CN110144588A - Etching liquid and lithographic method - Google Patents

Etching liquid and lithographic method Download PDF

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Publication number
CN110144588A
CN110144588A CN201910338221.2A CN201910338221A CN110144588A CN 110144588 A CN110144588 A CN 110144588A CN 201910338221 A CN201910338221 A CN 201910338221A CN 110144588 A CN110144588 A CN 110144588A
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CN
China
Prior art keywords
etching liquid
acid
etching
mass percent
hydrogen peroxide
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Pending
Application number
CN201910338221.2A
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Chinese (zh)
Inventor
赵芬利
秦文
张月红
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TCL China Star Optoelectronics Technology Co Ltd
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Shenzhen China Star Optoelectronics Technology Co Ltd
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Publication date
Application filed by Shenzhen China Star Optoelectronics Technology Co Ltd filed Critical Shenzhen China Star Optoelectronics Technology Co Ltd
Priority to CN201910338221.2A priority Critical patent/CN110144588A/en
Publication of CN110144588A publication Critical patent/CN110144588A/en
Pending legal-status Critical Current

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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
    • C23F1/02—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
    • C23F1/18—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
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
    • H05K3/06—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding the conductive material being removed chemically or electrolytically, e.g. by photo-etch process
    • H05K3/067—Etchants

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

Abstract

It includes deionized water, hydrogen peroxide, organic acid, amine substance, weak acid and mild base salt, hydrogen peroxide stabilizer and alcohols material that the present invention, which provides a kind of etching liquid and lithographic method, the etching liquid,.Etching liquid does not include fluorine in the program, avoids the corrosion to substrate, improves the yields of display panel.

Description

Etching liquid and lithographic method
Technical field
The present invention relates to etching fields, more particularly to a kind of etching liquid and lithographic method.
Background technique
With popularizing for intelligent mobile terminal, display panel technology is used widely, and is developed more and more rapider.
It in display panel processing procedure, generallys use copper metal and the cablings such as gate lines, data lines is made, to transmit various letters Number, realize the display function of display panel.Specifically, Copper thin film can be coated on substrate, pattern then is carried out to Copper thin film Change, forms various metal wires.
Wherein, the copper of redundance needs to perform etching using etching liquid, however existing etching liquid typically contains fluorine, right Glass material in substrate has corrosiveness, and the yields of display panel is caused to reduce.
Summary of the invention
The purpose of the present invention is to provide a kind of etching liquid and lithographic methods, and the yields of display panel can be improved.
The embodiment of the invention provides a kind of etching liquids comprising: deionized water, hydrogen peroxide, organic acid, amine substance, Weak acid and mild base salt, hydrogen peroxide stabilizer and alcohols material.
In one embodiment, mass percent range of the deionized water in the etching liquid be 60% to Between 88.35%；The hydrogen peroxide is between 5% to 8% in the mass percent range in the etching liquid；The organic acid It is between 5% to 15% in the mass percent range in the etching liquid；Matter of the amine substance in the etching liquid Measuring percentage range is between 1% to 10%；Mass percent range of the weak acid and mild base salt in the etching liquid be Between 0.1% to 1%；Mass percent range of the hydrogen peroxide stabilizer in the etching liquid be 0.05% to 1% it Between；The alcohols material is between 0.5% to 5% in the mass percent range in the etching liquid.
In one embodiment, the organic acid includes citric acid, malic acid, succinic acid, lactic acid, glycolic, in benzoic acid It is one or more.
In one embodiment, the amine substance includes diisopropanolamine (DIPA), isopropanolamine, antifebrin and 2- amino -2 One of methyl-1-propyl alcohol is a variety of.
In one embodiment, the weak acid and mild base salt includes diammonium hydrogen phosphate or ammonium acetate.
In one embodiment, the hydrogen peroxide stabilizer is phenylurea.
In one embodiment, the alcohols material includes ethyl alcohol, methanol, ethylene glycol, one of benzyl alcohol or a variety of.
The embodiment of the invention provides a kind of lithographic methods, are performed etching using etching liquid as described above comprising:
One substrate is provided；
The substrate is placed in the magnetic field of default magnetic field strength range；
The etching liquid for being used in preset temperature range performs etching the substrate, the substrate after being etched.
In one embodiment, the preset temperature range is between 30 degrees Celsius to 35 degrees Celsius.
In one embodiment, the default magnetic field strength range is 0.3 tesla between 0.7 tesla.
Compared to existing etching liquid and lithographic method, the etching liquid in etching liquid and lithographic method of the invention includes going Ionized water, hydrogen peroxide, organic acid, amine substance, weak acid and mild base salt, hydrogen peroxide stabilizer and alcohols material do not include fluorine, keep away Exempt from corrosion of the fluorine to substrate, improves the yields of display panel.
For above content of the invention can be clearer and more comprehensible, preferred embodiment is cited below particularly, and cooperate institute's accompanying drawings, makees Detailed description are as follows:
Detailed description of the invention
Fig. 1 is the flow diagram of lithographic method provided in an embodiment of the present invention.
Fig. 2 is the schematic diagram of a scenario of lithographic method provided in an embodiment of the present invention.
Fig. 3 is another schematic diagram of a scenario of lithographic method provided in an embodiment of the present invention.
Fig. 4 is the another schematic diagram of a scenario of lithographic method provided in an embodiment of the present invention.
Specific embodiment
The explanation of following embodiment is to can be used to the particular implementation of implementation to illustrate the present invention with reference to additional schema Example.The direction term that the present invention is previously mentioned, such as "upper", "lower", "front", "rear", "left", "right", "inner", "outside", " side " Deng being only the direction with reference to annexed drawings.Therefore, the direction term used be to illustrate and understand the present invention, rather than to The limitation present invention.
The similar unit of structure is to be given the same reference numerals in the figure.
Referenced herein " embodiment " is it is meant that a particular feature, structure, or characteristic described can wrap in conjunction with the embodiments Containing at least one embodiment of the present invention.Each position in the description occur the phrase might not each mean it is identical Embodiment, nor the independent or alternative embodiment with other embodiments mutual exclusion.Those skilled in the art explicitly and Implicitly understand, embodiment described herein can be combined with other embodiments.
The embodiment of the invention provides a kind of etching liquid, which is used to perform etching the substrate in display panel, Wherein there are copper Cu film and molybdenum Mo film on substrate.As shown in table 1 below, the constituent of etching liquid includes deionized water, dioxygen Water, organic acid, amine substance, weak acid and mild base salt, hydrogen peroxide stabilizer and alcohols material.
Table 1
The constituent of etching liquid Mass percent range
Deionized water 60%-88.35%
Hydrogen peroxide 5%-8%
Organic acid 5%-15%
Amine substance 1%-10%
Weak acid and mild base salt 0.1%-1%
Hydrogen peroxide stabilizer 0.05%-1%
Alcohols material 0.5%-5%
Molybdenum in substrate can be oxidized to molybdenum trioxide MoO3 by hydrogen peroxide, and copper is oxidized to copper oxide CuO.As shown in table 1, Hydrogen peroxide is between 5% to 8% in the mass percent range in etching liquid.In the present embodiment, hydrogen peroxide is in etching liquid Mass percent be lower than 8%, the safety in etching liquid production process can be improved.
Hydrogen peroxide stabilizer can be decomposed at high temperature to avoid hydrogen peroxide.Wherein, hydrogen peroxide stabilizer can be phenyl Urea.As shown in table 1, hydrogen peroxide stabilizer is between 0.05% to 1% in the mass percent range in the etching liquid.
Deionized water can not only be decomposed to avoid hydrogen peroxide, can also avoid introducing the dry of metal ion in etching liquid It disturbs.As shown in table 1, deionized water is between 60% to 88.35% in the mass percent range in etching liquid.
Organic acid can be with CuO, MoO3Reaction, obtains copper ion and molybdenum ion, and complex copper ion and molybdenum ion.It is organic Acid includes citric acid, malic acid, succinic acid, lactic acid, glycolic, one of benzoic acid or a variety of.As shown in table 1, organic acid It is between 5% to 15% in the mass percent range in etching liquid.Inorganic acid is not needed in the present embodiment, and quarter can be improved Lose the security performance in liquid production process.
Amine substance can make the etching of copper and molybdenum generate speed difference, even if the etching speed of copper is greater than the etching speed of molybdenum Degree.Wherein, amine substance includes diisopropanolamine (DIPA), isopropanolamine, one of antifebrin and 2- amino -2 methyl-1s-propyl alcohol Or it is a variety of.As shown in table 1, amine substance is between 1% to 10% in the mass percent range in the etching liquid.
Weak acid and mild base salt with release hydrogen ions, can adjust pH (Hydrogen ion concentration, the hydrogen of etching liquid Ion concentration index) value.The etching of molybdenum caused by pH value can be prevented excessively high is too fast.Wherein, weak acid and mild base salt includes phosphoric acid hydrogen two Ammonium or ammonium acetate.As shown in table 1, mass percent range of the weak acid and mild base salt in the etching liquid be 0.1% to 1% it Between.
Alcohols material can be such that the organic matters such as above-mentioned organic acid, weak acid and mild base salt or inorganic matter dissolve.Wherein, alcohols material Including ethyl alcohol, methanol, ethylene glycol, one of benzyl alcohol or a variety of.As shown in table 1, alcohols material is in the etching liquid Mass percent range is between 0.5% to 5%.
In one embodiment, etching liquid can be etching liquid A shown in table 2.As shown in table 2 below, the composition of etching liquid A Ingredient includes deionized water, hydrogen peroxide, citric acid, diisopropanolamine (DIPA), diammonium hydrogen phosphate, phenylurea and ethyl alcohol.Above-mentioned composition Mass percent of the ingredient in etching liquid A is followed successively by 70.7%, 7.5%, 10%, 9.5%, 0.8%, 0.5% and 1%. After being performed etching by etching liquid A to substrate, as shown in figure 3, the section gradient of copper 101 can achieve 34.5 in substrate 100 Degree, i.e. taper angle theta can achieve 34.5 degree, and CD loss (the wide loss of item) L is 0.8 micron.As shown in figure 4, molybdenum does not remain.
Table 2
The constituent of etching liquid A Mass percent
Deionized water 70.7%
Hydrogen peroxide 7.5%
Citric acid 10%
Diisopropanolamine (DIPA) 9.5%
Diammonium hydrogen phosphate 0.8%
Phenylurea 0.5%
Ethyl alcohol 1%
Do not include fluorine in the etching liquid of the embodiment of the present invention, can cause to corrode to avoid to the glass in substrate.Further , the mass percent of the etching liquid hydrogen peroxide in the embodiment of the present invention is lower than 8%, can be improved in etching liquid production process Safety.And the etching liquid in the embodiment of the present invention does not include inorganic acid, and the safety in etching liquid production process can be improved Performance.
The embodiment of the invention also provides a kind of lithographic method, which is performed etching using etching liquid as above. Fig. 1 is please referred to, Fig. 1 is the flow chart of lithographic method provided in an embodiment of the present invention, which includes the following steps:
Step S101 provides a substrate.
Wherein, there are copper Cu film and molybdenum Mo film on substrate.Wherein, molybdenum film setting substrate body and Copper thin film it Between, to increase the adhesion between copper and substrate body.By patterning to Copper thin film, gate lines, data lines etc. can be formed Metal wiring.For extra copper or molybdenum, can be performed etching using the etching liquid of the present embodiment.
Substrate is placed in the magnetic field of default magnetic field strength range by step S102.
As shown in Fig. 2, in one embodiment, substrate 1 can be placed in default magnetic field strength range be 0.3 tesla extremely In magnetic field 2 between 0.7 tesla.Wherein, magnetic field 2 can promote etching liquid convection current, and quickening etching liquid is reacted with copper.It needs Illustrate, within the scope of above-mentioned default magnetic field strength, the magnetic field strength in magnetic field 2 is bigger, and etching liquid and reacting for copper are faster, obtains The cone angle arrived is smaller.
Step S103, the etching liquid for being used in preset temperature range perform etching substrate, the substrate after being etched.
In one embodiment, etching liquid can be heated, etching liquid is made to reach pre- between 30 degrees Celsius to 35 degrees Celsius If temperature range.It should be noted that in above-mentioned preset temperature range, the etch rate of etching liquid as the temperature rises and It improves.Then etching liquid is uniformly sprayed onto substrate surface to perform etching.After about 100-120 seconds, it can complete to etch.In this reality It applies in example, does not need addition etching inhibitor, etch rate can be adjusted, be reduced by adjusting the temperature of etching liquid Etching cost.
After existing etching liquid performs etching substrate, the cone angle of 50 degree to 60 degree ranges, the cone of this range are typically resulted in Angle is larger, and the electric property of substrate is caused to reduce.Substrate is performed etching using the etching liquid of the present embodiment, available 33 degree To the cone angle of 45 degree of ranges, it can make substrate that there is preferable electric property.
Next, being performed etching by taking etching liquid A as shown in Table 2 as an example to substrate.It is strong that substrate 1 is placed in magnetic field first Degree is in the uniform magnetic field 2 of 0.6 tesla.Then etching liquid A is heated to 32 degrees Celsius.It is again that the etching liquid A after heating is equal The even surface for being sprayed onto substrate 1 performs etching.After etch period reaches 110 seconds, that is, complete etching.Wherein, as shown in figure 3, copper 10 section gradient can achieve 34.5 degree, i.e. taper angle theta can achieve 34.5 degree, and CD loss (the wide loss of item) L is 0.8 micro- Rice.As shown in figure 4, molybdenum does not remain.
The lithographic method of the embodiment of the present invention, by the convection current situation of flux control etching liquid and the temperature of etching liquid, The reaction rate of etching liquid and copper is controlled, so that the copper is obtained lesser cone angle.
In conclusion although the present invention has been disclosed above in the preferred embodiment, but above preferred embodiment is not to limit The system present invention, those skilled in the art can make various changes and profit without departing from the spirit and scope of the present invention Decorations, therefore protection scope of the present invention subjects to the scope of the claims.

Claims (10)

1. a kind of etching liquid characterized by comprising deionized water, hydrogen peroxide, organic acid, amine substance, weak acid and mild base salt, Hydrogen peroxide stabilizer and alcohols material.
2. etching liquid according to claim 1, which is characterized in that
The deionized water is between 60% to 88.35% in the mass percent range in the etching liquid；
The hydrogen peroxide is between 5% to 8% in the mass percent range in the etching liquid；
The organic acid is between 5% to 15% in the mass percent range in the etching liquid；
The amine substance is between 1% to 10% in the mass percent range in the etching liquid；
The weak acid and mild base salt is between 0.1% to 1% in the mass percent range in the etching liquid；
The hydrogen peroxide stabilizer is between 0.05% to 1% in the mass percent range in the etching liquid；
The alcohols material is between 0.5% to 5% in the mass percent range in the etching liquid.
3. etching liquid according to claim 1, which is characterized in that the organic acid includes citric acid, malic acid, fourth two Acid, lactic acid, glycolic, one of benzoic acid or a variety of.
4. etching liquid according to claim 1, which is characterized in that the amine substance includes diisopropanolamine (DIPA), isopropanol Amine, one of antifebrin and 2- amino -2 methyl-1s-propyl alcohol or a variety of.
5. etching liquid according to claim 1, which is characterized in that the weak acid and mild base salt includes diammonium hydrogen phosphate or acetic acid Ammonium.
6. etching liquid according to claim 1, which is characterized in that the hydrogen peroxide stabilizer is phenylurea.
7. etching liquid according to claim 1, which is characterized in that the alcohols material includes ethyl alcohol, methanol, ethylene glycol with And one of benzyl alcohol or a variety of.
8. a kind of lithographic method is performed etching using the etching liquid as described in claim 1-7 any one, which is characterized in that Include:
One substrate is provided；
The substrate is placed in the magnetic field of default magnetic field strength range；
The etching liquid for being used in preset temperature range performs etching the substrate, the substrate after being etched.
9. lithographic method according to claim 8, which is characterized in that the preset temperature range is 30 degrees Celsius to 35 and takes the photograph Between family name's degree.
10. lithographic method according to claim 8, which is characterized in that the default magnetic field strength range is 0.3 tesla To between 0.7 tesla.
CN201910338221.2A 2019-04-24 2019-04-24 Etching liquid and lithographic method Pending CN110144588A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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

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CN102732885A (en) * 2012-06-12 2012-10-17 华中科技大学 Magnetic-field-assisted silicon micro-nano processing technology and equipment
CN103952702A (en) * 2014-05-04 2014-07-30 深圳市实锐泰科技有限公司 Etching liquid and method for etching fine lines of flexible circuit board by using same
CN107075693A (en) * 2014-11-18 2017-08-18 关东化学株式会社 Copper, molybdenum stacked film etchant, the engraving method using said composition and extend said composition life-span method
CN107151795A (en) * 2017-06-02 2017-09-12 苏州晶瑞化学股份有限公司 A kind of copper-molybdenum alloy film etching solution
CN107217263A (en) * 2017-06-19 2017-09-29 江阴润玛电子材料股份有限公司 A kind of semicon industry lug manufacturing process copper titanium corrosive liquid
CN107304476A (en) * 2016-04-21 2017-10-31 关东化学株式会社 The etch combination or the engraving method using the composition of monofilm or stacked film
CN109234736A (en) * 2018-08-31 2019-01-18 深圳市华星光电技术有限公司 A kind of high life copper-molybdenum etching solution and engraving method
CN109554709A (en) * 2018-12-14 2019-04-02 江苏艾森半导体材料股份有限公司 TFT-LCD copper molybdenum alloy etching solution

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102569511A (en) * 2011-12-31 2012-07-11 常州天合光能有限公司 Texturing method of crystalline silicon solar cell
CN102732885A (en) * 2012-06-12 2012-10-17 华中科技大学 Magnetic-field-assisted silicon micro-nano processing technology and equipment
CN103952702A (en) * 2014-05-04 2014-07-30 深圳市实锐泰科技有限公司 Etching liquid and method for etching fine lines of flexible circuit board by using same
CN107075693A (en) * 2014-11-18 2017-08-18 关东化学株式会社 Copper, molybdenum stacked film etchant, the engraving method using said composition and extend said composition life-span method
CN107304476A (en) * 2016-04-21 2017-10-31 关东化学株式会社 The etch combination or the engraving method using the composition of monofilm or stacked film
CN107151795A (en) * 2017-06-02 2017-09-12 苏州晶瑞化学股份有限公司 A kind of copper-molybdenum alloy film etching solution
CN107217263A (en) * 2017-06-19 2017-09-29 江阴润玛电子材料股份有限公司 A kind of semicon industry lug manufacturing process copper titanium corrosive liquid
CN109234736A (en) * 2018-08-31 2019-01-18 深圳市华星光电技术有限公司 A kind of high life copper-molybdenum etching solution and engraving method
CN109554709A (en) * 2018-12-14 2019-04-02 江苏艾森半导体材料股份有限公司 TFT-LCD copper molybdenum alloy etching solution

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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

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Application publication date: 20190820