CN109136926A - Lithographic method and etching device for copper-molybdenum film layer - Google Patents
Lithographic method and etching device for copper-molybdenum film layer Download PDFInfo
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- CN109136926A CN109136926A CN201811013179.9A CN201811013179A CN109136926A CN 109136926 A CN109136926 A CN 109136926A CN 201811013179 A CN201811013179 A CN 201811013179A CN 109136926 A CN109136926 A CN 109136926A
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- etching
- copper
- film layer
- molybdenum film
- lithographic method
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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
-
- 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
- C23F1/08—Apparatus, e.g. for photomechanical printing surfaces
-
- 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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- 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)
- Weting (AREA)
- ing And Chemical Polishing (AREA)
Abstract
A kind of lithographic method and etching device for copper-molybdenum film layer, the lithographic method include: step S10, and copper-molybdenum film layer is formed on substrate；Step S20 forms the photoresist of predetermined pattern in the copper-molybdenum film layer；The substrate for being formed with the photoresist is placed in etching device by step S30；Step S40 fills ozone to progress ultraviolet light irradiation inside the etching device, and into the etching device；Step S50 performs etching the copper-molybdenum film layer using etching liquid.The present invention can be improved etching efficiency and production capacity, in addition, can also reduce the dosage of etching liquid, and then reduce the cost of etching liquid.
Description
Technical field
The present invention relates to copper wiring etching field more particularly to a kind of lithographic methods and etching dress for copper-molybdenum film layer
It sets.
Background technique
With the increase of display sizes, the length of the metal wirings such as the grid line and data line that are connect with thin film transistor (TFT)
It will increase, the resistance of metal wiring will increase therewith, the problems such as generating signal delay, generally use copper metal at present to make
Grid and data metal wiring, compared to aluminum metal, the resistance value of copper is lower, has excellent performance, and does not need the width for reaching aluminum conductor
Degree requires, and can improve the penetration of display and the service efficiency of backlight, therefore copper metal is more suitable high-resolution face
The production of plate.
The forming process of copper wiring pattern includes: the first formation copper-molybdenum film layer on substrate in TFT-LCD, then in copper-molybdenum film
The photoresist of predetermined pattern is formed on layer, finally copper-molybdenum film layer is performed etching using etching liquid, to form the gold of predetermined pattern
Belong to wiring.Wherein, the effect of molybdenum is to increase the adhesion of copper and substrate, prevents not specified regional diffusion of the copper to substrate.But
Contain fluoride in traditional etching liquid, all there is corrosivity to substrate and environment, and it is poor to etch low efficiency, stability.
Summary of the invention
The present invention provides a kind of lithographic method and etching device for copper-molybdenum film layer can by ultraviolet irradiation
The ability of the oxidation copper-molybdenum of hydrogen peroxide in enhanced etching liquid accelerates etching efficiency, to solve the mistake in existing etching liquid
The problem of rate of the oxidation copper-molybdenum of hydrogen oxide is slower, causes to etch inefficiency, and then influences the production capacity of display panel.
To solve the above problems, technical solution provided by the invention is as follows:
The present invention provides a kind of lithographic method of copper-molybdenum film layer, comprising:
Step S10 forms copper-molybdenum film layer on substrate；
Step S20 forms the photoresist of predetermined pattern in the copper-molybdenum film layer；
The substrate for being formed with the photoresist is placed in etching device by step S30；
Step S40 to carrying out ultraviolet light irradiation inside the etching device, and is filled into the etching device smelly
Oxygen；
Step S50 performs etching the copper-molybdenum film layer using etching liquid.
In at least one embodiment of the invention, in the step S40, the wavelength of the ultraviolet light is received for 200~390
Rice.
In at least one embodiment of the invention, in the step S40, the ultraviolet irradiation intensity is 0.5~2
Milliwatt is every square centimeter.
In at least one embodiment of the invention, in the step S40, the ozone in the etching device it is dense
Degree is 0.05~10 milligrams per liter.
In at least one embodiment of the invention, in the step S50, the etching temperature of the etching liquid is 25~35
Degree Celsius.
In at least one embodiment of the invention, the etching liquid includes uniformly mixed hydrogen peroxide, organic acid, tune
Save agent, inorganic salts, chelating agent, inhibitor and deionized water.
In at least one embodiment of the invention, relative to the total quality of the etching liquid, the hydrogen peroxide
Mass fraction is 5%~10%, and the mass fraction of the organic acid is 3%~10%, and the mass fraction of the regulator is
0.1%~3%, the mass fraction of the inorganic salts is 0.1%~5%, and the mass fraction of the inorganic salts is 0.1%~5%,
The mass fraction of the chelating agent is 0.5%~7%, and the mass fraction of the inhibitor is 0.001%~1%, and surplus is institute
State deionized water.
The present invention also provides a kind of etching devices for copper-molybdenum film layer, comprising:
The cavity of sealing；
Objective table is set to the cavity bottom, to carry substrate to be etched；
Etching liquid spray head is set to the top of the cavity, to eject etching liquid；
Ultraviolet lamp is set to the top of the cavity；
Ozone fill port is set on the cavity.
In at least one embodiment of the invention, the wavelength for the ultraviolet light of the ultraviolet lamp irradiated is 200~390
Nanometer, the exposure intensity of the ultraviolet light are that 0.5~2 milliwatt is every square centimeter.
In at least one embodiment of the invention, the ozone fill port to be filled with ozone to the inside cavity,
The concentration of the intracorporal ozone of chamber is 0.05~10 milligrams per liter.
The invention has the benefit that provided by the present invention for the lithographic method and etching device of copper-molybdenum film layer, it can
Etching efficiency and production capacity are improved, in addition, can also reduce the dosage of etching liquid, and then reduces the cost of etching liquid.
Detailed description of the invention
It, below will be to embodiment or the prior art in order to illustrate more clearly of embodiment or technical solution in the prior art
Attached drawing needed in description is briefly described, it should be apparent that, the accompanying drawings in the following description is only some of invention
Embodiment for those of ordinary skill in the art without creative efforts, can also be attached according to these
Figure obtains other attached drawings.
Fig. 1 is the step flow chart of the lithographic method for copper-molybdenum film layer of the invention；
Fig. 2 is that the Electronic Speculum that the copper-molybdenum film layer of the preferred embodiment of the present invention one etches detects figure；
Fig. 3 is the structural schematic diagram of the etching device for copper-molybdenum film layer of the invention.
Specific embodiment
The explanation of following embodiment is referred to the additional illustration, the particular implementation that can be used to implement to illustrate the present invention
Example.The direction term that the present invention is previously mentioned, such as [on], [under], [preceding], [rear], [left side], [right side], [interior], [outer], [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 with being given the same reference numerals in the figure.
The present invention causes to carve for existing etching liquid since the rate of the hydrogen peroxide oxidation copper-molybdenum in etching liquid is slower
The problem of losing inefficiency, and then influencing production capacity, the present embodiment is able to solve the defect.
As shown in Figure 1, the lithographic method of copper-molybdenum film layer provided in this embodiment, comprising:
Step S10 forms copper-molybdenum film layer on substrate；
Wherein, the substrate can be glass substrate, deposit the copper-molybdenum on the glass substrate by physical vaporous deposition
Film layer specifically first deposits molybdenum film in the substrate surface, then in the molybdenum film copper-depositing on surface film, the effect of molybdenum is
It is referred in the background technique of this specification, which is not described herein again.
Step S20 forms the photoresist of predetermined pattern in the copper-molybdenum film layer；
Wherein, first in the copper-molybdenum film surface coating photoresist film layer, then setting regions is somebody's turn to do using mask plate
Photoresist film layer is exposed, develops, and removes part photoresist, finally obtains the photoresist of predetermined pattern.
The substrate for being formed with the photoresist is placed in etching device by step S30；
Wherein, the etching device is sealing device.
Step S40 to carrying out ultraviolet light irradiation inside the etching device, and is filled into the etching device smelly
Oxygen；
Wherein, the wavelength of the ultraviolet light is 200~390 nanometers, and exposure intensity is that 0.5~2 milliwatt is every square centimeter, institute
Stating the ozone concentration in etching device is 0.05~10 milligrams per liter.
Step S50 performs etching the copper-molybdenum film layer using etching liquid；
Wherein, the etching temperature of the etching liquid is 25~35 degrees Celsius.
The etching liquid include uniformly mixed hydrogen peroxide, organic acid, regulator, inorganic salts, chelating agent, inhibitor,
And deionized water.
Wherein, the total quality relative to the etching liquid, the mass fraction of the hydrogen peroxide are 5%~10%, institute
The mass fraction for stating organic acid is 3%~10%, and the mass fraction of the regulator is 0.1%~3%, the matter of the inorganic salts
Measuring score is 0.1%~5%, and the mass fraction of the inorganic salts is 0.1%~5%, and the mass fraction of the chelating agent is
0.5%~7%, the mass fraction of the inhibitor is 0.001%~1%, and surplus is the deionized water.
Specifically, the organic acid is acetic acid, hydroxyacetic acid, 2- hydroxy propane -1,2,3- tricarboxylic acids, benzoic acid, second two
It is any one in acid, succinic acid, 2,3 dihydroxybutanedioic acid, 2- hydroxysuccinic acid, 2 hydroxy propanoic acid and phthalic acid
Kind or multiple combinations.
The regulator is in diisopropanolamine (DIPA), polyacrylamide, m-phenylene diamine (MPD), parachloroanilinum and monoisopropanolamine
Any one or more combination.
The inorganic salts be sodium chloride, magnesium chloride, potassium chloride, sodium sulphate, magnesium sulfate, potassium sulfate, sodium nitrate, magnesium nitrate,
Arbitrary one or more combinations in potassium nitrate, sodium acetate, magnesium acetate and potassium acetate.
The chelating agent is any one or more group in sodium stannate, sodium pyrophosphate, 8-hydroxyquinoline and chitosan
It closes.
The inhibitor be 6- nitrobenzimidazole, thiazolamine, 2- amino -5- nitrothiazole, 5- aminotetrazole,
One of 3- amino -1,2,4- triazole, benzotriazole, benzotriazole, triazole sodium and thin base benzotriazole are more
Kind combination.
Hydrogen peroxide in the etching liquid can generate hydroxyl radical free radical in the irradiation process of ultraviolet light, and hydroxyl is certainly
It is a kind of important active oxygen by base, there is extremely strong electronic capability, that is, oxidability, be the oxidation for being only second to fluorine in nature
Agent is reacted by the synergistic oxidation of electron beam and hydrogen peroxide, aoxidizes copper-molybdenum, in simple terms, peroxidating can be enhanced in ultraviolet light
The ability of hydroxide copper-molybdenum accelerates reaction rate, and then improves etching efficiency.
Ozone is strong oxidizer, cooperates with hydrogen peroxide and aoxidizes to copper-molybdenum, and etching efficiency, another party also can be improved
Face can reduce the dosage of each component in etching liquid, reduce the cost of etching liquid while increasing hydrogen peroxide oxidation ability,
It is also beneficial to improve etching liquid in production, the safety of storage and transport face to face.
Organic acid in the present embodiment is 2- hydroxy propane -1,2, and 3- tricarboxylic acids, regulator is diisopropanolamine (DIPA), chelating agent
For 8-hydroxyquinoline, inorganic salts are sodium chloride, and inhibitor is benzotriazole.
Each component accounts for the overall quality score of etching liquid are as follows: hydrogen peroxide 6%, 2- hydroxy propane -1,2,3- tricarboxylic acids
7%, diisopropanolamine (DIPA) 3.5%, 8-hydroxyquinoline 1.5%, sodium chloride 0.1%, benzotriazole 0.01%, deionized water
81.89%.
In etching process, copper is controlled by the concentration of the intensity of illumination of adjusting ultraviolet light, light application time and ozone
The etching speed of molybdenum film layer, in this embodiment, etching temperature are 30 degrees Celsius, the ultraviolet light irradiation for being 253.7 nanometers with wavelength,
Exposure intensity is that 1.0 milliwatts are per cubic centimeter, ozone is filled into the etching device, so that the ozone concentration in device is
0.4 milligrams per liter.
As shown in Fig. 2, being observed using scanning electron microscope the film layer in etching process, the copper after being etched
The cone angle (angle of the side of copper-molybdenum film layer and the plane formation where substrate) of the end of molybdenum film layer is 51.9 degree, CD Loss
(the wide loss of the item of metal wire, the length of the copper-molybdenum film layer being etched away under photoresist orthographic projection) is 1.048 microns, and is not had
The remaining trace of molybdenum, the cone angle range after general etching is 30~60 degree, CD Loss for 1.2 microns hereinafter, etching effect compared with
It is good.
As shown in figure 3, the present invention also provides a kind of etching devices of copper-molybdenum based on the above-mentioned lithographic method for copper-molybdenum
10, comprising: the cavity 11 of sealing；Objective table 12；Etching liquid spray head 15；Ultraviolet lamp 13；Ozone fill port 14.
The objective table 12 is set to the bottom of the cavity, and to carry substrate 17 to be etched, the substrate is heavy
Product has the glass substrate of copper-molybdenum film layer, and copper-molybdenum film surface is formed with the photoresist of predetermined pattern, to protect setting regions
Copper-molybdenum film layer be not etched.
The ultraviolet lamp 13 is set on the cavity 11, is preferably provided in the top of the cavity 11, described ultraviolet
13 space set of lamp is multiple, and particular number determines that the ultraviolet lamp 13 can be to the cavity with practical etching device size
Inside carries out the radiation of uniform ultraviolet light.
The etching liquid spray head 15 is set to the top of the cavity 11, be preferably provided in the substrate 17 just on
Side, so that the etching liquid ejected is evenly distributed on the substrate 17.
The ozone fill port 14 is set on the cavity 11, is preferably provided on the side wall of the cavity, described
Height where ozone fill port 14 is between the etching liquid spray head 15 and the substrate 17, so that the ozone fill port
The ozone of 14 injections adequately acts on the hydrogen peroxide in the etching liquid.
The ultraviolet wavelength that the ultraviolet lamp 13 gives off is 200~390 nanometers, and exposure intensity is that 0.5~2 milliwatt is often stood
Square centimetre, the concentration of the ozone inside the cavity 11 is 0.05~10 milligrams per liter.
When carrying out copper-molybdenum film layer etching, the temperature that the etching liquid acts on 17 surface of substrate is 25~35 Celsius
Degree, the irradiation time of the ultraviolet light is at least at 5 minutes or more.
Pass through the intensity and irradiation time and ozone of ultraviolet light of the control etching device in copper-molybdenum etching process
Concentration control, the speed of copper-molybdenum etching so that copper-molybdenum film layer has suitable et ch profiles, and is controlled in corresponding CD
Under Loss, remained without molybdenum.
The utility model has the advantages that can be improved etching effect provided by the present invention for the lithographic method and etching device of copper-molybdenum film layer
Rate and production capacity in addition, can also reduce the dosage of etching liquid, and then reduce the cost of etching liquid.
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 lithographic method for copper-molybdenum film layer characterized by comprising
Step S10 forms copper-molybdenum film layer on substrate；
Step S20 forms the photoresist of predetermined pattern in the copper-molybdenum film layer；
The substrate for being formed with the photoresist is placed in etching device by step S30；
Step S40 fills ozone to progress ultraviolet light irradiation inside the etching device, and into the etching device；
Step S50 performs etching the copper-molybdenum film layer using etching liquid.
2. lithographic method according to claim 1, which is characterized in that in the step S40, the wavelength of the ultraviolet light is
200~390 nanometers.
3. lithographic method according to claim 1, which is characterized in that in the step S40, the ultraviolet irradiation is strong
Degree is that 0.5~2 milliwatt is every square centimeter.
4. lithographic method according to claim 1, which is characterized in that the institute in the step S40, in the etching device
The concentration for stating ozone is 0.05~10 milligrams per liter.
5. lithographic method according to claim 1, which is characterized in that in the step S50, the etching temperature of the etching liquid
Degree is 25~35 degrees Celsius.
6. lithographic method according to claim 1, which is characterized in that the etching liquid includes uniformly mixed peroxidating
Hydrogen, organic acid, regulator, inorganic salts, chelating agent, inhibitor and deionized water.
7. lithographic method according to claim 6, which is characterized in that described relative to the total quality of the etching liquid
The mass fraction of hydrogen peroxide is 5%~10%, and the mass fraction of the organic acid is 3%~10%, the matter of the regulator
Measuring score is 0.1%~3%, and the mass fraction of the inorganic salts is 0.1%~5%, and the mass fraction of the inorganic salts is
0.1%~5%, the mass fraction of the chelating agent is 0.5%~7%, the mass fraction of the inhibitor is 0.001%~
1%, surplus is the deionized water.
8. a kind of etching device for copper-molybdenum film layer characterized by comprising
The cavity of sealing；
Objective table is set to the cavity bottom, to carry substrate to be etched；
Etching liquid spray head is set to the top of the cavity, to eject etching liquid；
Ultraviolet lamp is set to the top of the cavity；
Ozone fill port is set on the cavity.
9. etching device according to claim 8, which is characterized in that the wavelength for the ultraviolet light of the ultraviolet lamp irradiated
It is 200~390 nanometers, the exposure intensity of the ultraviolet light is that 0.5~2 milliwatt is every square centimeter.
10. etching device according to claim 8, which is characterized in that the ozone fill port is into the cavity
Portion is filled with ozone, and the concentration of the intracorporal ozone of chamber is 0.05~10 milligrams per liter.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811013179.9A CN109136926A (en) | 2018-08-31 | 2018-08-31 | Lithographic method and etching device for copper-molybdenum film layer |
| PCT/CN2018/107198 WO2020042257A1 (en) | 2018-08-31 | 2018-09-25 | Etching method and etching device for copper molybdenum film layer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811013179.9A CN109136926A (en) | 2018-08-31 | 2018-08-31 | Lithographic method and etching device for copper-molybdenum film layer |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109136926A true CN109136926A (en) | 2019-01-04 |
Family
ID=64826150
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811013179.9A Pending CN109136926A (en) | 2018-08-31 | 2018-08-31 | Lithographic method and etching device for copper-molybdenum film layer |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN109136926A (en) |
| WO (1) | WO2020042257A1 (en) |
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| EP0222347A2 (en) * | 1985-11-11 | 1987-05-20 | HANS HÖLLMÜLLER MASCHINENBAU GMBH & CO. | Process and apparatus for etching work pieces composed at least partly of metal, preferably of copper |
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2018
- 2018-08-31 CN CN201811013179.9A patent/CN109136926A/en active Pending
- 2018-09-25 WO PCT/CN2018/107198 patent/WO2020042257A1/en active Application Filing
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| WO2020042257A1 (en) | 2020-03-05 |
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Application publication date: 20190104 |