CN116180082A - Etching liquid composition - Google Patents

Etching liquid composition Download PDF

Info

Publication number
CN116180082A
CN116180082A CN202211678875.8A CN202211678875A CN116180082A CN 116180082 A CN116180082 A CN 116180082A CN 202211678875 A CN202211678875 A CN 202211678875A CN 116180082 A CN116180082 A CN 116180082A
Authority
CN
China
Prior art keywords
acid
etching
parts
etching solution
solution composition
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202211678875.8A
Other languages
Chinese (zh)
Inventor
金妍伶
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
TCL Huaxing Photoelectric Technology Co Ltd
Original Assignee
TCL Huaxing Photoelectric Technology Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by TCL Huaxing Photoelectric Technology Co Ltd filed Critical TCL Huaxing Photoelectric Technology Co Ltd
Priority to CN202211678875.8A priority Critical patent/CN116180082A/en
Publication of CN116180082A publication Critical patent/CN116180082A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • 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
    • C23F1/02—Local etching
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • ing And Chemical Polishing (AREA)

Abstract

The application provides an etching solution composition, which comprises hydrogen peroxide, a chelating agent, an etching inhibitor and a wetting agent. The etching solution composition provided by the application has no damage to the oxide film, and has good stability and etching property, so that the metal film forms a low TAPER, and the process yield is improved.

Description

Etching liquid composition
Technical Field
The application relates to the technical field of etching processes, in particular to an etching solution composition.
Background
In a thin film transistor (Thin Film Transistor, TFT), copper (Cu) is used as a metal wiring in order to reduce the resistance of a metal film and reduce signal delay. However, copper (Cu) has poor adhesion to glass and silicon layers, and diffusion of copper (Cu) has an influence on silicon layers, so that a copper-based/molybdenum-based multilayer structure metal film is formed as a metal wiring by using copper as a main metal film and molybdenum or a molybdenum alloy as a Barrier metal layer.
In order to effectively etch the multilayer metal film, a hydrogen peroxide etching solution is generally used. Since copper has a good etching efficiency in a low PH range, a typical PH range of a hydrogen peroxide etching solution is 1-3, but fluorine compounds are required to be used in the PH range to avoid the occurrence of defects in the panel manufacturing process due to molybdenum (or molybdenum alloy) residues.
However, when a fluorine-containing compound etching solution is used for an oxide thin film transistor (oxide TFT), the oxide film is damaged, and the performance of the oxide TFT is greatly affected.
Although there is an etching solution for etching copper-based/molybdenum-based multilayer metal films, which does not contain fluorine compounds and does not damage Oxide films, when such etching solution is applied to Oxide TFT processes, high levels of roughness are easily formed in metal wiring, which causes adverse effects in subsequent processes. Among them, one of the reasons for forming the high taper is that in the Oxide TFT process, in order to prevent copper ions of the source and drain from diffusing into the Oxide film of the active layer, a multi-layered structure of a molybdenum-based metal shield layer is formed on the top and bottom of a copper-based metal film, but the high taper is difficult to form by etching the side surface of the metal film due to strong adhesion between the top metal shield layer and the photoresist during etching. Another reason for forming the high-pitch is that the etching rate is slow because the fluorine compound is not added to the etching liquid, and the formation of the high-pitch is difficult due to difficulty in etching the side surface.
Disclosure of Invention
In view of this, the present application provides an etching solution composition, which has no damage to the oxide film, and has good stability and etching property, so that the metal film forms a low-tag structure, and further the process yield is improved.
The application provides an etching solution composition, which comprises the following components: hydrogen peroxide, chelating agents, etchants, etching inhibitors, and wetting agents.
In an alternative embodiment of the present application, the etching solution composition includes, in parts by weight: 10-25 parts of hydrogen peroxide, 1-4 parts of chelating agent, 0.5-5 parts of etchant, 0.01-1 part of etching inhibitor and 0.001-1 part of wetting agent.
In an alternative embodiment of the present application, the etching solution composition includes, in parts by weight: 17-23 parts of hydrogen peroxide, 2-3 parts of chelating agent, 0.5-2 parts of etchant, 0.1-0.6 part of etching inhibitor and 0.05-0.5 part of wetting agent.
In an alternative embodiment of the present application, the etching solution composition further includes a solvent, and the solvent is water.
In an alternative embodiment of the present application, the chelating agent comprises at least one of iminodiacetic acid, nitrilotriacetic acid, ethylenediamine tetraacetic acid, diethyl nitroacetic acid, aminotri (methylenephosphonic acid), (1-ethanol-diyl) bis (phosphonic acid), ethylenediamine tetraacetic acid (methylenephosphonic acid), diethylenetriamine penta (trimethylphosphoric acid), acetic acid, malic acid, formic acid, butyric acid, citric acid, glycolic acid, oxalic acid, malonic acid, valeric acid, propionic acid, tartaric acid, gluconic acid, and succinic acid.
In an alternative embodiment of the present application, the etchant includes at least one of ammonium sulfate, ammonium bisulfate, potassium sulfate, potassium bisulfate, sodium sulfate, and sodium bisulfate.
In an alternative embodiment of the present application, the residue removing agent includes at least one of potassium nitrate, sodium nitrate, aluminum nitrate, copper nitrate, silver nitrate, ferric nitrate, and tin nitrate.
In an alternative embodiment of the present application, the etching inhibitor is an azole compound comprising at least one 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.
In an alternative embodiment of the present application, the wetting agent comprises at least one of polypropylene glycol, dipropylene glycol, and poly (1, 2-butylene glycol).
In an alternative embodiment of the present application, the etching solution composition has a PH of 4-6.
The beneficial effects of this application lie in: the wetting agent is added into the etching solution composition, so that the wettability between the photoresist and the metal film layer interface is improved through the wetting agent, the etching capability on the side surface of the metal film layer is improved, and the problem that the metal film layer forms high super due to the fact that the side surface of the metal film layer is difficult to etch because the adhesiveness between the photoresist and the metal film layer interface is high is solved. The etching solution composition has the advantages of no damage to the oxide film, proper etching speed, good stability and etching property, and low taper structure of the metal film layer, thereby improving the process yield.
Drawings
In order to more clearly illustrate the embodiments or the technical solutions in the prior art, the following description will briefly introduce the drawings that are needed in the embodiments or the description of the prior art, it is obvious that the drawings in the following description are only some embodiments of the present application, and that other drawings can be obtained according to these drawings without inventive effort for a person skilled in the art.
Fig. 1 is a scanning electron micrograph of a MoTi/Cu/MoTi three-layer metal film etched by an etchant composition provided in example 2 of the present application.
Fig. 2 is a scanning electron micrograph of a MoTi/Cu/MoTi three-layer metal film etched with an etchant composition provided in comparative example 2 of the present application.
Detailed Description
The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application. It will be apparent that the described embodiments are only some, but not all, of the embodiments of the present application. All other embodiments, which can be made by those skilled in the art based on the embodiments herein without making any inventive effort, are intended to be within the scope of the present application.
In the description of the present application, it should be understood that the azimuth or positional relationship indicated by the terms "upper", "lower", etc. are based on the azimuth or positional relationship shown in the drawings, and are merely for convenience of description of the present application and to simplify the description, and do not indicate or imply that the apparatus or element referred to must have a specific azimuth, be configured and operated in a specific azimuth, and thus should not be construed as limiting the present application. Furthermore, the terms "first," "second," and the like, are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include one or more of the described features. In the description of the present application, the meaning of "a plurality" is two or more, unless specifically defined otherwise.
The present application may repeat reference numerals and/or letters in the various examples, and such repetition is for the purpose of simplicity and clarity and does not in itself dictate a relationship between the various embodiments and/or configurations discussed.
The application provides an etching solution composition, which comprises the following components: hydrogen peroxide, chelating agents, etchants, etching inhibitors, and wetting agents.
In some embodiments, the etchant composition further comprises a solvent.
The hydrogen peroxide is used as a main oxidant for oxidizing the metal film, and the weight part of the hydrogen peroxide in the etching solution composition is 10-25 parts. Preferably, the hydrogen peroxide is 17-23 parts by weight. When the hydrogen peroxide content of the etching solution composition is within the range, the multi-layer structure metal film can be fully oxidized, the etching efficiency is good, the etching speed is proper, the process is easy to control, the accumulated number of processed pieces is moderate, the process efficiency can be effectively improved, and the process benefit is improved. When the hydrogen peroxide content of the etching liquid composition is below the lower limit of the above range, the etching liquid cannot sufficiently oxidize and corrode the metal film, resulting in a problem of metal residue; when the hydrogen peroxide content of the etching solution composition is higher than the upper limit of the above range, the etching rate may be too fast to be advantageous for the whole process.
The chelating agent is used for chelating dissociated metal ions and reducing the decomposition of hydrogen peroxide. Too many metal ions generated during the etching process accelerate the attack on hydrogen peroxide and accelerate the decomposition of hydrogen peroxide, and the chelating agent inhibits the decomposition of hydrogen peroxide by inactivating the oxidized metal ions during the etching process, thereby ensuring the stability of the etching solution composition. The etching solution composition comprises 1-4 parts by weight of chelating agent. Preferably, the chelating agent is 2-3 parts by weight. When the chelating agent content of the etching liquid composition is within the above range, a high etching efficiency can be maintained, stability of the composition can be ensured, and the number of cumulative treatments can be increased. When the chelating agent content of the etching liquid composition is lower than the lower limit of the above range, the chelating agent content is too low to be advantageous in terms of the service life of the entire etching liquid composition, and when the chelating agent content of the etching liquid composition is higher than the upper limit of the above range, there is a possibility that the chelating agent content cannot be completely dissolved, affecting the etching performance.
The chelating agent may be, but is not limited to, iminodiacetic acid (iminodiacetic acid), nitrilotriacetic acid (nitrilotriacetic acid), ethylenediamine tetraacetic acid (ethylenediaminetetraacetic acid), diethyl endonitroacetic acid (diethylenetrinitrilacetic acid), aminotri (methylenephosphonic acid) (aminotris (methylenephosphonic acid)), (1-ethanol-diyl) di (phosphonic acid) ((1-hydroxy-silane-di) bis (phosphonic acid)), ethylenediamine tetraacetic acid (methylenephosphonic acid) (ethylenediamine tetra (methylenephosphonic acid)), diethylenetriamine penta (trimethylphosphoric acid) (Diethylenetriamine penta (methylene phosphonicacid), iminodisuccinic acid (iminodisuccinic acid), acetic acid (acetic acid), hydroxysuccinic acid (maleic acid), formic acid (butyric acid), butyric acid (Citric acid), glycolic acid (glyconic acid), oxalic acid (oxalic acid), malonic acid (maleic acid), valeric acid (valeric acid), propionic acid (propionic acid), succinic acid (Succinic acid) or a combination of hydrogen peroxide (Succinic acid) or the like that may be used to inhibit decomposition of one or more of the acids, and the etching solution has better stability.
The etchant is used for etching the metal film, and can improve the etching speed and adjust the PH value of the etching liquid composition. The etching agent in the etching liquid composition is 0.5-5 parts by weight. Preferably, the etchant is 0.5-2 parts by weight. When the content of the etchant of the etching liquid composition is within the above range, the original etching efficiency can be maintained, the etching liquid can have a proper etching speed, the etching section of the metal film is good, and the process efficiency is improved. When the content of the etchant in the etching liquid composition is lower than the lower limit of the range, the etching speed is slower, so that the processing time is increased, and the process efficiency is affected; when the content of the etchant in the etchant composition is higher than the upper limit of the above range, the etching rate is too high, and problems such as line break and Peeling (PR Peeling) are likely to occur.
The etchant is a sulfuric acid based compound, which may be, but is not limited to, ammonium sulfate ((NH) 4 ) 2 SO 4 ) Hydrogen sulfateAmmonium (NH) 4 HSO 4 ) Potassium sulfate (K) 2 SO 4 ) Potassium bisulfate (KHSO) 4 ) Sodium sulfate (Na) 2 SO 4 ) Or sodium bisulfate (NaHSO) 4 ) And the like. Preferably, the etchant employs ammonium bisulfate (NH 4 HSO 4 ). The use of the above compounds can improve etching rate to increase process efficiency.
The etching inhibitor is used for protecting the metal wire formed by etching, and the etching inhibitor is combined with the metal on the surface of the metal wire to inhibit the corrosion of the metal wire caused by the etching solution composition. The etching inhibitor is 0.01-1 part by weight in the etching liquid composition. Preferably, the etching inhibitor is 0.1 to 0.6 parts by weight. When the etching inhibitor content of the etching liquid composition is within the above range, the etching rate can be adjusted to maintain a proper etching rate and inhibit the metal wiring from being corroded. When the etching inhibitor content of the etching solution composition is lower than the lower limit of the range, poor linearity of the metal wiring is caused; when the etching inhibitor content of the etching liquid composition is higher than the upper limit of the above range, a problem of metal residue is easily caused.
The etching inhibitor is an azole compound, the azole compound can adjust the etching speed between metal films, increase the accumulated processing number, reduce the critical dimension deviation (critical dimension bias, CD bias) and improve the process benefit.
The etching inhibitor may be, but is not limited to, 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. Preferably, the etching inhibitor is 5-aminotetrazole, which has a better effect on improving the stability or etching efficiency of the etching solution.
The wetting agent is used for adjusting the wettability between the photoresist and the metal film interface to form a low tar. In the etching process, the top metal shielding layer (top) of the metal film in contact with the photoresist has strong adhesiveness, so that the side etching of the metal film is difficult, and the formed metal wiring layer is high. The wetting agent added by the method can improve the wettability of the etching solution composition between the photoresist and the interface of the shielding metal film, so that the etching capability of the side surface of the metal film is improved, and the metal wiring is prevented from forming high particles.
The weight part of the wetting agent in the etching liquid composition is 0.001-1 part. Preferably, the wetting agent is 0.05-0.5 parts by weight. When the content of the wetting agent in the etching liquid composition is within the above range, the metal film can be reduced while not affecting the etching of the metal film. When the content of the wetting agent of the etching liquid composition is lower than the lower limit of the above range, the effect of lowering the tip is not obvious; when the content of the wetting agent of the etching liquid composition is higher than the upper limit of the above range, excessive addition results in enhancement of etching ability, adverse effect on the top metal shielding layer, poor coverage of the PV layer, and the like.
The wetting agent may be, but is not limited to, one or a combination of several of polypropylene glycol (polypropylene glycol), dipropylene glycol (dipropylene glycol), dipropylene glycol and poly (1, 2-butylene glycol). Preferably, the wetting agent is polypropylene glycol (polypropylene glycol).
The remaining components in the etching liquid composition are solvents, and the solvents may be water, preferably deionized water, and more preferably deionized water having a non-resistance value of 18mΩ·cm or more.
The pH value of the etching liquid composition ranges from 4 to 6. Preferably, the pH value of the etching solution composition is in the range of 4-5.
The etching solution composition according to the present application may further contain usual additives such as a pH adjuster and a preservative as required within a range to achieve the objects and effects of the present invention.
The present application also provides an etching method, comprising:
forming an oxide semiconductor film on a substrate, forming a metal film on the oxide semiconductor film, and forming a photoresist pattern of a predetermined shape on the metal film by photolithography;
etching the metal film by using the photoresist pattern as a mask and adopting an etching solution composition to pattern the metal film so as to form a metal wiring;
wherein, the etching liquid composition comprises the following components in parts by weight: 10-25 parts of hydrogen peroxide, 1-4 parts of chelating agent, 0.5-5 parts of etchant, 0.01-1 part of etching inhibitor, 0.001-1 part of wetting agent and the balance of water.
Preferably, the etching solution composition comprises, by weight: the etching solution composition comprises the following components in parts by weight: 17-23 parts of hydrogen peroxide, 2-3 parts of chelating agent, 0.5-2 parts of etchant, 0.1-0.6 part of etching inhibitor, 0.05-0.5 part of wetting agent and the balance of water.
The oxide semiconductor film may be an indium gallium zinc oxide semiconductor film in this application. The oxide semiconductor is an oxide series consisting of indium, gallium and zinc, wherein the ratio of indium to gallium to zinc is 1:1:1 based on the molecular weight.
In some embodiments, the oxide semiconductor film may be one of an Indium Tin Oxide (ITO) semiconductor film, an Indium Zinc Oxide (IZO) semiconductor film, and an Indium Tin Zinc Oxide (ITZO) semiconductor film.
In the present application, the metal film is a multilayer structure of a copper-based metal film and a molybdenum-based metal film. The metal film may be a copper metal film/molybdenum-based metal film or a molybdenum-based metal film/copper metal film two-layer structure. The metal film may have a three-layer or more multilayer structure in which a molybdenum-based metal film and a copper-based metal film are alternately stacked. Preferably, the metal film is a three-layer film structure of molybdenum metal film/copper metal film/molybdenum metal film which are sequentially overlapped, the top and the bottom of the metal film structure are shielding metal film layers with the same material, and the film layers have better adhesion, so that the copper diffusion phenomenon of the copper metal film is improved, and the device performance can be further improved.
In an Oxide thin film transistor (Oxide TFT) structure, a metal film with a three-layer structure is used as a metal wiring, so that the device has better stability, but in the etching process, the side surface of a copper metal film is difficult to etch due to strong adhesion between a photoresist and a top shielding metal film, so that a high taper is formed on the copper metal film, and further, a bad problem is generated in a later stage process.
The wetting agent is added into the etching solution composition, so that the wettability between the photoresist and the top shielding metal layer interface is improved through the wetting agent, the etching capability on the side surface of the copper metal film is improved, and the problem that the copper metal film forms a high taper due to the fact that the side surface of the copper metal film is difficult to etch due to the fact that the adhesiveness between the photoresist and the top shielding metal film layer interface is large is solved.
The present application is described in further detail below by way of specific examples.
Example 1
Preparing an etching solution composition, wherein the etching solution composition comprises the following components in parts by weight: 22 parts of hydrogen peroxide, 2 parts of diethylenetriamine penta (trimethyl phosphoric acid), 0.5 part of succinic acid, 0.15 part of 5-aminotetrazole, 1.5 parts of ammonium sulfate, 0.2 part of polypropylene glycol, 0.75 part of potassium hydroxide and the balance of water.
Example 2
Preparing an etching solution composition, wherein the etching solution composition comprises the following components in parts by weight: 22 parts of hydrogen peroxide, 2.5 parts of diethylenetriamine penta (trimethyl phosphoric acid), 0.3 part of succinic acid, 0.2 part of 5-aminotetrazole, 1.5 parts of ammonium sulfate, 0.3 part of polypropylene glycol, 0.9 part of potassium hydroxide and the balance of water.
Example 3
Preparing an etching solution composition, wherein the etching solution composition comprises the following components in parts by weight: 22 parts of hydrogen peroxide, 2.5 parts of diethylenetriamine penta (trimethyl phosphoric acid), 0.3 part of succinic acid, 0.15 part of 5-aminotetrazole, 1 part of ammonium sulfate, 0.2 part of polypropylene glycol, 0.7 part of potassium hydroxide and the balance of water.
Comparative example 1
Preparing an etching solution composition, wherein the etching solution composition comprises the following components in parts by weight: 22 parts of hydrogen peroxide, 2.5 parts of diethylenetriamine penta (trimethyl phosphoric acid), 0.3 part of succinic acid, 0.2 part of 5-aminotetrazole, 1.5 parts of ammonium sulfate, 0.9 part of potassium hydroxide and the balance of water.
Comparative example 2
Preparing an etching solution composition, wherein the etching solution composition comprises the following components in parts by weight: 22 parts of hydrogen peroxide, 2.5 parts of diethylenetriamine penta (trimethyl phosphoric acid), 0.3 part of succinic acid, 0.2 part of 5-aminotetrazole, 1.5 parts of ammonium sulfate, 2 parts of polypropylene glycol, 0.9 part of potassium hydroxide and the balance of water.
Comparative example 3
Preparing an etching solution composition, wherein the etching solution composition comprises the following components in parts by weight: 10 parts of hydrogen peroxide, 2.5 parts of diethylenetriamine penta (trimethyl phosphoric acid), 0.3 part of succinic acid, 0.2 part of 5-aminotetrazole, 1.5 parts of ammonium sulfate, 0.3 part of polypropylene glycol, 0.9 part of potassium hydroxide and the balance of water.
Comparative example 4
Preparing an etching solution composition, wherein the etching solution composition comprises the following components in parts by weight: 22 parts of hydrogen peroxide, 4 parts of diethylenetriamine penta (trimethyl phosphoric acid), 0.3 part of succinic acid, 0.2 part of 5-aminotetrazole, 1.5 parts of ammonium sulfate, 0.3 part of polypropylene glycol, 0.9 part of potassium hydroxide and the balance of water.
The total weight of the etching solution composition is 100 parts.
Etching characteristics of the etching liquid compositions of examples 1 to 3 and comparative examples 1 to 4 were evaluated by etching tests.
Specifically, an organic insulating film is firstly evaporated on a glass substrate, an IGZO oxide film is then evaporated on the organic insulating film, and then source electrode and drain electrode metal films are evaporated, wherein the source electrode and drain electrode metal films have a three-layer film structure of MoTi/Cu/MoTi (thickness: 150/7,000/300). A photoresist layer was formed on the metal film, the photoresist was patterned by photolithography, and the patterned substrate was cut into test samples of 4cm X3 cm size using a diamond knife.
1kg of each of the etching liquid compositions of examples 1 to 3 and comparative examples 1 to 4 was placed in the corresponding 7 beakers, respectively, an equal amount of the test sample was placed in the corresponding 7 beakers, and the beakers were placed in a water bath (water bath temperature 32 ℃) to perform etching, and the end point detection (End Point Detection, EPD) observation was performed during the total etching time, wherein 100% etching was performed during the end point detection time in order to confirm the characteristics of the copper metal film tap.
And cleaning the etched test sample, drying, and observing the etching characteristics of the section of the dried test sample by using a scanning electron microscope.
FIG. 1 is a scanning electron micrograph of a MoTi/Cu/MoTi trilayer metal film etched with the etchant composition of example 2. It can be seen from fig. 1 that the etched copper metal film has a lower tip.
FIG. 2 is a scanning electron micrograph of a MoTi/Cu/MoTi three-layer metal film etched with the etchant composition of comparative example 2. It can be seen from fig. 2 that the copper metal film top etchant after etching precipitated, and Data open defects were observed, and the formed TAPER was higher.
Etching performance of the etching solution compositions of examples 1 to 3 and comparative examples 1 to 4 was evaluated by the following experimental data of etching completion time, critical deviation (Critical dimension bias, CD bias), moTi film Tip (MoTi Tip), copper metal film etching taper angle (Cu Tip) and IGZO damage rate. The experimental results are detailed in table 1.
TABLE 1 etching completion time, CD bias, moTi Tip, cu Tip and IGZO damage test results
Figure BDA0004018260930000091
Figure BDA0004018260930000101
The excellent level criteria for judging the etched metal film were: the MoTi Tip range is below 0.05 mu m, and the Cu Tip range is 55-65 degrees.
As is clear from table 1, the etchant composition of comparative example 1 was free from the addition of a wetting agent, and had a higher taper of approximately 90 ° in the copper metal film after etching; the addition of excess wetting agent in comparative example 2 resulted in the MoTi Tip having NG; when the hydrogen peroxide in comparative example 3 is below the limit of the present application, and when the chelating agent in comparative example 4 is beyond the limit of the present application, the copper metal film TAPER is high. In embodiment 1, embodiment 2 and embodiment 3, the wetting agent is added, and the wettability between the photoresist and the top MoTi film interface is improved due to the addition of the wetting agent, so that the etching capability on the side surface of the copper metal film is improved, the etched metal film has good MoTi Tip and copper metal film Tip, the etching solution composition does not contain fluorine compounds, the IGZO oxide film is not damaged, the etching speed is proper, and the stability and the etching performance are good, so that the metal film layer forms a low Tip structure, and the process yield is improved.
In summary, although the present application has been described with reference to the preferred embodiments, the preferred embodiments are not intended to limit the application, and those skilled in the art can make various modifications and adaptations without departing from the spirit and scope of the application, and the scope of the application is therefore defined by the claims.

Claims (10)

1. An etching solution composition, characterized in that the etching solution composition comprises: hydrogen peroxide, chelating agents, etchants, etching inhibitors, and wetting agents.
2. The etching solution composition according to claim 1, wherein the etching solution composition comprises, in parts by weight: 10-25 parts of hydrogen peroxide, 1-4 parts of chelating agent, 0.5-5 parts of etchant, 0.01-1 part of etching inhibitor and 0.001-1 part of wetting agent.
3. The etching liquid composition according to claim 2, wherein the etching liquid composition comprises, in parts by weight: 17-23 parts of hydrogen peroxide, 2-3 parts of chelating agent, 0.5-2 parts of etchant, 0.1-0.6 part of etching inhibitor and 0.05-0.5 part of wetting agent.
4. The etchant composition of claim 1, further comprising a solvent, wherein the solvent is water.
5. The etching solution composition according to any one of claims 1 to 4, wherein the chelating agent comprises at least one of iminodiacetic acid, nitrilotriacetic acid, ethylenediamine tetraacetic acid, diethyl endonitroacetic acid, aminotri (methylenephosphonic acid), (1-ethanol-diyl) bis (phosphonic acid), ethylenediamine tetraacetic acid (methylenephosphonic acid), diethylenetriamine penta (trimethylphosphoric acid), acetic acid, hydroxysuccinic acid, formic acid, butyric acid, citric acid, glycolic acid, oxalic acid, malonic acid, valeric acid, propionic acid, tartaric acid, grape acid, and succinic acid.
6. The etching solution composition according to any one of claims 1 to 4, wherein the etchant comprises at least one of ammonium sulfate, ammonium bisulfate, potassium sulfate, potassium bisulfate, sodium sulfate, and sodium bisulfate.
7. The etching solution composition according to any one of claims 1 to 4, wherein the residue removing agent comprises at least one of potassium nitrate, sodium nitrate, aluminum nitrate, copper nitrate, silver nitrate, iron nitrate, and tin nitrate.
8. The etching solution composition according to any one of claims 1 to 4, wherein the etching inhibitor is an azole compound comprising at least one 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.
9. The etchant composition of any of claims 1-4, wherein the wetting agent comprises at least one of polypropylene glycol, dipropylene glycol, and poly (1, 2-butylene glycol).
10. The etching solution composition according to any one of claims 1 to 4, wherein the pH of the etching solution composition is 4 to 6.
CN202211678875.8A 2022-12-26 2022-12-26 Etching liquid composition Pending CN116180082A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202211678875.8A CN116180082A (en) 2022-12-26 2022-12-26 Etching liquid composition

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202211678875.8A CN116180082A (en) 2022-12-26 2022-12-26 Etching liquid composition

Publications (1)

Publication Number Publication Date
CN116180082A true CN116180082A (en) 2023-05-30

Family

ID=86441346

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202211678875.8A Pending CN116180082A (en) 2022-12-26 2022-12-26 Etching liquid composition

Country Status (1)

Country Link
CN (1) CN116180082A (en)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104513981A (en) * 2013-10-02 2015-04-15 易安爱富科技有限公司 Etching liquid composition for copper-and-molybdenum-containing film
KR20190031698A (en) * 2017-09-18 2019-03-27 주식회사 이엔에프테크놀로지 Etching composition
CN114182259A (en) * 2021-12-10 2022-03-15 Tcl华星光电技术有限公司 Etching solution
CN114540817A (en) * 2022-02-11 2022-05-27 Tcl华星光电技术有限公司 Etching solution composition, display panel and preparation method thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104513981A (en) * 2013-10-02 2015-04-15 易安爱富科技有限公司 Etching liquid composition for copper-and-molybdenum-containing film
KR20190031698A (en) * 2017-09-18 2019-03-27 주식회사 이엔에프테크놀로지 Etching composition
CN114182259A (en) * 2021-12-10 2022-03-15 Tcl华星光电技术有限公司 Etching solution
CN114540817A (en) * 2022-02-11 2022-05-27 Tcl华星光电技术有限公司 Etching solution composition, display panel and preparation method thereof

Similar Documents

Publication Publication Date Title
KR20100040352A (en) Cu or cu alloy ething liquid with high selectivity and method for fabricating lcd thereof
JP2011228618A (en) Etchant composition for metal wiring, and method for manufacturing thin-film transistor display panel using the same
KR102293674B1 (en) Etching solution composition for copper-based metal layer and method for etching copper-based metal layer using the same
KR102293675B1 (en) Etching solution composition for copper-based metal layer and method for etching copper-based metal layer using the same
KR102400343B1 (en) Metal film etchant composition and manufacturing method of an array substrate for display device
KR102323941B1 (en) Etching solution composition for copper-based metal layer and method for etching copper-based metal layer using the same
KR102493061B1 (en) Metal layer etchant composition
KR20150024764A (en) Manufacturing method of an array substrate for liquid crystal display
KR20110026050A (en) Etchant for thin film transistor-liquid crystal display
CN116180082A (en) Etching liquid composition
KR20130021322A (en) Method for forming metal line
KR20170042933A (en) Manufacturing method of an array substrate for liquid crystal display
US7419768B2 (en) Methods of fabricating integrated circuitry
KR102459685B1 (en) Etchant for cupper-based metat layer, manufacturing method of an array substrate for display using the same and an array substrate for display
TWI758342B (en) Etching composition
KR102310093B1 (en) Manufacturing method of an array substrate for liquid crystal display
KR20080107502A (en) Etchant composition for molybdenum-titanium alloy layer and indium oxide layer, etching method using the same, and method for fabricating panel display device using the same
CN115821264A (en) Etching solution composition
KR102450288B1 (en) Fluorine-free etching composition for multylayer metal film and method for etching of multylayer metal film using the composition
KR102269325B1 (en) Etching solution composition for molybdenum-containing layer and manufacturing method of an array substrate for liquid crystal display using the same
KR102371075B1 (en) Composition for Etching Aluminum-Containing Metal Layer
KR102459681B1 (en) Etchant for cupper-based metat layer, manufacturing method of an array substrate for liquid crystal display using the same and an array substrate for liquid crystal display
KR102343735B1 (en) Etchant for cupper-based metat layer, manufacturing method of an array substrate for display using the same and an array substrate for display
KR102368367B1 (en) Etchant for cupper-based metat layer, manufacturing method of an array substrate for display device using the same and an array substrate for display device
KR101170382B1 (en) Etchant for thin film transistor-liquid crystal display

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination