Furthermore, the organic acid is component C and component D in a mass ratio of preferably 19-30:1-3.
[0018] Furthermore, the organic acid is component C and component D in a mass ratio of preferably 30:1.
[0019] Furthermore, the organic acid is acetic acid and p-aminobenzenesulfonic acid.
[0020] Furthermore, the organic acid is acetic acid and p-aminobenzenesulfonic acid in a mass ratio of preferably 19-30:1-3.
[0021] Furthermore, the organic acid is acetic acid and p-aminobenzenesulfonic acid in a mass ratio of more preferably 30:1.
[0022] Furthermore, the organic acid is 5-6.2 parts.
[0023] The organic acid described in the present invention adopts a composite acid, for example, a combination of acetic acid and p-aminobenzenesulfonic acid. Acetic acid, as an organic weak acid, stabilizes the hydrogen ion concentration in the solution and thus stabilizes the reaction rate; p-aminobenzenesulfonic acid, as another oxidizing acid, provides the necessary oxidizing environment for metal corrosion. At the same time, the amino group on p-aminobenzenesulfonic acid can also participate in the reaction of fluorinated ester compounds and organic amines to a certain extent, thereby promoting the reaction. If the acetic acid content is too high / low, the etching solution will have a low hydrogen ion concentration / poor life; if the p-aminobenzenesulfonic acid content is too high / low, the metal oxidation process will be violent / weakened, affecting the reaction rate of metal oxides and hydrogen ions. The "content" here refers to the mass ratio relationship exceeding the limit.
[0024] Furthermore, the fluorine-containing ester compound is one or more of methyl trifluoromethanesulfonate, phenyl trifluoromethanesulfonate, benzyl trifluoromethanesulfonate and isopropyl trifluoromethanesulfonate.
[0025] Furthermore, the fluorine-containing ester compound is preferably methyl trifluoromethanesulfonate.
[0026] Furthermore, the fluorine-containing ester compound is 3.6-5 parts.
[0027] Furthermore, the molecular weight of the organic amine is less than 180.
[0028] Further, the organic amine is one or more of 1-azetidinylpropylamine (CAS No.: 54262-75-8), 2-azetidinylmethylamine (CAS No.: 92398-47-5), 3-azetidinylmethylamine (CAS No.: 116770-48-0), 1-ethyl-3-azetidinamine (CAS No.: 55438-58-9) and 4-(1-azetidinyl)-1-butylamine (CAS No.: 1565-55-5).
[0029] Furthermore, the organic amine is preferably 1-azetidinylpropylamine.
[0030] Furthermore, the organic amine is 2-4 parts.
[0031] Fluorinated ester compounds react with organic amines in the etching solution to ionize F ions, promote the ionization of F ions into the solution, and maintain the Ti etching rate; at the same time, the oxygen atoms in the fluorinated ester compounds and the nitrogen atoms in the organic amines have lone pairs of electrons, which can adsorb with Mo and Al with strong chemical activity to prevent pitting of Mo and Al in the F-containing environment; thereby achieving the control of the etching rates of Mo, Al, and Ti. The etching rate of Ti at 35-45°C is: The etching rate of Mo is: The etching rate of Al is: The same etching solution can be used to etch MoAlMo and TiAlTi metal layers.
[0032] Furthermore, the ultrapure water is 30-40 parts.
[0033] Furthermore, the ultrapure water is deionized water with a resistance of ≥18 MΩ.
[0034] Another object of the present invention is to disclose a method for preparing a compatible display panel aluminum etching solution, comprising the following steps:
[0035] Step 1: Weigh each component in its respective amount;
[0036] Step 2: Mix all components and stir until all materials are completely dissolved to obtain a compatible display panel aluminum etching solution.
[0037] Another object of the present invention is to disclose an application of a compatible display panel aluminum etching solution in the field of MoAlMo or TiAlTi etching.
[0038] Furthermore, a method for etching a substrate plated with MoAlMo or TiAlTi material using a compatible display panel aluminum etching solution comprises the following steps:
[0039] Step 1: Immerse the MoAlMo or TiAlTi-plated substrate in a compatible display panel aluminum etching solution for etching; the etching time is 40-80s, and the etching temperature is 35-45°C;
[0040] Step 2: Use pure water to clean the MoAlMo or TiAlTi substrate after etching in step 1 above, and finally blow dry it with compressed nitrogen.
[0041] Furthermore, the etching time in step 1 is 50-70s.
[0042] Furthermore, the etching temperature in step 1 is 40°C.
[0043] The compatible display panel aluminum etching liquid of the present invention, its preparation method and application have the following advantages compared with the prior art:
[0044] 1) The present invention adopts a combination of fluorinated ester compounds and organic amines. The fluorinated ester compounds react with the organic amines in the solution to ionize F ions, promote the ionization of F ions into the solution, and maintain the Ti etching rate; at the same time, the oxygen atoms in the fluorinated ester compounds and the nitrogen atoms in the organic amines have lone pairs of electrons, which can be adsorbed with Mo and Al with strong chemical activity to prevent pitting of Mo and Al in the F-containing environment; thereby achieving the control of the etching rates of Mo, Al, and Ti. At 40°C, Ti: Mo: Al: That is, the etching solution of the present invention is compatible with etching MoAlMo and TiAlTi metal layers.
[0045] 2) The present invention adopts a mixed acid system to avoid the strong alkaline system solution from reacting with the "photoacid" in the photoresist to damage the photoresist. In the TFT manufacturing process, the insulating layer is SiO2. The etching solution of the present invention provides a F ion source through a fluorinated ester compound. The F ion concentration in the etching solution can also be dynamically controlled by the reaction of the fluorinated ester compound with the organic amine to prevent the F ion concentration from being too high to cause damage to the insulating layer.
[0046] Therefore, the compatible display panel aluminum etching liquid of the present invention has a stable and controllable etching rate for Mo, Al, and Ti materials, has no damage to the insulating layer and the photoresist, and has very good application prospects and large-scale industrial promotion potential in the field of display panels. BRIEF DESCRIPTION OF THE DRAWINGS
[0047] Figure 1 This is a SEM picture of the cross section of TiAlTi treated with the phosphoric acid-nitric acid-acetic acid system etching solution described in Comparative Example 6, with a magnification of 40,000 times;
[0048] Figure 2 This is a top view SEM picture of the TiAlTi surface treated with the phosphoric acid-nitric acid-acetic acid system etching solution described in Comparative Example 6, with a magnification of 40,000 times;
[0049] Figure 3 This is a SEM picture of the MoAlMo cross section treated with the F-containing mixed acid system etching solution described in Example 7, with a magnification of 40,000 times;
[0050] Figure 4 This is a top view SEM picture of the MoAlMo surface treated with the F-containing mixed acid system etching solution described in Example 7, with a magnification of 40,000 times;
[0051] Figure 5 SEM image of the TiAlTi cross section treated with the etching solution described in Example 1, magnified 40,000 times;
[0052] Figure 6Top view SEM image of the TiAlTi surface treated with the etching solution described in Example 1, magnified 40000 times;
[0053] Figure 7 SEM image of the MoAlMo cross section treated with the etching solution described in Example 1, magnified 40,000 times;
[0054] Figure 8 Top view SEM image of the MoAlMo surface treated with the etching solution described in Example 1, with a magnification of 40,000 times. DETAILED DESCRIPTION
[0055] The present invention is further described below with reference to the examples. The description of the technical features described below is based on representative embodiments and specific examples of the present invention, but the present invention is not limited to these embodiments and specific examples. It should be noted that:
[0056] Unless otherwise stated, the units used in this specification are all international standard units, and the numerical values and numerical ranges appearing in the present invention should be understood to include the inevitable systematic errors in industrial production.
[0057] In this specification, the numerical range expressed using "a numerical value A to a numerical value B" means a range including the endpoints numerical values A and B.
[0058] In the present specification, a numerical range expressed using "above" or "below" means a numerical range including the number.
[0059] In this specification, the word "may" means both performing a certain process and not performing a certain process.
[0060] In this specification, the use of "optional" or "optional" indicates that certain substances, components, execution steps, application conditions and other factors are used or not used.
[0061] In this specification, when "normal temperature" or "room temperature" is used, the temperature may be 15-25°C.
[0062] In this manual, the reagents or instruments used without indicating the manufacturer are all conventional products that can be obtained through commercial purchase.
[0063] Examples 1-5
[0064] Examples 1-5 disclose a variety of compatible display panel aluminum etching liquids, the components and proportions of which are shown in Table 1, and the preparation method thereof is as follows: weigh each component in its respective amount; mix all components and stir at a speed of 500r / min until all materials are completely dissolved to obtain a compatible display panel aluminum etching liquid.
[0065] Table 1 Components and ratios of compatible display panel aluminum etching solutions of Examples 1-5
[0066]
[0067]
[0068] Comparative Examples 1-7
[0069] Comparative Examples 1-7 disclose a variety of etching solutions, the components and proportions of which are shown in Table 2, and the preparation methods thereof are the same as those of Example 1.
[0070] Table 2 Components and mass ratios of etching solutions in comparative examples 1-7
[0071]
[0072]
[0073] The etching solutions of Examples 1-5 and Comparative Examples 1-7 were tested respectively, and the test results are shown in Table 3.
[0074] Table 3 Test data
[0075]
[0076] Based on Table 3, it can be seen that the Ti etching rate of the compatible display panel aluminum etching solution of Examples 1-5 at 40°C is controlled at The Mo etching rate is controlled at The Al etching rate is controlled at Although the systems of Examples 1-5 contain F, the corrosion rate of Mo is still maintained at 2 to 5 times that of metal Al, and no top Ti protrusions appear when etching MoAlMo or TiAlTi. Regular steps are formed in the cross-section SEM after etching.
[0077] Comparative Example 1 does not add fluorinated ester compounds. Since it does not contain a F ion source, the Ti etching rate of Comparative Example 1 is too low, resulting in a Ti protruding morphology. Comparative Example 6 uses a phosphonitric acid system, and its Ti etching rate is still too low, resulting in a Ti protruding morphology.
[0078] Comparative Example 2 does not add 1-azetidinylpropylamine. Since it cannot promote the further reaction of the fluorinated ester compound, the F ion concentration in the solution cannot be maintained, and the Ti etching rate is low. Comparative Example 3 uses bis(4-(2-pyridyl)-3-azetidinyl)amine. Although it can further react with methyl trifluoromethanesulfonate to maintain the F ion concentration in the solution, it has a large molecular weight and a complex spatial structure. It may be adsorbed on the metal surface, resulting in a decrease in the etching rate. The Ti etching rate is lower than that of 1-azetidinylpropylamine. Experiments have shown that compared with heterocyclic organic amines with larger molecular weights, the organic amines with a molecular weight of less than 180 used in the present invention have better etching compatibility.
[0079] Comparative Example 4 uses a combination of phosphoric acid and sulfuric acid as the inorganic acid. Since sulfuric acid is less oxidizing than nitric acid, the Mo etching rate is low, resulting in a top Mo protrusion.
[0080] In Comparative Example 5, acetic acid is used as the organic acid. Since the oxidizing property of the etching solution is weakened, the Mo etching rate is low, and a top Mo protrusion is formed.
[0081] Comparative Example 7 uses a conventional F-containing mixed acid system. Although it has a stable etching rate for Ti, the high F ion concentration causes severe corrosion of Mo, resulting in serious damage to the Mo and Al layers.
[0082] Analysis of attached pictures: Figure 1 This is a SEM picture of the cross section of TiAlTi treated with the phosphoric acid-nitric acid-acetic acid system etching solution described in Comparative Example 6, with a magnification of 40,000 times; Figure 2 This is a top-down SEM picture of the TiAlTi surface treated with the phosphoric acid-nitric acid-acetic acid system etching solution described in Example 6, with a magnification of 40,000 times.
[0083] The two figures show the etching effect of the mixed acid system etching solution of phosphoric acid, nitric acid and acetic acid on the TiAlTi film layer. The etching rate of the top and bottom layers of Ti in the phosphoric acid, nitric acid and acetic acid system is too low, resulting in a protruding top morphology, which affects the performance of the metal circuit part in the subsequent overlap.
[0084] Figure 3 This is a SEM picture of the MoAlMo cross section treated with the F-containing mixed acid system etching solution described in Example 7, with a magnification of 40,000 times; Figure 4 This is a top view SEM picture of the MoAlMo surface treated with the F-containing mixed acid system etching solution described in Example 7, with a magnification of 40,000 times.
[0085] The two figures show the etching effect of the F-containing mixed acid system etching solution on the MoAlMo film layer. Since the corrosion rate of Mo in the etching solution is too fast, the top Mo shrinks severely and the Al surface of the middle layer is also corroded in large quantities, resulting in an increase in the overall resistance of the metal circuit.
[0086] Figure 5 SEM image of the TiAlTi cross section treated with the etching solution described in Example 1 of the present invention, magnified 40,000 times; Figure 6 Top view SEM picture of the TiAlTi surface treated with the etching solution described in Example 1 of the present invention, with a magnification of 40,000 times.
[0087] The two figures show the etching effect of the TiAlTi film layer treated with the etching solution of the present invention. After etching, the cross-sectional step morphology is regular, and there is no protruding morphology of the top Ti layer.
[0088] Figure 7 SEM image of the MoAlMo cross section treated with the etching solution described in Example 1 of the present invention, magnified 40,000 times; Figure 8 Top view SEM image of the MoAlMo surface treated with the etching solution described in Example 1 of the present invention, with a magnification of 40,000 times.
[0089] The two figures show the etching effect of the MoAlMo film layer treated by the etching solution of the present invention. After etching, no obvious corrosion occurs on the top Mo layer, and only a small Mo step appears due to the rate difference.
[0090] Combination Figure 5 and Figure 7 , proving that the etching solution described in Example 1 of the present invention is compatible with TiAlTi and MoAlMo, and still has a good morphology after etching.
[0091] in:
[0092] The test method for the morphology after etching of performance 1 is:
[0093] The etching solution of the above embodiment and comparative example of the present invention is used for etching, and the specific steps are as follows:
[0094] Step 1: Immerse the substrates plated with MoAlMo and TiAlTi materials in the above etching solutions for etching respectively; the etching time is 60s and the etching temperature is 40°C.
[0095] Step 2: Use pure water to clean the etching solution residue from the etched MoAlMo and TiAlTi substrates, and blow dry them with compressed nitrogen.
[0096] Step 3: Observe the sample morphology under SEM.
[0097] The ultrapure water used in the above steps is deionized water with a resistance of at least 18 MΩ.
[0098] The test method for performance 2 etching rate is:
[0099] The specific steps are as follows:
[0100] Step 1: Heat the etching solutions of Examples 1-5 and Comparative Examples 1-7 to 40° C. in a water bath, immerse the MoAlMo and TiAlTi substrates in the etching solutions and shake them at a gradient of 10 seconds until the metal on the surface of the MoAlMo and TiAlTi substrates is completely etched;
[0101] Step 2: Rinse the substrate in ultrapure water at least twice and blow dry with nitrogen.
[0102] Step 3: Measure the thickness of the substrate under SEM, and calculate the average etching rates of Ti, Mo, and Al respectively based on the thickness difference before and after etching / etching time.
[0103] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or replace some or all of the technical features therein with equivalents. However, these modifications or replacements do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.
Claims
1. A compatible display panel aluminum etching solution, characterized in that: The composition includes the following components in weight ratio:
2. The compatible display panel aluminum etching liquid according to claim 1, characterized in that: The inorganic acid comprises component A and component B, wherein component A is one or more of phosphoric acid, sulfuric acid, carbonic acid and perchloric acid, and component B is nitric acid.
3. The compatible display panel aluminum etching solution according to claim 1 or 2, characterized in that: The inorganic acids are phosphoric acid and nitric acid.
4. The compatible display panel aluminum etching liquid according to claim 1, characterized in that: The organic acid comprises component C and component D, wherein component C is one or more of formic acid, acetic acid, propionic acid and lactic acid; and component D is one or more of 2-aminoethanesulfonic acid, p-aminobenzenesulfonic acid and aminonaphthalenesulfonic acid.
5. The compatible display panel aluminum etching solution according to claim 1 or 4, characterized in that: The organic acids are acetic acid and p-aminobenzenesulfonic acid.
6. The compatible display panel aluminum etching liquid according to claim 1, characterized in that: The fluorine-containing ester compound is one or more of methyl trifluoromethanesulfonate, phenyl trifluoromethanesulfonate, benzyl trifluoromethanesulfonate and isopropyl trifluoromethanesulfonate.
7. The compatible display panel aluminum etching liquid according to claim 1, characterized in that: The organic amine is one or more of 1-azetidinylpropylamine, 2-azetidinylmethylamine, 3-azetidinylmethylamine, 1-ethyl-3-azetidinamine and 4-(1-azetidinyl)-1-butylamine.
8. A method for preparing the compatible display panel aluminum etching solution according to any one of claims 1 to 7, comprising the following steps: Step 1: Weigh the respective amounts of each component; Step 2: Mix all components and stir until all materials are completely dissolved to obtain a compatible display panel aluminum etching solution.
9. Application of the compatible display panel aluminum etching solution according to any one of claims 1 to 7 in the field of MoAlMo or TiAlTi etching.
10. The use according to claim 9, characterized in that: A method for etching a substrate plated with MoAlMo or TiAlTi material using a compatible display panel aluminum etching solution comprises the following steps: Step 1: Immerse the substrate coated with MoAlMo or TiAlTi material in a compatible display panel aluminum etching solution for etching; Etching temperature 35~45℃; Step 2: Use pure water to clean the MoAlMo or TiAlTi substrate after etching in step 1 above, and finally blow dry it with compressed nitrogen.