CN108004550A - Etching solution and its application for copper/molybdenum film layer - Google Patents
Etching solution and its application for copper/molybdenum film layer Download PDFInfo
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- CN108004550A CN108004550A CN201711483863.9A CN201711483863A CN108004550A CN 108004550 A CN108004550 A CN 108004550A CN 201711483863 A CN201711483863 A CN 201711483863A CN 108004550 A CN108004550 A CN 108004550A
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- Prior art keywords
- acid
- etching solution
- etching
- copper
- film layer
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Classifications
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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
- C23F1/44—Compositions for etching metallic material from a metallic material substrate of different composition
-
- 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
-
- 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
Abstract
The invention belongs to liquid crystal panel processing technique field, in particular discloses a kind of etching solution for copper/molybdenum film layer, it includes following component mixed uniformly by weight percent：0.1%~40% oxidant, 0.1%~5% inorganic acid, 0.1%~30% organic acid, 0.001%~5% etching stabilizer and 0.1%~5% chelating agent.Etching solution according to the present invention is a kind of floride-free etching solution, its is environmentally friendly, will not cause the damage of the special materials such as substrate and the IGZO of the materials such as glass.In addition, etching solution adjusts the etching speed of copper/molybdenum film layer according to the present invention, the etching outline with appropriate cone angle is become, and controls and ensures no Mo residuals under corresponding CD Loss, is particularly suitable for the larger situation of Mo layer thickness.Present invention also offers a kind of application based on above-mentioned etching solution in liquid crystal display panel.
Description
Technical field
The invention belongs to liquid crystal display panel processing technique field, it relates in particular to be used in a kind of liquid crystal display panel
Etching solution and its application in copper/molybdenum film layer.
Background technology
With the increase of LCD display board size, wherein grid and data metal wiring usually using copper metal, with
Compared toward the aluminium chromium distribution in technology, copper can do line width lower, be more suitable for the making of resolution panels；But
The adhesion of copper and glass substrate and dielectric film is relatively low, the problems such as easily diffusing into active layer, so usually using conducts such as molybdenums
The lower film metal of copper.
The generation type of copper wiring pattern is generally in liquid crystal display panel：First, on substrate by PVD formed copper/
Molybdenum film, the adhesion for acting as increase copper and substrate of molybdenum, stops diffusion of the copper to substrate；Then, formed by photoresist
Pattern；Wherein, removing copper/molybdenum film of unnecessary portion needs to complete by etching solution.
However, traditional copper/molybdenum etching liquid is generally fluorine-containing, can all have a negative impact to environment and device；And it loses
Quarter, efficiency was low, and stability is poor；Can be to avoid the above problem, at present although having developed brand-new floride-free copper/molybdenum etching liquid at present
General floride-free copper/molybdenum etching liquid but there are etching power it is relatively low the problem of, when running into the larger situation of molybdenum layer thickness, easily
There is the problem of molybdenum is residual, as depicted in figs. 1 and 2.
The content of the invention
, should the present invention provides a kind of etching solution for copper/molybdenum film layer to solve the above-mentioned problems of the prior art
Etching solution is floride-free etching solution, which can control ensures do not have under corresponding CD Loss (corroding the influence wide to bar)
There are Mo residuals, be particularly suitable for the larger situation of Mo layer thickness.
In order to reach foregoing invention purpose, present invention employs following technical solution：
A kind of etching solution for copper/molybdenum film layer, including mixed uniformly oxidant, inorganic acid, organic acid, etching stabilization
Agent and chelating agent；
Wherein, in the etching solution, the mass percent of the oxidant is 0.1%~40%, the inorganic acid
Mass percent is 0.1%~5%, and the mass percent of the organic acid is 0.1%~30%, the matter of the etching stabilizer
It is 0.001%~5% to measure percentage, and the mass percent of the chelating agent is 0.1%~5%.
Further, the oxidant is oxidizing acid and/or the water soluble salt of the oxidizing acid.
Further, the oxidant is selected from hydrogen peroxide, hypochlorous acid, perchloric acid, permanganic acid, persulfuric acid, Peracetic acid
At least one of.
Further, the water soluble salt is selected from least one of sodium salt, sylvite, calcium salt, ammonium salt.
Further, the inorganic acid is selected from least one of sulfuric acid, hydrochloric acid, phosphoric acid；The organic acid be selected from formic acid,
Acetic acid, propionic acid, butyric acid, valeric acid, citric acid, malic acid, glycolic, oxalic acid, ethanedioic acid, malonic acid, succinic acid, glutaric acid, wine
At least one of stone acid, gluconic acid, glycine, butanedioic acid.
Further, the etching stabilizer is imidazoline quaternary ammonium salt and/or thin base benzotriazole.
Further, the chelating agent is selected from iminodiacetic acid, nitrilotriacetic acid, ethylenediamine tetra-acetic acid, diethylenetriamine
Pentaacetic acid, aminotrimethylenephosphonic acid, 1- hydroxy ethylene -1,1- diphosphonic acid, ethylenediamine tetraacetic methylene phosphoric acid, diethylenetriamines
At least one of pentamethylene phosphoric acid, methyl amimoacetic acid, alanine, glutamic acid, aminobutyric acid and glycine.
Further, the pH of the etching solution is 3.5~5.5.
Another object of the present invention is to provide a kind of as above any etching solution answering in liquid crystal display panel
With.
Oxidant, inorganic acid, organic acid, etching control agent and chelating of the invention by allocating different quality percentage
A variety of organic and inorganic composition such as agent, you can preparation obtains the etching solution of copper/molybdenum film layer；It is general in compared with prior art
Etching solution, etching solution of the invention is a kind of floride-free etching solution, environmentally friendly, will not cause the materials such as glass substrate and
The damage of the special materials such as IGZO (indium gallium zinc oxide)；Meanwhile the special formulation of etching solution of the invention is also particularly suitable for
The larger situation of Mo layer thickness, ensures no Mo residuals after etching.
Brief description of the drawings
What is carried out in conjunction with the accompanying drawings is described below, above and other aspect, feature and advantage of the embodiment of the present invention
It will become clearer, in attached drawing：
Fig. 1 is the SEM pictures of copper/molybdenum film layer when etching solution of the prior art is etched；
Fig. 2 is another SEM pictures of copper/molybdenum film layer when etching solution of the prior art is etched；
Fig. 3 is copper/molybdenum film layer schematic cross-section when etching solution according to the present invention is etched；
Fig. 4 is the SEM pictures of copper/molybdenum film layer when according to an embodiment of the invention 1 etching solution is etched；
Fig. 5 is another SEM pictures of copper/molybdenum film layer when according to an embodiment of the invention 1 etching solution is etched.
Embodiment
Hereinafter, with reference to the accompanying drawings to detailed description of the present invention embodiment.However, it is possible to come in many different forms real
Apply the present invention, and the specific embodiment of the invention that should not be construed as limited to illustrate here.Conversely, there is provided these implementations
Example is in order to explain the principle of the present invention and its practical application, so that others skilled in the art are it will be appreciated that the present invention
Various embodiments and be suitable for the various modifications of specific intended application.In the accompanying drawings, for the sake of clarity, element can be exaggerated
Shape and size, and identical label will be used to indicate the same or similar element all the time.
The present invention provides a kind of etching solution for copper/molybdenum film layer, the active ingredient in the etching solution includes uniformly mixed
Oxidant, inorganic acid, organic acid, etching stabilizer and the chelating agent of conjunction.
Specifically, in the etching solution, the mass percent of oxidant is 0.1%~40%, the quality percentage of inorganic acid
Number is 0.1%~5%, and the mass percent of organic acid is 0.1%~30%, and the mass percent for etching stabilizer is
0.001%~5%, the mass percent of chelating agent is 0.1%~5%；Surplus is water.
Further, oxidant is oxidizing acid and/or the water soluble salt of the oxidizing acid, and oxidant is preferably peroxide
Change at least one of hydrogen, hypochlorous acid, perchloric acid, permanganic acid, persulfuric acid, Peracetic acid, water soluble salt is preferably sodium salt, potassium
At least one of salt, calcium salt, ammonium salt.
When oxidant is hydrogen peroxide, it derives from hydrogen peroxide, i.e., prepares the etching solution, and this pair using hydrogen peroxide
The concentration of oxygen water is preferably 27%~30% (wt%).
Further, inorganic acid is selected from least one of sulfuric acid, hydrochloric acid, phosphoric acid；Organic acid is selected from formic acid, acetic acid, third
Acid, butyric acid, valeric acid, citric acid, malic acid, glycolic, oxalic acid, ethanedioic acid, malonic acid, succinic acid, glutaric acid, tartaric acid, Portugal
At least one of grape saccharic acid, glycine, butanedioic acid；It is imidazoline quaternary ammonium salt and/or thin base benzotriazole to etch stabilizer；
Chelating agent is selected from iminodiacetic acid, nitrilotriacetic acid, ethylenediamine tetra-acetic acid, diethylene triamine pentacetic acid (DTPA), aminotrimethylene phosphine
Acid, 1- hydroxy ethylene -1,1- diphosphonic acid, ethylenediamine tetraacetic methylene phosphoric acid, diethylenetriamine pentamethylene phosphoric acid, methyl amimoacetic acid,
At least one of alanine, glutamic acid, aminobutyric acid and glycine.
The pH of the etching solution is 3.5~5.5, other films are damaged when in use to prevent too low pH from causing acidity excessive
Layer and excessive pH can cause the hydrogen peroxide in the etching solution to decompose.
The invention also discloses application of the above-mentioned etching solution in liquid crystal display panel, i.e., using above-mentioned etching solution to copper/
The method that molybdenum film layer is etched, including step：Copper/molybdenum film layer is contacted with etching solution as above.
Specifically, the device with copper/molybdenum film layer is contacted with the etching solution, such as can be by this with copper/molybdenum film layer
Device be dipped in etching solution.
With reference to Fig. 3, which includes substrate 1 and lamination is provided with barrier film 21, wiring 22, resists successively on substrate 1
Layer 3 is lost, the material of wherein barrier film 21 is generally Mo metals, and the material for connecting up 22 is Cu metals；Thus, barrier film 21 and wiring
22 combinations are copper of the present invention/molybdenum film layer.
What deserves to be explained is good etching solution should make the wiring cross sectional shape after etching be in defined scope, obtain
Good wiring cross sectional shape after to etching；In general, following both sides requirements should be met：(1) 22 ends are connected up
Etching face and lower floor substrate 1 where angle (cone angle) α for being formed of plane be 30 °~60 ° positive cone；(2) from against corrosion
Play the distance a (CD Loss) contacted with the barrier film 21 being arranged under wiring 22 untill the end of substrate 1 in 3 end of layer
For less than 1.2 μm, preferably less than 1 μm.
Hereinafter, the etching solution and its etching that are used for copper/molybdenum film layer according to the present invention will be imitated with reference to specific embodiment
Fruit is described in detail.
Embodiment 1
The etching solution for copper/molybdenum film layer that the present embodiment is provided includes the mass percent shown in table 1 below
Each material：
The composition of the etching solution of 1 embodiment 1 of table
Based on the above-mentioned requirement to etching solution, copper/molybdenum film layer is etched using the etching solution in embodiment 1, and it is right
The different angle of copper/molybdenum film layer after etching has carried out sem test (SEM) respectively, its test result respectively such as Fig. 4 and
Shown in Fig. 5；Figure 4, it is seen that 37.09 ° of cone angle can be formed through the etching solution in overetch embodiment 1, and CD is damaged
Lose as 952.5nm；From figure 5 it can be seen that remained through the etching solution in overetch embodiment 1 without Mo.
It can thus be seen that the etch effect according to the present invention for the etching solution of copper/molybdenum film layer is good, meanwhile, should
The engraving method of etching solution is simple, easily operated.
Although the present invention has shown and described with reference to specific embodiment, it should be appreciated by those skilled in the art that：
In the case where not departing from the spirit and scope of the present invention limited by claim and its equivalent, can carry out herein form and
Various change in details.
Claims (9)
1. a kind of etching solution for copper/molybdenum film layer, it is characterised in that including mixed uniformly oxidant, inorganic acid, organic
Acid, etching stabilizer and chelating agent；
Wherein, in the etching solution, the mass percent of the oxidant is 0.1%~40%, the quality of the inorganic acid
Percentage is 0.1%~5%, and the mass percent of the organic acid is 0.1%~30%, the quality hundred of the etching stabilizer
Fraction is 0.001%~5%, and the mass percent of the chelating agent is 0.1%~5%.
2. etching solution according to claim 1, it is characterised in that the oxidant is oxidizing acid and/or the oxidation
Property acid water soluble salt.
3. etching solution according to claim 2, it is characterised in that the oxidant is selected from hydrogen peroxide, hypochlorous acid, high chlorine
At least one of acid, permanganic acid, persulfuric acid, Peracetic acid.
4. etching solution according to claim 3, it is characterised in that the water soluble salt is selected from sodium salt, sylvite, calcium salt, ammonium
At least one of salt.
5. etching solution according to claim 1, it is characterised in that the inorganic acid in sulfuric acid, hydrochloric acid, phosphoric acid extremely
Few one kind；The organic acid is selected from formic acid, acetic acid, propionic acid, butyric acid, valeric acid, citric acid, malic acid, glycolic, oxalic acid, second two
At least one of acid, malonic acid, succinic acid, glutaric acid, tartaric acid, gluconic acid, glycine, butanedioic acid.
6. etching solution according to claim 1, it is characterised in that the etching stabilizer for imidazoline quaternary ammonium salt and/or
Dredge base benzotriazole.
7. etching solution according to claim 1, it is characterised in that the chelating agent is selected from iminodiacetic acid, three second of ammonia
Acid, ethylenediamine tetra-acetic acid, diethylene triamine pentacetic acid (DTPA), aminotrimethylenephosphonic acid, 1- hydroxy ethylene -1,1- diphosphonic acid, second
Diamines tetramethylene phosphoric acid, diethylenetriamine pentamethylene phosphoric acid, methyl amimoacetic acid, alanine, glutamic acid, aminobutyric acid and glycine
At least one of.
8. according to any etching solutions of claim 1-7, it is characterised in that the pH of the etching solution is 3.5~5.5.
A kind of 9. application of etching solution as described in claim 1-8 is any in liquid crystal display panel.
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| CN201711483863.9A CN108004550A (en) | 2017-12-29 | 2017-12-29 | Etching solution and its application for copper/molybdenum film layer |
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| CN201711483863.9A CN108004550A (en) | 2017-12-29 | 2017-12-29 | Etching solution and its application for copper/molybdenum film layer |
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108893741A (en) * | 2018-06-12 | 2018-11-27 | 江苏理工学院 | A kind of floride-free copper-molybdenum etching solution applied to thin film transistor line |
| CN109023372A (en) * | 2018-08-31 | 2018-12-18 | 深圳市华星光电技术有限公司 | Copper/molybdenum film layer etchant |
| CN109136926A (en) * | 2018-08-31 | 2019-01-04 | 深圳市华星光电技术有限公司 | Lithographic method and etching device for copper-molybdenum film layer |
| CN110644001A (en) * | 2019-10-22 | 2020-01-03 | 湖北兴福电子材料有限公司 | Copper etching solution |
| CN110846663A (en) * | 2019-11-14 | 2020-02-28 | Tcl华星光电技术有限公司 | Etching solution composition and method for forming metal circuit |
| CN110993614A (en) * | 2019-11-27 | 2020-04-10 | 深圳市华星光电半导体显示技术有限公司 | Display panel preparation device and method |
| CN111472003A (en) * | 2020-05-27 | 2020-07-31 | 湖北兴福电子材料有限公司 | Etching solution for adjusting etching cone angle in copper process panel and adjusting method |
| CN111472000A (en) * | 2020-04-15 | 2020-07-31 | Tcl华星光电技术有限公司 | Etching method of copper-molybdenum film layer and array substrate |
| CN111876780A (en) * | 2020-08-31 | 2020-11-03 | 武汉迪赛新材料有限公司 | Ammonium persulfate system etching solution for etching TFT copper-molybdenum layer |
| CN113072306A (en) * | 2021-04-08 | 2021-07-06 | 烟台远东精细化工有限公司 | Preparation method of electronic grade mixed acid etching solution |
| CN114411151A (en) * | 2022-01-19 | 2022-04-29 | 福建中安高新材料研究院有限公司 | Copper-molybdenum metal film etching solution, application method thereof and display panel |
| CN114855169A (en) * | 2022-05-16 | 2022-08-05 | 江苏和达电子科技有限公司 | Copper etching liquid composition and use method thereof |
| CN115948746A (en) * | 2022-12-30 | 2023-04-11 | 浙江奥首材料科技有限公司 | Al/Mo etching solution, and preparation method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104513983A (en) * | 2013-10-07 | 2015-04-15 | 易安爱富科技有限公司 | Etching liquid composition for copper-and-molybdenum-containing film |
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2017
- 2017-12-29 CN CN201711483863.9A patent/CN108004550A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104513983A (en) * | 2013-10-07 | 2015-04-15 | 易安爱富科技有限公司 | Etching liquid composition for copper-and-molybdenum-containing film |
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108893741A (en) * | 2018-06-12 | 2018-11-27 | 江苏理工学院 | A kind of floride-free copper-molybdenum etching solution applied to thin film transistor line |
| CN109023372A (en) * | 2018-08-31 | 2018-12-18 | 深圳市华星光电技术有限公司 | Copper/molybdenum film layer etchant |
| CN109136926A (en) * | 2018-08-31 | 2019-01-04 | 深圳市华星光电技术有限公司 | Lithographic method and etching device for copper-molybdenum film layer |
| CN110644001A (en) * | 2019-10-22 | 2020-01-03 | 湖北兴福电子材料有限公司 | Copper etching solution |
| CN110846663A (en) * | 2019-11-14 | 2020-02-28 | Tcl华星光电技术有限公司 | Etching solution composition and method for forming metal circuit |
| CN110993614B (en) * | 2019-11-27 | 2022-06-10 | 深圳市华星光电半导体显示技术有限公司 | Display panel preparation device and method |
| CN110993614A (en) * | 2019-11-27 | 2020-04-10 | 深圳市华星光电半导体显示技术有限公司 | Display panel preparation device and method |
| CN111472000A (en) * | 2020-04-15 | 2020-07-31 | Tcl华星光电技术有限公司 | Etching method of copper-molybdenum film layer and array substrate |
| CN111472000B (en) * | 2020-04-15 | 2021-07-27 | 苏州华星光电技术有限公司 | Etching method of copper-molybdenum film layer and array substrate |
| CN111472003A (en) * | 2020-05-27 | 2020-07-31 | 湖北兴福电子材料有限公司 | Etching solution for adjusting etching cone angle in copper process panel and adjusting method |
| CN111876780A (en) * | 2020-08-31 | 2020-11-03 | 武汉迪赛新材料有限公司 | Ammonium persulfate system etching solution for etching TFT copper-molybdenum layer |
| CN113072306A (en) * | 2021-04-08 | 2021-07-06 | 烟台远东精细化工有限公司 | Preparation method of electronic grade mixed acid etching solution |
| CN114411151A (en) * | 2022-01-19 | 2022-04-29 | 福建中安高新材料研究院有限公司 | Copper-molybdenum metal film etching solution, application method thereof and display panel |
| CN114855169A (en) * | 2022-05-16 | 2022-08-05 | 江苏和达电子科技有限公司 | Copper etching liquid composition and use method thereof |
| CN114855169B (en) * | 2022-05-16 | 2024-02-23 | 江苏和达电子科技有限公司 | Copper etching solution composition and use method thereof |
| CN115948746A (en) * | 2022-12-30 | 2023-04-11 | 浙江奥首材料科技有限公司 | Al/Mo etching solution, and preparation method and application thereof |
| CN115948746B (en) * | 2022-12-30 | 2024-04-30 | 浙江奥首材料科技有限公司 | Al/Mo etching solution, and preparation method and application thereof |
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Application publication date: 20180508 |