CN102392248B - Etchant of molybdenum and/ or aluminum containing metal film for OLED (Organic Light Emitting Diode) and preparation method thereof - Google Patents
Etchant of molybdenum and/ or aluminum containing metal film for OLED (Organic Light Emitting Diode) and preparation method thereof Download PDFInfo
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- CN102392248B CN102392248B CN 201110316299 CN201110316299A CN102392248B CN 102392248 B CN102392248 B CN 102392248B CN 201110316299 CN201110316299 CN 201110316299 CN 201110316299 A CN201110316299 A CN 201110316299A CN 102392248 B CN102392248 B CN 102392248B
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Abstract
The invention discloses an etchant of a molybdenum and/ or aluminum containing metal film for an OLED (Organic Light Emitting Diode) and a preparation method thereof. The etchant comprises nitric acid aqueous solution, phosphoric acid aqueous solution, betaine ampholytic surfactant and water, wherein the nitric acid aqueous solution accounts for 1-10%, preferably 2-8%, of the total weight of the etchant; the phosphoric acid aqueous solution accounts for 40-80%, preferably 50-70%, of the total weight of the etchant,; the betaine ampholytic surfactant accounts for 0.1-5%, preferably 0.5-2%, of the total weight of the etchant; and the balance is water. By the adoption of the etchant, solid liquid interface tension between the etchant and the metal film can be effectively improved, and the surface wettability of metal is improved. The etching speed is stabilized, and etching precision is improved; and more importantly, a taper angle can be effectively controlled to 20-70 degrees, and no etching residue is generated. The etchant has the advantages of high efficacy, high precision and important application value.
Description
Technical field
The present invention relates to a kind of organic electroluminescence device by using in the formation method of the stacked distribution of signal wiring, particularly relate to a kind of OLED with containing etching solution of molybdenum and/or aluminum metal film and preparation method thereof.
Background technology
In the flat pannel display field, OLED because of thin, the full curing of its ultralight, luminous, the visual angle is wide, response speed is fast, thermal adaptability is wide, can realize many outstanding performances such as soft demonstration, therefore its application prospect than common liquid-crystal display (Liquid Crystal Display, LCD) abundanter.OLED success at present to be applied to commerce, communication, computer, consumer electronics product, industry, traffic etc. multi-field, regarded as one of following technique of display that has competitive power.
The structure of OLED is made of negative electrode, electron transfer layer, organic luminous layer, hole transmission layer, anode usually.Anode transparent conductive metal oxide compound commonly used constitutes, such as tin indium oxide (Indium-Tin Oxide, ITO) nesa coating.Because the square resistance of ITO is bigger, when the main electrode lead-in wire is long or meticulous, will produce bigger volts lost on it, the luminous intensity of display space is weakened.In order to reduce resistance as much as possible, can cover the supporting electrode lead-in wire at all or part of ITO as the main electrode lead-in wire, consider the anti-oxidation employing molybdenum of protection against corrosion/aluminum metal lead-in wire usually.
Along with in recent years, in OLED assembly manufacturing process, be accompanied by that height becomes more meticulous, the highly integrated and ultra micro refinement tendency of the figure that causes, the etched controlled and precision of metallic membrane being made lead-in wire has had requirements at the higher level.In addition, in the etching to the metal stacking film, in order to prevent the broken string of upper strata distribution, obtain the high distribution of reliability, need be with the cone angle control of the cross-sectional shape of metal stacking film at 20 °-70 °.
Existing molybdenum film and aluminum metal film etching solution adopt the mixture of nitric acid, phosphoric acid, acetic acid and water more, as Japanese patent laid-open 7-176500 communique, this mixture etching solution is difficult to the cone angle of molybdenum film is controlled at 20 °-70 ° when the etching stacked film.
In addition, the etching solution mixture that adopts phosphoric acid, nitric acid and acetic acid or alkylsulphonic acid is arranged, open the 2005-85811 communique to molybdenum class and the etching of aluminium metal film stacked film as the Japanese Patent spy, but it is easy to generate residue, influences the etching precision.
Summary of the invention
The purpose of this invention is to provide a kind of OLED with containing etching solution of molybdenum and/or aluminum metal film and preparation method thereof.
OLED provided by the invention comprises aqueous nitric acid, phosphate aqueous solution, beet alkali ampholytic surface active agent and water with the etching solution that contains molybdenum and/or aluminum metal film.
Described etching solution also can only be made up of said components.
Wherein, the mass percentage concentration of described aqueous nitric acid is 63-67%, preferred 65%; Described aqueous nitric acid accounts for the 1-10% of described etching solution gross weight, and preferred 2-8% specifically can be 1-2%, 1-5%, 1-8%, 2-5%, 5-8%, 5-10% or 8-10%.The effect of nitric acid is the etching to the molybdenum metal film, and too slow to molybdenum metal film etching speed, be higher than at 10% o'clock when its mass percent is lower than 1%, etching speed is too fast, is difficult to control accuracy, and infringement strengthens to the photo-resist layer.
The mass percentage concentration of described phosphate aqueous solution is 50-54%, preferred 52%.Described phosphate aqueous solution accounts for the 40-80% of described etching solution gross weight, specifically can be 40-50%, 40-60%, 40-70%, 50-80%, 50-70%, 50-60%, 60-80%, 60-70% or 70-80%, preferred 50-70%.The effect of phosphoric acid is the etching to the aluminium metal film, and too slow to aluminium metal film etching speed, be higher than at 80% o'clock when its mass percent is lower than 40%, etching speed improves, but the cone angle of metal stacking film becomes more than 70 ° easily.
Described beet alkali ampholytic surface active agent is selected from least a in dodecanamide propyl hydroxy sulfo lycine, dodecanamide propyl trimethyl-glycine and the cocamidopropyl propyl amide hydroxy sulfo lycine.Described beet alkali ampholytic surface active agent accounts for the 0.1-5% of described etching solution gross weight, specifically can be 0.1-0.5% or 0.5-1%, preferred 0.5-2%, more preferably 0.5-1%.Above-mentioned beet alkali ampholytic surface active agent all can get from open commercial sources.The effect of betaines amphoterics is the surface tension of improving etchant and metallic film surface, increase the wettability of metallic film surface, effectively the cone angle of control metallic membrane is at 20 °-70 °, and the stability of raising etching speed, increase etched controlledly, when its mass percent was lower than 0.1%, action effect was not obvious, be higher than at 10% o'clock, residue be can occur in the etching process, etching quality and precision influenced.
Surplus is described water.Described water is deionized water, and described water is at least 18 megaohms 25 ℃ resistivity.
The method of the above-mentioned etching solution of preparation provided by the invention comprises the steps: the component mixing of aforementioned etching solution is obtained described etching solution.
The etching solution that the invention described above provides contains application in molybdenum and/or the aluminum metal film in etching, also belongs to protection scope of the present invention.
Wherein, constitute the described material that contains the molybdenum film by at least a composition the in molybdenum and the following element: chromium, copper, tungsten and niobium; Described containing in the molybdenum film, the quality percentage composition of molybdenum is not less than 80%;
The material that constitutes described aluminiferous metals film is by at least a composition the in aluminium and the following element: zinc, copper, neodymium and silicon; In the described aluminiferous metals film, the quality percentage composition of aluminium is not less than 80%.
Describedly contain molybdenum and/or the aluminum metal film is the film that contains molybdenum and/or aluminum metal that is positioned on the insulating film substrate; In the described film that contains molybdenum and/or aluminum metal, the described molybdenum film that contains is positioned on the described aluminiferous metals film;
Described insulating film substrate is the OLED glass substrate.
Described engraving method is not particularly limited, as can be whole wet etching, can adopt existing various known engraving methods and condition.For example metallic membrane be impregnated in etching solution 0.5-5 minute under 25-60 ℃.Concrete etching condition can suitably be selected after the test according to the type of the stacked film that uses and thickness etc.
Etching solution provided by the invention, can effectively improve solid-liquid interfacial tension between etching solution and the metallic membrane, improve the wettability of metallic surface, not only stablized etching speed, improved the etching precision, the most important thing is, can effectively control cone angle at 20 °-70 °, and not having etch residue, is a kind of etching solution of high-efficiency high-accuracy, has important use and is worth.
Embodiment
The present invention is further elaborated below in conjunction with specific embodiment, but the present invention is not limited to following examples.Described method is ordinary method if no special instructions.Described material all can get from open commercial sources if no special instructions.
As follows embodiment and reference examples gained etching solution are carried out the mensuration of etching speed:
(thickness is metallic membrane to adopt sputtering method to form aluminium zinc (99.0 quality %Al, 1.0 quality %Zn) at glass substrate
) after, (thickness is metallic membrane to form molybdenum tungsten (85.0 quality %Mo, 15.0 quality %W) by the spatter film forming method thereon again
).The painting photoresist layer, exposure is developed, and forms the etch-resistant coating pattern.This substrate is immersed in the etchant shown in the table 11 minute after washing of etching, drying treatment under 40 ℃ temperature condition, after peeling off etch-resistant coating, decide etch quantity with contact pin type section difference instrumentation, and calculate rate of etch (nm/min of unit) according to following formula: rate of etch=etch quantity/etching period.
As follows embodiment gained etching solution being carried out the etching cone angle measures:
(thickness is metallic membrane to adopt sputtering method to form aluminium zinc (99.0 quality %Al, 1.0 quality %Zn) at glass substrate
) after, (thickness is metallic membrane to form molybdenum tungsten (85.0 quality %Mo, 15.0 quality %W) by the spatter film forming method thereon again
).The painting photoresist layer, exposure is developed, and forms the etch-resistant coating pattern.This substrate is immersed in the etchant shown in the table 11 minute after washing of etching, drying treatment under 40 ℃ temperature condition, after peeling off etch-resistant coating, observe etching state with electron microscope (SEM), measure the cone angle of the film with conical in shape that forms by etching.
As follows embodiment gained etching solution is carried out the detection of the effect of etch residue and anti-etching dose of infringement:
(thickness is metallic membrane to adopt sputtering method to form aluminium zinc (99.0 quality %Al, 1.0 quality %Zn) at glass substrate
) after, (thickness is metallic membrane to form molybdenum tungsten (85.0 quality %Mo, 15.0 quality %W) by the spatter film forming method thereon again
).The painting photoresist layer, exposure is developed, and forms the etch-resistant coating pattern.Observe embodiment gained etching solution to the etch residue of film and the effect of anti-etching dose of infringement with electron microscope (SEM) this substrate immersed in the etchant shown in the table 11 minute after washing of etching, drying treatment under 40 ℃ temperature condition after.
Embodiment 1-11
Be after 52% phosphate aqueous solution 50 weight parts, mass percentage concentration are 65% aqueous nitric acid 1 weight part, beet alkali ampholytic surface active agent dodecanamide propyl hydroxy sulfo lycine 1 weight part and deionized water 48 weight part mixings, to obtain etching solution provided by the invention with mass percentage concentration.
According to last identical step, only with above-mentioned each raw material according to replacing shown in the table 1, obtain the etching solution that embodiment 2-11 and comparative example 1-7 provide.
Table 1, etching solution are formed and the etch effect tabulation
Surfactant A---dodecanamide propyl hydroxy sulfo lycine
Surfactant B---dodecanamide propyl trimethyl-glycine
Tensio-active agent C---cocamidopropyl propyl amide hydroxy sulfo lycine
Etching angle zero---cone angle is at 20 °-70 °
The etching angle *---cone angle is less than 20 ° or greater than 70 °
Etch residue zero---no residue
Etch residue *---residue is arranged
Resist infringement zero---harmless
The resist infringement *---infringement is arranged
The water yield is the surplus of mass percent, not expression in the table 1.
As can be known from Table 1, use etching solution of the present invention, when the stacked film that contains at least a aluminium metal film and at least a molybdenum metal film is carried out whole wet etching, when obtaining high-precision stacked film distribution, do not have etch residue, can effectively control cone angle at 20 °-70 °.
Claims (8)
1. an etching solution is made up of described aqueous nitric acid, phosphate aqueous solution, beet alkali ampholytic surface active agent and water; Described beet alkali ampholytic surface active agent is selected from least a in dodecanamide propyl hydroxy sulfo lycine, dodecanamide propyl trimethyl-glycine and the cocamidopropyl propyl amide hydroxy sulfo lycine; The mass percentage concentration of described aqueous nitric acid is 63-67%; The mass percentage concentration of described phosphate aqueous solution is 50-54%;
Described aqueous nitric acid accounts for the 1-10% of described etching solution gross weight;
Described phosphate aqueous solution accounts for the 40-80% of described etching solution gross weight;
Described beet alkali ampholytic surface active agent accounts for the 0.1-5% of described etching solution gross weight;
Surplus is described water.
2. etching solution according to claim 1, it is characterized in that: the mass percentage concentration of described aqueous nitric acid is 65%; The mass percentage concentration of described phosphate aqueous solution is 52%.
3. etching solution according to claim 2, it is characterized in that: described aqueous nitric acid accounts for the 2-8% of described etching solution gross weight; Described phosphate aqueous solution accounts for the 50-70% of described etching solution gross weight; Described beet alkali ampholytic surface active agent accounts for the 0.5-2% of described etching solution gross weight.
4. etching solution according to claim 3, it is characterized in that: described water is deionized water, described water is at least 18 megaohms 25 ℃ resistivity.
5. a method for preparing the arbitrary described etching solution of claim 1-4 comprises the steps: the component mixing of the arbitrary described etching solution of claim 1-4 is obtained described etching solution.
6. the arbitrary described etching solution of claim 1-4 contains application in molybdenum and/or the aluminum metal film in etching.
7. application according to claim 6 is characterized in that: constitute the described material that contains the molybdenum film by at least a composition the in molybdenum and the following element: chromium, copper, tungsten and niobium; Described containing in the molybdenum film, the quality percentage composition of molybdenum is not less than 80%;
The material that constitutes described aluminiferous metals film is by at least a composition the in aluminium and the following element: zinc, copper, neodymium and silicon; In the described aluminiferous metals film, the quality percentage composition of aluminium is not less than 80%.
8. application according to claim 7 is characterized in that: describedly contain molybdenum and/or the aluminum metal film is the film that contains molybdenum and/or aluminum metal that is positioned on the insulating film substrate; In the described film that contains molybdenum and/or aluminum metal, the described molybdenum film that contains is positioned on the described aluminiferous metals film;
Described insulating film substrate is the OLED glass substrate.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110316299 CN102392248B (en) | 2011-10-18 | 2011-10-18 | Etchant of molybdenum and/ or aluminum containing metal film for OLED (Organic Light Emitting Diode) and preparation method thereof |
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| CN 201110316299 CN102392248B (en) | 2011-10-18 | 2011-10-18 | Etchant of molybdenum and/ or aluminum containing metal film for OLED (Organic Light Emitting Diode) and preparation method thereof |
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| CN102392248A CN102392248A (en) | 2012-03-28 |
| CN102392248B true CN102392248B (en) | 2013-08-21 |
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| CN109852969A (en) * | 2019-02-18 | 2019-06-07 | 湖北兴福电子材料有限公司 | A kind of ternary component etching solution of high etch rates |
| CN114107991A (en) * | 2021-11-29 | 2022-03-01 | 清华大学 | Molybdenum-copper double-layer film material etching method and corrosive liquid |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US3839112A (en) * | 1973-04-16 | 1974-10-01 | Texas Instruments Inc | Temperature stable compositions and processes for brightening metals and alloys |
| KR100944300B1 (en) * | 2001-10-22 | 2010-02-24 | 미츠비시 가스 가가쿠 가부시키가이샤 | Etching method for aluminum-molybdenum laminate film |
| TWI245071B (en) * | 2002-04-24 | 2005-12-11 | Mitsubishi Chem Corp | Etchant and method of etching |
| JP2007191773A (en) * | 2006-01-20 | 2007-08-02 | Kanto Chem Co Inc | Solution for etching stacked film of aluminum-based metallic film and molybdenum-based metallic film |
| JP4755659B2 (en) * | 2008-01-31 | 2011-08-24 | 磯部塗装株式会社 | Substrate adjustment method |
| CN101634030B (en) * | 2009-01-22 | 2011-03-30 | 湖南省湘电试验研究院有限公司 | Acid-cleaning inhibiter for cleaning boiler and use method thereof |
| CN102108512B (en) * | 2009-12-25 | 2013-09-18 | 比亚迪股份有限公司 | Chemical etching liquid for metals and etching method |
| CN101792907A (en) * | 2010-04-01 | 2010-08-04 | 江阴市江化微电子材料有限公司 | Aluminium-molybdenum etching liquid |
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