CN101130870A - Laminated film - Google Patents
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- CN101130870A CN101130870A CNA2006101216371A CN200610121637A CN101130870A CN 101130870 A CN101130870 A CN 101130870A CN A2006101216371 A CNA2006101216371 A CN A2006101216371A CN 200610121637 A CN200610121637 A CN 200610121637A CN 101130870 A CN101130870 A CN 101130870A
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Abstract
The present invention relates to a compound etching liquor which can be used for etching metal laminated film formed on the semiconductor substrate. Said compound etching liquor contains fluoride and oxidant. The described fluoride is at least one kind selected from metal salt or ammonium salt of hydrofluoric acid, hexafluorosilicic acid, metal salt or ammonium salt of hexafluorosilicic acid, tetrafluoroboric acid and metal salt or ammonium salt of tetrafluoroboric acid.
Description
Technical field
The present invention relates to be used for the etchant of metal stacking film of grid, source electrode and the drain electrode etc. of liquid-crystal display.
Background technology
Because aluminium or to be added with the alloy price of impurity such as neodymium, silicon or copper in aluminium cheap and resistance is very low, therefore be used in the material of grid, source electrode and drain electrode etc. of liquid-crystal display.
But, because aluminum or aluminum alloy and as the adaptation between the glass substrate of basilar membrane (adhesivity) some is poor, and corroded by soup and heat easily, therefore use the film of molybdenum or molybdenum alloy to be used for electrode materials in the top and/or the bottom of aluminum or aluminum alloy, carry out the etching of stacked film together by the etching solution that has used phosphoric acid etc. as stacked film.
In recent years, because the rising of the price of molybdenum or molybdenum alloy, and seek by soup and the hot reasons such as corrosive further improvement that caused, titanium or titanium alloy are gazed at.The phosphoric acid that the molybdenum etching is used etc. can not be used for the etching of titanium or titanium alloy, but has carried out as the use of the engraving method of titanium in the semiconductor substrate-aluminum-based metal stacked film the dry-etching of the reactive ion etching of halogen gas (RIE) etc.In RIE, can control taper to a certain extent by anisotropic etching, but owing to need the vacuum unit and the high frequency generation device of high price, unfavorable aspect cost, that wishes therefore that exploitation is more cheap and also can reduce the treatment time carries out etching solution for etching together.
On the other hand, known will be the metallic film of principal constituent when carrying out etching with the titanium in the manufacturing process of semiconductor device, and generally using hydrofluoric acid is etching solution (for example patent documentation 1).In addition, also known to having used the etching solution of ammoniacal liquor-aquae hydrogenii dioxidi, can carry out the etching (for example patent documentation 2) of titanium or titanium alloy.
But, when using hydrofluoric acid to be etching solution,, therefore can not use because glass substrate, silicon substrate and the compound semiconductor substrate of bottom caused damage.When using ammoniacal liquor-aquae hydrogenii dioxidi, because the decomposition of aquae hydrogenii dioxidi produces bubble, because bubble is to the adhering to of substrate, etching becomes not exclusively, and the life-span of etching solution is short, so is difficult to use.
Other are different with purposes of the present invention as the etching solution of glass substrate etc., as employed with the surface rust of removing titanium or titanium alloy with make it smoothly turn to the etching solution of purpose in ornament and the electronic component, disclosing with hydrogen peroxide, fluorochemical, inorganic acids and fluorine is that tensio-active agent is the composition (patent documentation 3) of neccessary composition, but can not be alloy constituted the layer of principal constituent and be that the metal stacking film of the layer that alloy constituted of principal constituent carries out etching and gives enlightenment by aluminium or with aluminium containing by titanium or with the titanium.In addition, as the etching solution of the metal stacking film that is constituted by titanium layer and copper layer, disclose the aqueous solution (patent documentation 4) that contains peroxydisulfate and fluorochemical, but be not carrying out etched solution by the metal stacking film that aluminium lamination and titanium layer constituted.
As titanium-aluminium cascade metal films being carried out etching solution for etching together, disclose containing hydrofluoric acid, Periodic acid and vitriolic etching solution (patent documentation 5).But this etching solution is that each metallic membrane with the metal stacking film carries out etching with same etch-rate, and therefore, the cone angle after the etching becomes roughly 90 degree.Recently, for short circuit between the broken string, gate line and the source electrode line that prevent to be formed at the source electrode line on the gate line etc., often carry out the distribution on the substrate is made taper (cone angle is less than 90 degree) (patent documentation 6), but the etching solution in the patent documentation 5 can not satisfy this purpose.In addition, also there is the problem that glass substrate is caused damage in this etching solution.
As a rule, etching solution is greater than etch-rate to titanium or titanium alloy to the etch-rate of aluminum or aluminum alloy.Therefore, also do not know at present and can will contain the layer that constitutes by titanium or titanium alloy and carry out etching together and make the etching solution of taper by the metal stacking film of the 3-tier architecture that metal stacking film, for example titanium or titanium alloy/aluminum or aluminum alloy/titanium or titanium alloy constituted of the layer that aluminum or aluminum alloy constituted.
Patent documentation 1: the spy opens clear 59-124726 communique
Patent documentation 2: the spy opens flat 6-310492 communique
Patent documentation 3: the spy opens the 2004-43850 communique
Patent documentation 4: the spy opens the 2001-59191 communique
Patent documentation 5: the spy opens the 2000-133635 communique
Patent documentation 6: the spy opens the 2004-165289 communique
Summary of the invention
That is, the object of the present invention is to provide and a kind ofly solved the problems referred to above point and titanium-aluminum-based metal stacked film can be carried out together etching and make the etching solution of taper.
In studying with keen determination, find in order to address the above problem, can be suitably be the layer that alloy constituted of principal constituent with containing and be that the metal stacking film of the layer that alloy constituted of principal constituent carries out etching together by aluminium or with aluminium being selected from etching solution that the metal-salt of the metal-salt of the metal-salt of hydrofluoric acid or ammonium salt, hexafluorosilicic acid, hexafluorosilicic acid or ammonium salt, Tetrafluoroboric acid, Tetrafluoroboric acid or at least a fluorochemical in the ammonium salt and oxygenant combine by titanium or with the titanium, by further studying, the result has finished the present invention.
Promptly, the present invention relates to a kind of etchant, it is used for containing by titanium or with the titanium is alloy constituted the layer of principal constituent and is that the metal stacking film of the layer that alloy constituted of principal constituent carries out etching together by aluminium or with aluminium, above-mentioned etchant contains fluorochemical and oxygenant, and wherein above-mentioned fluorochemical is to be selected from least a in the metal-salt of the metal-salt of the metal-salt of hydrofluoric acid or ammonium salt, hexafluorosilicic acid, hexafluorosilicic acid or ammonium salt, Tetrafluoroboric acid, Tetrafluoroboric acid or the ammonium salt.
The invention still further relates in above-mentioned etchant, only use fluorochemical, oxygenant and water as constituting raw material, described fluorochemical is to be selected from least a in the metal-salt of the metal-salt of the metal-salt of hydrofluoric acid or ammonium salt, hexafluorosilicic acid, hexafluorosilicic acid or ammonium salt, Tetrafluoroboric acid, Tetrafluoroboric acid or the ammonium salt.
The invention still further relates in above-mentioned etchant, oxygenant is at least a for what select among nitric acid, ammonium nitrate, ammonium sulfate, ammonium peroxydisulfate, Potassium Persulfate, perchloric acid, ammoniumper chlorate, sodium perchlorate, potassium perchlorate, Periodic acid, sodium periodate, potassium periodate, methylsulfonic acid, aquae hydrogenii dioxidi, sulfuric acid and ethylenediamine sulfate.
The invention still further relates in above-mentioned etchant, the concentration of fluorochemical is 0.01～5 quality %, and the concentration of oxygenant is 0.1～50 quality %.
The invention still further relates in above-mentioned etchant, oxygenant is nitric acid or methylsulfonic acid.
The invention still further relates in above-mentioned etchant, it further contains as oxygenant select among ammonium nitrate, ammonium sulfate, ammonium peroxydisulfate, Potassium Persulfate, perchloric acid, ammoniumper chlorate, sodium perchlorate, potassium perchlorate, Periodic acid, sodium periodate, potassium periodate, aquae hydrogenii dioxidi, sulfuric acid and the ethylenediamine sulfate at least a kind.
The invention still further relates to above-mentioned etchant, it further contains at least a kind that selects among thionamic acid, the acetate and hydrochloride.
The invention still further relates to above-mentioned etchant, wherein, the bottom substrate is a liquid crystal display glass substrate.
The invention still further relates to above-mentioned etchant, wherein, the bottom substrate is a semiconductor device with silicon substrate or compound semiconductor substrate.
The invention still further relates to above-mentioned etchant, wherein, can be alloy constituted the layer of principal constituent with containing and be that the cone angle of metal stacking film after etching of the layer that alloy constituted of principal constituent is controlled in the scopes of 30～90 degree by aluminium or with aluminium by titanium or with the titanium.
The invention still further relates to above-mentioned etchant, wherein cone angle can be controlled in the scope of 30～85 degree.
As mentioned above, etchant of the present invention contains the metal-salt of the metal-salt of the metal-salt that is selected from hydrofluoric acid or ammonium salt, hexafluorosilicic acid, hexafluorosilicic acid or ammonium salt, Tetrafluoroboric acid, Tetrafluoroboric acid or at least a fluorochemical in the ammonium salt and oxygenant as constituting raw material.This formation by etchant of the present invention, be alloy constituted the layer of principal constituent and be in the etching of metal stacking film of the layer that alloy constituted of principal constituent by aluminium or with aluminium containing by titanium or with the titanium, can make etch-rate is Ti＞Al, thus, also the metal stacking film of for example titanium or the 3-tier architecture that titanium alloy/aluminum or aluminum alloy/titanium or titanium alloy constituted can be formed taper by etching together.
Among the present invention,, then can cause damage, so not use etching acid among the present invention as constituting raw material to glass substrate if use etching acid as the fluorochemical that constitutes raw material.Oxygenant can suitably be selected or combination according to desirable cone angle.For example, use nitric acid or methylsulfonic acid when following cone angle being controlled at 40 degree, cone angle is being controlled at 50 degree oxygenant such as use peroxydisulfate when above.In addition, by combination nitric acid or methylsulfonic acid and other oxygenant, also can be controlled at desirable cone angle.
Etching solution of the present invention can not bring bad influence to the bottom substrate, and can be alloy constituted the layer of principal constituent with containing and be that the metal stacking film of the layer that alloy constituted of principal constituent carries out etching together and makes taper by aluminium or with aluminium by titanium or with the titanium, therefore in the spreadability that improves grid, can make high-quality product in, also be excellent at economic aspect.Also can easily carry out the control of cone angle in addition.
Description of drawings
Fig. 1 is illustrated in that formed containing by titanium or with the titanium is alloy constituted the layer of principal constituent and is the distribution operation of metal stacking film of the layer that alloy constituted of principal constituent by aluminium or with aluminium on the insulativity substrate.
Nomenclature
(1) glass substrate (2) titanium or titanium alloy film
(3) aluminum or aluminum alloy film (4) resist
(a) by the grid after the etching solution etching of the present invention (much the same taper and the following taper of 40 degree)
(b) by source electrode after the etching solution etching of the present invention or drain electrode (cone angles of 90 degree)
Embodiment
Etchant of the present invention is made of fluorochemical, oxygenant and water.
Employed fluorochemical in the etching solution of the present invention owing to will be used as titanium oxide dissolving on the metal stacking film of oxygenant institute oxidation of composition of this etching solution, can be considered to mainly carry out etched material.Employed fluorochemical is to be selected from least a in the metal-salt of the metal-salt of the metal-salt of hydrofluoric acid or ammonium salt, hexafluorosilicic acid, hexafluorosilicic acid or ammonium salt, Tetrafluoroboric acid, Tetrafluoroboric acid or the ammonium salt in the etching solution of the present invention, fluorochemical for example is preferably Neutral ammonium fluoride, Potassium monofluoride, Calcium Fluoride (Fluorspan), ammonium acid fluoride, potassium bifluoride, Sodium Fluoride, magnesium fluoride, lithium fluoride, hexafluorosilicic acid, ammonium hexafluorosilicate, sodium hexafluorisilicate, potassium silicofluoride, Tetrafluoroboric acid, ammonium tetrafluoroborate, sodium tetrafluoroborate, potassium tetrafluoroborate etc., is preferably Neutral ammonium fluoride or ammonium acid fluoride especially.
In addition, in the etching solution of the present invention employed oxygenant by titanium on the metal stacking film or titanium alloy oxidation are brought into play as the etching action of evocating.Employed oxygenant is preferably select among nitric acid, ammonium nitrate, ammonium sulfate, ammonium peroxydisulfate, Potassium Persulfate, perchloric acid, ammoniumper chlorate, sodium perchlorate, hyperoxia acid potassium, Periodic acid, sodium periodate, potassium periodate, methylsulfonic acid, aquae hydrogenii dioxidi, sulfuric acid and the ethylenediamine sulfate at least a in the etching solution of the present invention, wherein more preferably nitric acid, ammonium peroxydisulfate, methylsulfonic acid.
Organic compounds containing nitrogen vitriol except ammonium sulfate, ethylenediamine sulfate, for example the vitriol of piperazine, 1-(2-amino-ethyl) piperazine, 1-amino-methyl piperazine etc. also can be used as the oxygenant use, but consider preferably sulfuric acid ammonium, ethylenediamine sulfate from easy acquisition aspect.
Even nitric acid or methylsulfonic acid since lower concentration also can reduce cone angle, for example be 40 degree or below, therefore preferred especially.Though it is less that the oxygenant except nitric acid and methylsulfonic acid reduces the effect of cone angle, because little to the damage of resist, and can control side facet etch amount, therefore preferably.The etching solution that contains above-mentioned fluorochemical and nitric acid or methylsulfonic acid can be controlled at cone angle below 40 degree, by further interpolation except nitric acid and methylsulfonic acid oxygenant or select among thionamic acid, acetic acid, the hydrochloric acid at least a, cone angle can be controlled between 30～90 degree, it is above but less than 90 degree preferably to be controlled at 30 degree, more preferably 30～85 degree further preferably are controlled between 30～80 degree.
As the preferably combination of etchant of the present invention, can list Neutral ammonium fluoride and nitric acid, Neutral ammonium fluoride and methylsulfonic acid, in addition, the combination as using oxygenant more than 2 kinds can list Neutral ammonium fluoride, nitric acid and perchloric acid; Neutral ammonium fluoride, nitric acid and sulfuric acid; Neutral ammonium fluoride, nitric acid, perchloric acid and methylsulfonic acid; Neutral ammonium fluoride, nitric acid, perchloric acid and sulfuric acid etc.
In addition, in order to improve the wettability with substrate, also can in this etching solution, add general employed tensio-active agent and organic solvent.
Etching solution of the present invention is suitable for and will carrying out etching by the formed following metal stacking film of for example sputtering method on the insulated substrate that is made of glass substrate etc. and on the silicon, compound semiconductor substrate, this metal stacking film contains by titanium or with the titanium be the layer that alloy constituted of principal constituent and be the layer that alloy constituted of principal constituent by aluminium or with aluminium, for example by titanium/aluminium, aluminium/titanium, metal stacking film that titanium/aluminium/titanium constituted.The concentration of the fluorochemical of this etching solution is 0.01～5 quality %, is preferably 0.1～1 quality %, and the concentration of oxygenant is 0.1～50 quality %, is preferably 0.5～10 quality %.
In fluoride concn is that 5 quality % are when following, can not cause damage, and can suppress to contain by titanium or with the titanium and be alloy constituted the layer of principal constituent and be the side etching amount of metal stacking film of the layer that alloy constituted of principal constituent by aluminium or with aluminium bottom glass; When 0.01 quality % was above, the etching inequality of titanium or titanium alloy tailed off, and the shape after the etching improves.The content of oxygenant is that 50 quality % are when following, can suppress to contain by titanium or with the titanium and be alloy constituted the layer of principal constituent and be the side etching amount of metal stacking film of the layer that alloy constituted of principal constituent by aluminium or with aluminium, and, the damage to resist can not take place yet; 0.1 when quality % was above, the etching speed of titanium or titanium alloy was fast and effective.
For suitably control cone angle, particularly in order to make it reach 30～90 degree, by with nitric acid or methylsulfonic acid uses separately or nitric acid or methylsulfonic acid and other oxygenant appropriate combination are carried out.At this moment, nitric acid or methylsulfonic acid are preferably 0.1～30 quality %, are preferably 0.5～15 quality % especially, and other oxygenant is preferably 0.1～20 quality %, are preferably 0.5～15 quality % especially.
Particularly, preferably use nitric acid or methylsulfonic acid for cone angle is reached below 40 degree.
In addition, further containing under at least a kind the situation of selecting among thionamic acid, the acetate and hydrochloride, their concentration is preferably 0.01～10 quality %, is preferably 0.5～5 quality % especially.
Etching solution of the present invention not special qualification of bottom substrate of etched metal stacking film, at titanium, preferred glass substrate when aluminium cascade metal films is used for liquid-crystal display, preferred silicon substrate and compound semiconductor substrate when being used for semiconductor device.
Below, enumerate embodiment and comparative example the present invention is described in further detail, but the present invention is not limited to these embodiment.
Embodiment
Embodiment 1～26
As shown in Figure 1, the substrate that titanium (700 )/aluminium (2500 )/titanium (200 ) is arranged by sputtering film-forming is gone up in preparation at glass substrate (1).
Then, on the stacked film of glass/titanium/aluminium/titanium metal, form figure, and be immersed in the etching solution (aqueous solution that contains the composition of putting down in writing among each embodiment) of the embodiment 1～26 of table 1 (etch temperature is 30 ℃) with resist (4).Afterwards, after ultrapure water washing, nitrogen blowing drying, by the electron microscope observation substrate shape.The results are shown in the table 1.
Comparative example 1～2
Will be on glass substrate be immersed in respectively the becoming in the etching solution that branch forms of comparative example 1～2 of table 1, similarly handle with embodiment by employed glass/titanium/aluminium/titanium among the formed embodiment of sputtering method.The result is shown in Table 1 together.
Table 1
| Etching solution is formed (quality %) | Cone angle (°) | Damage to glass substrate | Damage to resist | |
| Embodiment 1 | Neutral ammonium fluoride: nitric acid=0.2 quality %: 3 quality % | 35 | Do not have | Do not have |
| |
Neutral ammonium fluoride: nitric acid=0.2 quality %: 10 quality % | 30 | Do not have | Do not have |
| |
Hexafluorosilicic acid: nitric acid=2.0 quality %: 10 quality % | 30 | Do not have | Do not have |
| |
Neutral ammonium fluoride: ammonium peroxydisulfate=0.5 quality %: 20 quality % | 85 | Do not have | Do not have |
| Embodiment 5 | Neutral ammonium fluoride: methylsulfonic acid=0.5 quality %: 20 quality % | 30 | Do not have | Do not have |
| Embodiment 6 | Neutral ammonium fluoride: nitric acid: ammonium peroxydisulfate=0.3 quality %: 5 quality %: 10 quality % | 40 | Do not have | Do not have |
| Embodiment 7 | Neutral ammonium fluoride: nitric acid: ammonium nitrate=0.3 quality %: 5 quality %: 10 quality % | 30 | Do not have | Do not have |
| Embodiment 8 | Neutral ammonium fluoride: nitric acid: ammonium peroxydisulfate=0.3 quality %: 1 quality %: 5 quality % | 80 | Do not have | Do not have |
| Embodiment 9 | Neutral ammonium fluoride: nitric acid: ammonium peroxydisulfate=0.3 quality %: 3 quality %: 5 quality % | 55 | Do not have | Do not have |
| Embodiment 10 | Neutral ammonium fluoride: nitric acid: ammonium peroxydisulfate=0.3 quality %: 5 quality %: 5 quality % | 40 | Do not have | Do not have |
| Embodiment 11 | Neutral ammonium fluoride: nitric acid: thionamic acid=0.15 quality %: 2 quality %: 0.75 quality % | 35 | Do not have | Do not have |
| Embodiment 12 | Neutral ammonium fluoride: nitric acid: perchloric acid: thionamic acid=0.15 quality %: 1 quality %: 1 quality %: 0.5 quality % | 35 | Do not have | Do not have |
| Embodiment 13 | Neutral ammonium fluoride: nitric acid: perchloric acid: thionamic acid=0.2 quality %: 1 quality %: 1 quality %: 0.75 quality % | 40 | Do not have | Do not have |
| Embodiment 14 | Neutral ammonium fluoride: nitric acid: perchloric acid: methylsulfonic acid=0.2 quality %: 1 quality %: 1 quality %: 2 quality % | 40 | Do not have | Do not have |
| Embodiment 15 | Neutral ammonium fluoride: nitric acid: perchloric acid: methylsulfonic acid=0.15 quality %: 0.5 quality %: 0.5 quality %: 1 quality % | 45 | Do not have | Do not have |
| Embodiment 16 | Neutral ammonium fluoride: perchloric acid: methylsulfonic acid=0.2 quality %: 4 quality %: 0.5 quality % | 55 | Do not have | Do not have |
| Embodiment 17 | Neutral ammonium fluoride: perchloric acid: sulfuric acid=0.2 quality %: 4 quality %: 1 quality % | 50 | Do not have | Do not have |
| Embodiment 18 | Neutral ammonium fluoride: nitric acid: perchloric acid: sulfuric acid=0.2 quality %: 0.5 quality %: 4 quality %: 2 quality % | 50 | Do not have | Do not have |
| Embodiment 19 | Neutral ammonium fluoride: nitric acid: perchloric acid: sulfuric acid=0.3 quality %: 0.5 quality %: 5 quality %: 2 quality % | 50 | Do not have | Do not have |
| Embodiment 20 | Neutral ammonium fluoride: nitric acid: sulfuric acid: acetic acid=0.3 quality %: 2 quality %: 5 quality %: 5 quality % | 30 | Do not have | Do not have |
| Embodiment 21 | Neutral ammonium fluoride: nitric acid: sulfuric acid: methylsulfonic acid=0.3 quality %: 1 quality %: 4 quality %: 1 quality % | 35 | Do not have | Do not have |
| Embodiment 22 | Neutral ammonium fluoride: nitric acid: ammonium sulfate=0.25 quality %: 0.5 quality %: 0.5 quality % | 45 | Do not have | Do not have |
| Embodiment 23 | Neutral ammonium fluoride: nitric acid: ethylenediamine sulfate=0.2 quality %: 3.0 quality %: 0.5 quality % | 40 | Do not have | Do not have |
| Embodiment 24 | Neutral ammonium fluoride: nitric acid: perchloric acid: ethylenediamine sulfate=0.2 quality %: 5.0 quality %: 1.0 quality %: 0.3 quality % | 35 | Do not have | Do not have |
| Embodiment 25 | Neutral ammonium fluoride: nitric acid: perchloric acid: ammonium sulfate=0.2 quality %: 5.0 quality %: 2.0 quality %: 0.5 quality % | 40 | Do not have | Do not have |
| Embodiment 26 | Tetrafluoroboric acid: nitric acid: perchloric acid: sulfuric acid=1.75 quality %: 0.4 quality %: 2.0 quality %: 0.1 quality % | 55 | Do not have | Do not have |
| Comparative example 1 | Hydrofluoric acid: nitric acid=0.2 quality %: 3 quality % | 25 | Have | Do not have |
| Comparative example 2 | Ammoniacal liquor: aquae hydrogenii dioxidi=5 quality %: 10 quality % | * | Do not have | Have |
*: the dispersion that becomes of 3 layers of shape
As known from Table 1, the etching solution of the application of the invention carries out etching, can will pass through the etching together in short time of the formed titanium/aluminium of sputtering method/titanium stacked film.And, by suitable selective oxidation agent, can be controlled at desirable cone angle.
Comparative example 3～5
In order further to test the etching solution described in the patent documentation 5, prepared the etching solution (aqueous solution) of following composition.
Comparative example 3: hydrofluoric acid (0.3 quality %)+Periodic acid (0.5 quality %)+sulfuric acid (0.54 quality %)
Comparative example 4: hydrofluoric acid (15 quality %)+Periodic acid (1.5 quality %)+sulfuric acid (5.4 quality %)
Comparative example 5: hydrofluoric acid (0.03 quality %)+Periodic acid (0.05 quality %)+sulfuric acid (0.06 quality %)
Then, prepare Al plate (the independent class of Al: 20 * 10 * 0.1mm), Ti plate (the independent class of Ti: 20 * 10 * 0.1mm), with they two Al/Ti contact substrate (Al-Ti contacts class) and sheet glass (20 * 18 * 0.1mm) that couple together and obtain.These 4 kinds of substrates are immersed in respectively in the etching solution of comparative example 3 and 4, measure etch-rate (etch temperature is 30 ℃).The results are shown in table 2.In addition, be reference electrode with Ag/AgCl, be counter electrode with the platinum plate, measure the electropotential of titanium and aluminium in the etching solution of comparative example 3, obtain the potential difference of titanium and aluminium.
Table 2
| The independent class of Al | The independent class of Ti | Al-Ti contacts class | Sheet glass E.R. nm/min | ||||||||||
| Al | Ti | ||||||||||||
| E.R. nm/min | I.T. sec | E.R. (I.T.) nm/min | E.R. nm/min | I.T. sec | E.R. (I.T.) nm/min | E.R. nm/min | I.T. sec | E.R. (I.T.) nm/min | E.R. nm/min | I.T. sec | E.R. (I.T.) nm/min | ||
| Comparative example 3 | 960 | 4 | 990 | 140 | - | - | 960 | 5 | 1000 | 120 | - | - | 57 |
| Comparative example 4 | 6590 | ||||||||||||
E.R.: etch-rate; I.T.: induction time (time before etching begins);
E.R. (I.T.): the clean etch-rate of removing induction time
Then, preparation is formed with the substrate (glass/Al/Ti substrate) of aluminium (1800 ) and titanium (900 ) successively by sputtering method on glass substrate, be immersed in respectively in the etching solution of comparative example 3～5, confirm the metallic membrane dissolving and see time (JET: the etching period that records) till the glass basis.The etching shape of the stacked film when then, observing in 1.25 times the time of JET separately dip treating.It the results are shown in table 3.
Table 3
| JET (second) | JET * 1.25 (second) | The etching situation of stacked film | S.E. (μm) | |
| Comparative example 3 | 52 | 65 | The etching section approximate vertical of Al/Ti | 1.1 |
| Comparative example 4 | 5 | 6 | Substrate glass becomes white | - |
| Comparative example 5 | 639 | 799 | - | - |
S.E.: side etching
For the etching solution of comparative example 3, from the etch-rate of each metal sheet more as can be known, the etch-rate of the etching solution described in the patent documentation 5 be Ti＜＜Al.Under the situation of the stacked film of metal of the same race not, because battery effect, sometimes metal is different with the etch-rate that contacts class separately, but in the etching solution of comparative example 3, do not see independent class and the etch-rate that contacts class than big-difference, even as can be known on multilayer board, etch-rate also be Ti＜＜Al.The potential difference that can confirm to try to achieve from the electropotential of Al and Ti is less than 400mV, but after the Ti on the upper strata dissolving, the etching of the Al of lower floor is carried out at a high speed, so the etching shape do not become taper, but approximate vertical.In addition, the etching solution of comparative example 4 is violent to the etch of glass substrate, even on glass/Al/Ti multilayer board, by the etching of short period of time, bottom glass is just become opaque by etch, and the etch-rate of the etching solution of comparative example 5 is slow, and is all impracticable.
In sum, etching solution of the present invention can use as the etching solution that forms distribution or the isochronous metal stacking film of electrode in the manufacturing process of electronic installations such as semiconductor device and liquid-crystal display.
Claims (11)
1. etchant, it is used for containing by titanium or with the titanium is alloy constituted the layer of principal constituent and is that the metal stacking film of the layer that alloy constituted of principal constituent carries out etching together by aluminium or with aluminium, described etchant contains fluorochemical and oxygenant, and described fluorochemical is at least a kind that is selected from the metal-salt of the metal-salt of the metal-salt of hydrofluoric acid or ammonium salt, hexafluorosilicic acid, hexafluorosilicic acid or ammonium salt, Tetrafluoroboric acid, Tetrafluoroboric acid or the ammonium salt.
2. etchant as claimed in claim 1, wherein, only use fluorochemical, oxygenant and water as constituting raw material, described fluorochemical is at least a kind that is selected from the metal-salt of the metal-salt of the metal-salt of hydrofluoric acid or ammonium salt, hexafluorosilicic acid, hexafluorosilicic acid or ammonium salt, Tetrafluoroboric acid, Tetrafluoroboric acid or the ammonium salt.
3. etchant as claimed in claim 1 or 2, wherein, oxygenant is at least a kind that selects among nitric acid, ammonium nitrate, ammonium sulfate, ammonium peroxydisulfate, Potassium Persulfate, perchloric acid, ammoniumper chlorate, sodium perchlorate, potassium perchlorate, Periodic acid, sodium periodate, potassium periodate, methylsulfonic acid, aquae hydrogenii dioxidi, sulfuric acid and ethylenediamine sulfate.
4. etchant as claimed in claim 1 or 2, wherein, the concentration of fluorochemical is 0.01～5 quality %, the concentration of oxygenant is 0.1～50 quality %.
5. etchant as claimed in claim 1 or 2, wherein, oxygenant is nitric acid or methylsulfonic acid.
6. etchant as claimed in claim 5, wherein, it further contains as oxygenant select among ammonium nitrate, ammonium sulfate, ammonium peroxydisulfate, Potassium Persulfate, perchloric acid, ammoniumper chlorate, sodium perchlorate, potassium perchlorate, Periodic acid, sodium periodate, potassium periodate, aquae hydrogenii dioxidi, sulfuric acid and the ethylenediamine sulfate at least a kind.
7. etchant as claimed in claim 1, wherein, it further contains at least a kind that selects among thionamic acid, the acetate and hydrochloride.
8. etchant as claimed in claim 1 or 2, wherein, the bottom substrate is a liquid crystal display glass substrate.
9. etchant as claimed in claim 1 or 2, wherein, the bottom substrate is a semiconductor device with silicon substrate or compound semiconductor substrate.
10. as each described etchant in the claim 1～9, wherein, can be alloy constituted the layer of principal constituent with containing and be that the cone angle of metal stacking film after etching of the layer that alloy constituted of principal constituent is controlled in the scopes of 30～90 degree by aluminium or with aluminium by titanium or with the titanium.
11. etchant as claimed in claim 10 wherein, can be controlled at cone angle in the scope of 30～85 degree.
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| CNA2006101216371A CN101130870A (en) | 2006-08-23 | 2006-08-23 | Laminated film |
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| CNA2006101216371A CN101130870A (en) | 2006-08-23 | 2006-08-23 | Laminated film |
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| CNA2006101216371A Pending CN101130870A (en) | 2006-08-23 | 2006-08-23 | Laminated film |
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| CN101845630A (en) * | 2009-03-25 | 2010-09-29 | 关东化学株式会社 | The selection etching solution of gold and nickel |
| CN102326235A (en) * | 2009-02-23 | 2012-01-18 | 关东化学株式会社 | Etching solution compositions for metal laminate films |
| CN102471686A (en) * | 2009-07-22 | 2012-05-23 | 东友Fine-Chem股份有限公司 | Etchant composition for the formation of a metal line |
| CN102586780A (en) * | 2012-02-21 | 2012-07-18 | 上海正帆科技有限公司 | Acidic etching solution, as well as preparation method and application thereof |
| CN102686780A (en) * | 2009-12-28 | 2012-09-19 | 汉高股份有限及两合公司 | Pretreatment process for aluminum and high etch cleaner used therein |
| CN103668209A (en) * | 2013-12-07 | 2014-03-26 | 江阴江化微电子材料股份有限公司 | Etching solution composition for titanium-aluminum-titanium metal laminated membrane |
| KR101621534B1 (en) | 2009-07-22 | 2016-05-17 | 동우 화인켐 주식회사 | Etching solution composition for formation of metal line |
| CN105676601A (en) * | 2014-12-03 | 2016-06-15 | 东京应化工业株式会社 | Pretreatment method of glass substrate used for forming etching mask |
| KR101733804B1 (en) | 2009-08-20 | 2017-05-08 | 동우 화인켐 주식회사 | Etching solution composition for formation of metal line |
| CN108468049A (en) * | 2018-03-29 | 2018-08-31 | 山西银光华盛镁业股份有限公司 | A kind of plastic deformation Mg alloy surface sand surface treatment liquid and its application |
| CN109554711A (en) * | 2019-01-31 | 2019-04-02 | 武汉华星光电半导体显示技术有限公司 | Etchant |
| CN114717559A (en) * | 2022-03-03 | 2022-07-08 | 深圳市金泉益科技有限公司 | Titanium etching solution and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102326235A (en) * | 2009-02-23 | 2012-01-18 | 关东化学株式会社 | Etching solution compositions for metal laminate films |
| CN102326235B (en) * | 2009-02-23 | 2015-05-20 | 关东化学株式会社 | Etching solution compositions for metal laminate films |
| US9039915B2 (en) | 2009-02-23 | 2015-05-26 | Kanto Kagaku Kabushiki Kaisha | Etching solution compositions for metal laminate films |
| CN101845630A (en) * | 2009-03-25 | 2010-09-29 | 关东化学株式会社 | The selection etching solution of gold and nickel |
| KR101621534B1 (en) | 2009-07-22 | 2016-05-17 | 동우 화인켐 주식회사 | Etching solution composition for formation of metal line |
| CN102471686A (en) * | 2009-07-22 | 2012-05-23 | 东友Fine-Chem股份有限公司 | Etchant composition for the formation of a metal line |
| CN102471686B (en) * | 2009-07-22 | 2014-08-27 | 东友Fine-Chem股份有限公司 | Etchant composition for the formation of a metal line |
| KR101733804B1 (en) | 2009-08-20 | 2017-05-08 | 동우 화인켐 주식회사 | Etching solution composition for formation of metal line |
| CN102686780A (en) * | 2009-12-28 | 2012-09-19 | 汉高股份有限及两合公司 | Pretreatment process for aluminum and high etch cleaner used therein |
| CN102686780B (en) * | 2009-12-28 | 2015-04-08 | 汉高股份有限及两合公司 | Pretreatment process for aluminum and high etch cleaner used therein |
| US9163315B2 (en) | 2009-12-28 | 2015-10-20 | Henkel Ag & Co. Kgaa | Pretreatment process for aluminum and high etch cleaner used therein |
| CN102586780A (en) * | 2012-02-21 | 2012-07-18 | 上海正帆科技有限公司 | Acidic etching solution, as well as preparation method and application thereof |
| CN103668209A (en) * | 2013-12-07 | 2014-03-26 | 江阴江化微电子材料股份有限公司 | Etching solution composition for titanium-aluminum-titanium metal laminated membrane |
| CN103668209B (en) * | 2013-12-07 | 2016-01-20 | 江阴江化微电子材料股份有限公司 | Titanium-aluminium-titanium metal stacked film etchant |
| CN105676601A (en) * | 2014-12-03 | 2016-06-15 | 东京应化工业株式会社 | Pretreatment method of glass substrate used for forming etching mask |
| CN105676601B (en) * | 2014-12-03 | 2020-08-07 | 东京应化工业株式会社 | Pretreatment method of glass substrate for forming etching mask |
| CN108468049A (en) * | 2018-03-29 | 2018-08-31 | 山西银光华盛镁业股份有限公司 | A kind of plastic deformation Mg alloy surface sand surface treatment liquid and its application |
| CN108468049B (en) * | 2018-03-29 | 2020-03-10 | 山西银光华盛镁业股份有限公司 | Plastic deformation magnesium alloy surface sand surface treatment fluid and application thereof |
| CN109554711A (en) * | 2019-01-31 | 2019-04-02 | 武汉华星光电半导体显示技术有限公司 | Etchant |
| US11136504B2 (en) | 2019-01-31 | 2021-10-05 | Wuhan China Star Optoelectronics Semiconductor Display Technology Co., Ltd. | Etchant composition |
| CN114717559A (en) * | 2022-03-03 | 2022-07-08 | 深圳市金泉益科技有限公司 | Titanium etching solution and application thereof |
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Application publication date: 20080227 |