CN110230059B - Method for manufacturing metal pattern of display panel - Google Patents
Method for manufacturing metal pattern of display panel Download PDFInfo
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- CN110230059B CN110230059B CN201910585008.1A CN201910585008A CN110230059B CN 110230059 B CN110230059 B CN 110230059B CN 201910585008 A CN201910585008 A CN 201910585008A CN 110230059 B CN110230059 B CN 110230059B
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/02—Local etching
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/16—Acidic compositions
- C23F1/18—Acidic compositions for etching copper or alloys thereof
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/16—Acidic compositions
- C23F1/26—Acidic compositions for etching refractory metals
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/46—Regeneration of etching compositions
Abstract
A method for manufacturing a metal pattern of a display panel is provided, which comprises adding an etching functional agent or an etching maintaining agent into an etching solution continuously or intermittently when metal ions of a metal layer reach a corresponding content in the etching solution during etching of a copper/molybdenum metal layer until the etching functional agent or the etching maintaining agent accounts for 2-5 wt% of the total amount of the etching solution and the added etching functional agent or the etching maintaining agent.
Description
[ technical field ] A method for producing a semiconductor device
The invention relates to the technical field of display panel manufacturing, in particular to the technical field of metal pattern manufacturing.
[ background of the invention ]
With the increase in size of thin film transistor liquid crystal displays (TFT-LCDs), the amount of etching solution used in the etching process for forming metal patterns on display panels is increasing, and therefore, it is necessary to reduce the consumption of etching solution to reduce the manufacturing cost.
During the process of continuously etching the copper/molybdenum substrate in the etching solution with high copper/molybdenum ion concentration, the defects such as critical dimension loss (CD loss), etching angle (taper), undercut (undercut), and molybdenum residue, which do not meet the specification of the etching process, are easily generated, so it is necessary to develop the etching solution process for maintaining the etching characteristics based on the original etching solution during the continuous etching process to save the amount of the etching solution.
[ summary of the invention ]
In order to solve the above problems, the present invention provides a method for manufacturing a metal pattern of a display panel, including:
in the etching process of a substrate metal layer, when metal ions of the metal layer reach a corresponding content in an etching solution, an etching functional agent or an etching maintaining agent is additionally and continuously or intermittently added into the etching solution until the etching functional agent or the etching maintaining agent accounts for 2-5 wt% of the total amount of the original etching solution and the added etching functional agent or etching maintaining agent.
The etching functional agent refers to a beneficial substance composition which can make the etching effect meet the specification requirement in the etching solution.
The "etching-maintaining agent" refers to a solution used together with the etching solution to make the etching solution maintain its etching characteristics.
The "corresponding content" refers to the content of metal ions dissolved in the etching solution, which is determined by the actual etching substrate and can be obtained by experiment, so that the etching capability of the etching solution is affected, and the etched product can not meet the specification.
Preferably, the metal is a copper molybdenum alloy; the metal ions are copper ions or molybdenum ions; the corresponding content is between 5500 and 7500 ppm.
Preferably, the etching solution comprises: 5-20 wt% of hydrogen peroxide, 0.1-2 wt% of hydrogen peroxide stabilizer, 5-20 wt% of organic acid, 5-10 wt% of chelating agent, 0.001-0.2 wt% of etching inhibitor, 3-15 wt% of taper regulator and the balance of deionized water.
Preferably, the hydrogen peroxide stabilizer is at least one selected from the group consisting of N-phenylurea, N' -diphenylurea, 1, 3-diethyl-1, 3-diphenylurea, 4-methylthiosemicarbazide, and diphenylsemicarbazide.
Preferably, the organic acid is at least one selected from succinic acid, benzoic acid, malic acid, glycolic acid, cystine, aspartic acid, malonic acid, lactic acid, acetic acid, phthalic acid, salicylic acid alanine, asparagine and arginine.
Preferably, the chelating agent is at least one selected from citric acid, tartaric acid, gluconic acid, aminotrimethylene phosphonic acid, 1-hydroxyethylidene-1, 1-diphosphonic acid, sarcosine and alanine.
Preferably, the etching inhibitor is at least one selected from amino tetrazole, pyrimidine, 1, 3-thiazole, benzotriazole, 1,2, 4-1H-triazole, 3-amino-1H-1, 2, 4-triazole, imidazole and 1,2, 4-triazole.
Preferably, the conicity regulator is selected from at least one of isopropanolamine, N-ethylethanolamine, diglycolamine, diethanolamine, triisopropanolamine and monoethanolamine.
Preferably, the etching functional agent is a composition composed of at least two selected from organic acid, chelating agent and taper regulator.
Preferably, the etching maintaining agent is composed of the etching functional agent, hydrogen peroxide and water.
[ description of the drawings ]
FIG. 1 is a photograph showing a cross section of a substrate observed by a scanning electron microscope after etching under a condition that a copper ion content is 3500ppm in the example of the present invention;
FIG. 2 is a photograph showing a cross-section of a substrate observed by a scanning electron microscope after etching under a condition that a copper ion content is 5500ppm in accordance with an embodiment of the present invention; and
FIG. 3 is a photograph showing a cross section of a substrate observed with a scanning electron microscope after etching under a condition that the copper ion content is 7500ppm in the example of the present invention.
[ detailed description ] embodiments
The technical solution in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
Embodiments of the present invention and comparative embodiments 1 to 3 use a method for fabricating a metal pattern in an Array process of a thin film transistor liquid crystal display (TFT-LCD), comprising:
when copper ions of a copper/molybdenum alloy metal layer reach 3500ppm, 5500ppm and 7500ppm in an etching solution in the etching process of the metal layer, an etching maintaining agent is additionally and continuously or intermittently added in the etching solution until the etching maintaining agent accounts for 3 wt% of the total amount of the etching solution and the added etching maintaining agent.
The "etching solution" refers to a solution used for reducing the thickness of a copper/molybdenum alloy metal layer used for a TFT-LCD, or for forming a metal pattern (or wiring) therein.
As shown in table 1, the etching solution in comparative example 1 of the present invention includes: 7% by weight of hydrogen peroxide (H)2O2) 2% by weight of glycolic acid (organic acid), 0.5% by weight of benzoic acid (organic acid), 6% by weight of citric acid (chelating agent), 5% by weight of isopropanolamine (conicity modifier), 0.002% by weight of aminotetrazole (etching inhibitor), 0.25% by weight of N-phenylurea (hydrogen peroxide)Stabilizer) and the remaining deionized water.
Table 1 is provided only to better illustrate the utility of the present invention, and the range of the materials that can be used for the etching solution and the etching-maintaining agent of the present invention is not limited to table 1.
Specification for etch angle (taper angle) 30-70 ° is specification compliant, more preferably 40-60 °; for critical dimension loss (CD loss), the CD loss is 1 +/-0.25 μm, more preferably 1 +/-0.1 μm, according to the specification; for Mo residues, B (tiny) is adopted as the meeting specification, more preferably A (tiny and trace), C (visible and obvious) is adopted as the not meeting specification; for undercutting (undercut), a is specification compliant, B (minimal undercut) and C (significant and greater undercut) are both out of specification.
TABLE 1
Comparative example 1
Referring to Table 2, in the comparative example 1, the copper/molybdenum thickness is 5500 ^ and/or greater
The substrate of (2) was used as an etching sample, and the substrate was etched with 100% of the etching solution at 35 ℃ for 145 seconds,
the etching solution comprises: 7% by weight of hydrogen peroxide (H)2O2) 2 wt% glycolic acid (organic acid), 0.5 wt% benzoic acid (organic acid), 6 wt% citric acid (chelating agent), 5 wt% isopropanolamine (taper modifier), 0.002 wt% aminotetrazole (etch inhibitor), 0.25 wt% N-phenylurea (hydrogen peroxide stabilizer), and the remainder deionized water. And observing whether the copper ion content meets the specification requirements by using a scanning electron microscope after etching under the conditions that the copper ion content in the etching solution is 3500ppm, 5500ppm and 7500ppm respectively.
As shown in Table 2, under the condition that the copper ion content in the etching solution is 3500ppm, 5500ppm and 7500ppm respectively, the critical dimension loss (CD loss) is 0.95 μm, 0.99 μm and 0.97 μm respectively, which all meet the specification requirements; the etching angles (taper angle) are respectively 44 degrees, 48 degrees and 48 degrees, which meet the specification requirements; the molybdenum residue items are A, B and C (not meeting the specification requirement), and it can be known that under the condition that the copper ion content in the etching solution is 7500ppm, the etched copper circuit has visible and obvious molybdenum residue and does not meet the specification requirement; the undercut (under) items are A, A and B (out of specification), respectively, and it can be seen that the undercut (under) item of the copper circuit after etching is out of specification under the condition that the copper ion content in the etching solution is 7500 ppm.
TABLE 2
Comparative example 2
Referring to Table 2, in comparative example 2, the copper/molybdenum thickness is 5500-
When the copper ion content of the etching solution was 3500ppm, 5500ppm and 7500ppm at 35 ℃, respectively, the addition of the etching supporting agent 1 was continued until the etching supporting agent 1 was stopped at 3 wt% of the total amount of the etching solution and the added etching supporting agent 1, followed by etching the substrate for 145 seconds.
The etching maintenance agent 1 contains 7 wt% of hydrogen peroxide (H)2O2) 3 wt% glycolic acid (organic acid) and the remainder deionized water.
And observing whether the etching meets the specification requirements by using a scanning electron microscope after the etching is finished.
As shown in Table 2, under the conditions that the copper ion content is 3500ppm, 5500ppm and 7500ppm respectively, the critical dimension loss (CD loss) is 1.19 μm, 1.17 μm and 1.01 μm respectively, which all meet the specification; the etching angles (taper angle) are respectively 54 degrees, 57 degrees and 63 degrees, which meet the specification requirements; the molybdenum residue items are A, B and B, which both meet the specification requirements; the undercut (out of specification) items are B (out of specification), B (out of specification) and a, respectively, and it can be seen that the undercut (out of specification) items of the copper wiring after etching do not meet the specification under the condition that the copper ion content in the etching solution is 3500ppm and 5500 ppm.
Comparative example 3
Referring to Table 2, in comparative example 3, the copper/molybdenum thickness is 5500-
When the copper ion content of the etching solution was 3500ppm, 5500ppm and 7500ppm at 35 ℃, respectively, the addition of the etching supporting agent 2 was continued until the etching supporting agent 2 was stopped at 3 wt% of the total amount of the etching solution and the added etching supporting agent 2, followed by etching the substrate for 145 seconds.
The etch-maintaining agent 2 includes:
7% by weight of hydrogen peroxide (H)2O2) 3 wt% glycolic acid (organic acid), 1 wt% benzoic acid (organic acid) and the remainder deionized water.
And observing whether the etching meets the specification requirements by using a scanning electron microscope after the etching is finished.
As shown in Table 2, under the condition that the copper ion content in the etching solution is 3500ppm, 5500ppm and 7500ppm respectively, the critical dimension loss (CD loss) is 1.04 μm, 0.92 μm and 0.95 μm respectively, which all meet the specification requirements; the etching angles (taper angle) are 47 degrees, 51 degrees and 58 degrees respectively, which meet the specification requirements; the molybdenum residue items are A, B and B, which both meet the specification requirements; the undercut (out of specification) items are C (out of specification), B (out of specification) and B (out of specification), respectively, and it can be seen that the copper ion content in the etching solution is 3500ppm, 5500ppm and 7500ppm, and the undercut (out of specification) items of the copper circuit after etching do not meet the specification.
Examples of the invention
Referring to Table 2, in the embodiment of the present invention, the copper/molybdenum thickness is 5500 ^ according to the present invention
When the copper ion content of the etching solution was 3500ppm, 5500ppm and 7500ppm at 35 ℃, respectively, the addition of the etching supporting agent 3 was continued until the etching supporting agent 3 was stopped at 3 wt% of the total amount of the etching solution and the added etching supporting agent 3, followed by etching the substrate for 145 seconds.
The etch-maintaining agent 3 contains 7 wt% of hydrogen peroxide (H)2O2) 3 wt% glycolic acid (organic acid), 7 wt% citric acid (chelating agent), 7 wt% isopropanolamine (conicity modifier) and the remainder deionized water.
And observing whether the etching meets the specification requirements by using a scanning electron microscope after the etching is finished.
As shown in Table 2, the critical dimension loss (CD loss) was 0.97 μm, 1.01 μm and 0.94 μm, respectively, all of which meet the specification, under the condition that the copper ion content in the etching solution was 3500ppm, 5500ppm and 7500ppm, respectively; the etching angles (taper angle) are respectively 45 degrees, 45 degrees and 44 degrees, which all meet the specification; the molybdenum residue items are A, A and B, which both meet the specification requirements; the undercut (undercut) entries are A, A and A, respectively, meet specification requirements.
Compared with comparative example 1, the molybdenum residue items (the molybdenum residue items are all above grade B, and C is out of specification) of comparative example 2, comparative example 3 and the invention example are greatly improved, and all meet the product specification under the condition of 7500ppm, however, as can be seen from comparative example 2 and comparative example 3, the undercut degree is more serious compared with comparative example 1, and the product does not meet the specification at 3500 ppm; since the undercut (undercut) phenomenon can cause the bad processes such as the connection short wire of the subsequent process, the specification requirement is more severe, and the parameter requirement is all above class A.
As shown in table 2 and fig. 1 to 3, the present invention examples showed no undercut under 3500ppm, 5500ppm and 7500ppm conditions, and only a small amount of molybdenum residue, which better satisfies the requirement of the etching solution to maintain its specification characteristics at higher metal ion concentration (above 5000 ppm) based on comparative example 2 and comparative example 3.
As described above, the method of the embodiment of the invention can maintain the specification requirement required by etching in the metal pattern manufacturing process, so as to reduce the consumption of the etching solution in the TFT-LCD manufacturing process, thereby saving the production cost.
In summary, although the present invention has been described with reference to the preferred embodiments, the above-described preferred embodiments are not intended to limit the present invention, and those skilled in the art can make various changes and modifications without departing from the spirit and scope of the present invention, so that the scope of the present invention shall be determined by the appended claims.
Claims (6)
1. A method for manufacturing a metal pattern of a display panel includes:
at 35 ℃ to a thickness of
Etching the copper/molybdenum metal layer for 145 seconds, when the concentration of metal ions of the copper/molybdenum metal layer in the etching solution reaches between 5500-7500ppm, additionally continuously or intermittently adding an etching functional agent or an etching maintaining agent in the etching solution until the etching functional agent or the etching maintaining agent accounts for 3 wt% of the total amount of the etching solution and the added etching functional agent or the added etching maintaining agent, wherein the metal ions are copper ions or molybdenum ions; the etching solution comprises:
5-20 wt% of hydrogen peroxide, 0.1-2 wt% of hydrogen peroxide stabilizer, 5-20 wt% of organic acid, 5-10 wt% of chelating agent, 0.001-0.2 wt% of etching inhibitor, 3-15 wt% of taper regulator and the balance of deionized water; the etching functional agent consists of 3 wt% of organic acid, 7 wt% of chelating agent and 7 wt% of taper regulator; and
the etching maintaining agent consists of the etching functional agent, 7 wt% of hydrogen peroxide and the balance of deionized water.
2. The method for fabricating a metal pattern of a display panel according to claim 1, wherein the hydrogen peroxide stabilizer is at least one selected from the group consisting of N-phenylurea, N' -diphenylurea, 1, 3-diethyl-1, 3-diphenylurea, 4-methylthiosemicarbazide, and diphenylsemicarbazide.
3. The method for fabricating a metal pattern of a display panel according to claim 1, wherein the organic acid is at least one selected from the group consisting of benzoic acid, malic acid, cystine, aspartic acid, lactic acid, acetic acid, phthalic acid, salicylic acid, asparagine, and arginine.
4. The method of claim 1, wherein the chelating agent is selected from aminotrimethylene phosphonic acid.
5. The method of claim 1, wherein the etching inhibitor is at least one selected from the group consisting of 1, 3-thiazole, benzotriazole, 1,2, 4-1H-triazole, and 3-amino-1H-1, 2, 4-triazole.
6. The method of claim 1, wherein the taper modifier is at least one selected from the group consisting of isopropanolamine, N-ethylethanolamine, diglycolamine, diethanolamine, triisopropanolamine, and monoethanolamine.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910585008.1A CN110230059B (en) | 2019-07-01 | 2019-07-01 | Method for manufacturing metal pattern of display panel |
| PCT/CN2019/103986 WO2021000421A1 (en) | 2019-07-01 | 2019-09-02 | Method for manufacturing metal pattern of display panel |
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| CN201910585008.1A CN110230059B (en) | 2019-07-01 | 2019-07-01 | Method for manufacturing metal pattern of display panel |
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| CN110230059B true CN110230059B (en) | 2020-11-24 |
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| CN111155091A (en) * | 2020-02-13 | 2020-05-15 | Tcl华星光电技术有限公司 | Etching solution, additive and method for manufacturing metal wiring |
| CN113529085A (en) * | 2021-07-15 | 2021-10-22 | 深圳市华星光电半导体显示技术有限公司 | Etching solution and etching method |
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| KR101391023B1 (en) * | 2007-08-06 | 2014-05-02 | 동우 화인켐 주식회사 | Manufacturing method of array substrate for liquid crystal display |
| KR101243847B1 (en) * | 2011-08-18 | 2013-03-20 | 주식회사 이엔에프테크놀로지 | Method for etching cu/mo alloy film with etching capacity of etching solution improved |
| CN108950557A (en) * | 2018-07-19 | 2018-12-07 | 深圳市华星光电半导体显示技术有限公司 | A kind of copper/molybdenum etching liquid composition and its application |
| CN109082663A (en) * | 2018-07-19 | 2018-12-25 | 深圳市华星光电半导体显示技术有限公司 | A kind of copper/molybdenum etching liquid composition and its application |
| CN109234736B (en) * | 2018-08-31 | 2020-08-11 | 深圳市华星光电技术有限公司 | Long-life copper-molybdenum etching solution and etching method |
| CN109930153B (en) * | 2019-04-24 | 2021-01-01 | 深圳市华星光电技术有限公司 | Etching liquid and etching device |
| CN109930154A (en) * | 2019-04-24 | 2019-06-25 | 深圳市华星光电技术有限公司 | Etching liquid, etch combinations liquid and lithographic method |
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| CN110230059A (en) | 2019-09-13 |
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Address after: 9-2 Tangming Avenue, Guangming New District, Shenzhen City, Guangdong Province Patentee after: TCL Huaxing Photoelectric Technology Co.,Ltd. Address before: 9-2 Tangming Avenue, Guangming New District, Shenzhen City, Guangdong Province Patentee before: Shenzhen China Star Optoelectronics Technology Co.,Ltd. |