CN103060805A - Method for forming metal wire harness - Google Patents
Method for forming metal wire harness Download PDFInfo
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- CN103060805A CN103060805A CN201210300024XA CN201210300024A CN103060805A CN 103060805 A CN103060805 A CN 103060805A CN 201210300024X A CN201210300024X A CN 201210300024XA CN 201210300024 A CN201210300024 A CN 201210300024A CN 103060805 A CN103060805 A CN 103060805A
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Abstract
The invention provides a method for forming a wire harness for a copper-based metal film through an etching liquid compound, so that in a double layer coating of a metallic oxide layer and a copper layer, erosion of the metallic oxide at a lower part is minimized and only the copper layer at an upper part is eroded. In addition, the etching liquid compound for the copper-based metal film is provided.
Description
Technical field
The present invention relates to the etchant of copper base metal film and use the method for forming wiring of the copper base metal film of above-mentioned etchant.
Background technology
In liquid crystal indicator, the process that forms metal wiring at substrate forms technique by the metallic membrane based on sputter etc. usually, form technique based on the photoresist material in the selective area of photoresist material coating, exposure and development, and consist of based on the step of etch process, comprise cleaning before and after other unit technique etc.This etch process refers to photoresist material as mask (mask), and stays the technique of metallic membrane in zone optionally, usually uses the dry-etching that utilizes plasma etc., or utilizes the Wet-type etching of etchant.
The resolving power that these distributions maybe will be realized according to type of drive etc. propose to have multiple membranous.Modal is grid and the source/drain electrode distribution that utilizes the stacked film of molybdenum Base Metal film and aluminum-based metal film, uses copper as conductive film, and uses molybdenum or titanium etc. as the distribution of barrier metal (barrier metal) etc.In addition, although in FFS pattern or a part of in-plane switching mode (in-plane switching mode), use the distribution based on the multilayer film of copper and indium oxide film, but in the situation that above-mentioned multilayer film also has a copper film on etching top to form the situation of multilayer film as required.But, do not carry out the exploitation for this etching solution.
The etching solution that is used for batch etch copper metal level and transparency conducting layer that comprises nitric acid, hydrochloric acid, hydrogen peroxide, azole compounds is disclosed in Korea S publication 2005-0067934.But, in the situation that above-mentioned patent, exist except the copper film on top, as the indium oxide film of lower film also etched problem.
[prior art document]
[patent documentation]
(patent documentation 1) KR2005-0067934A
Summary of the invention
When the object of the present invention is to provide a kind of Wet-type etching of the multiple layer metal layer being consisted of by metal oxide film and copper base metal film, erosion (Attack) to metal oxide film is minimized, when the etching of copper layer, form the taper profile (Taper Profile) of grazing excellence, after etching, do not leave the etchant of copper base metal film of the residue of metallic membrane.
And, the object of the present invention is to provide a kind of method for forming wiring that uses the copper base metal film of above-mentioned etchant.
The invention provides a kind of copper base metal film etchant, it is characterized in that, with respect to composition total weight, comprise: A) hydrogen peroxide (H
2O
2) 5.0～25.0wt%; B) azole compounds 0.1～5.0wt%; C) water of surplus; And D) additive.
And, the invention provides a kind of method for forming wiring of copper base metal film, comprise step: I) form metal oxide film at substrate; II) form the copper base metal film at above-mentioned metal oxide film; III) on above-mentioned copper base metal film, optionally stay the photoresponse material; And IV) the above-mentioned copper base metal film on a use etchant of the present invention etching top.
Etchant of the present invention is when the copper base metal film of the duplicature middle and upper part that etching is made of metal oxide film and copper base metal film, in the situation that the lower metal oxide film is not consisted of erosion (Attack), realize the taper profile of etch uniformity and grazing excellence, and do not produce residue, therefore, can not cause the problems such as minimizing of bad, the brightness of electrical short or distribution.
Therefore, etchant of the present invention can very usefully use when the manufacturing of the array substrate for liquid crystal display device of the circuit of realizing large picture, high brightness.
Description of drawings
Fig. 1 is the photo that the etching section of the etched Cu/ITO duplicature of the etchant that utilizes embodiment 4 is shown;
Fig. 2 is the photo that the etching section of the etched Cu/ITO duplicature of the etchant that utilizes embodiment 11 is shown;
Fig. 3 is the photo that the etching section of the etched Cu/ITO duplicature of the etchant that utilizes embodiment 18 is shown.
Embodiment
Below, it is as follows that the present invention is described in detail.
The present invention relates to a kind of etchant and method for forming wiring that improves significantly stability, so that without superheating phenomenon ground etch copper Base Metal film.Wherein, above-mentioned etchant maximum is characterised in that, except hydrogen peroxide, also comprises azole compounds and water, and also comprises additive in addition.
In the present invention, the copper base metal film includes copper in the constituent of film, and above-mentioned copper base metal film refers to the nitride of fine copper, copper, the oxide compound of copper or the alloy of copper.
The oxide compound that the alloy of above-mentioned copper refers to the nitride of fine copper, copper or copper and more than one the alloy of metal of from the group that is consisted of by aluminium (Al), magnesium (Mg), calcium (Ca), titanium (Ti), silver (Ag), chromium (Cr), manganese (Mn), iron (Fe), zirconium (Zr), niobium (Nb), molybdenum (Mo), palladium (Pd), hafnium (Hf), tantalum (Ta) and tungsten (W), selecting.
In the present invention, the etchant of copper base metal film refers in the multilayer film that is made of above-mentioned copper base metal film and metal oxide film, make the erosion (attack) as the metal oxide film of lower layer is minimized, and only the copper as upper layer is carried out etching solution compound for etching.
In the present invention, metal oxide film is the film that is made of the ternary of following formula 1 expression or quaternary oxide compound, the film that it can be called the film of oxide semiconductor layer or consist of oxide semiconductor layer.
[formula 1] AxByCzO
In above-mentioned formula, A, B and C are respectively Zn, Cd, Ga, In, Sn, Hf, Zr or Ta independently, and x, y and z are respectively the rational number more than or equal to 0 independently.
In the present invention, as the multilayer film of copper base metal film and metal oxide film, can enumerate copper indium oxide film (ITO), copper Indium sesquioxide alloy film, copper gallium oxide zinc film (IGZO) etc.Above-mentioned copper indium oxide film refers to the multilayer film that comprises the copper base metal film that forms on Indium sesquioxide Base Metal film and the above-mentioned Indium sesquioxide Base Metal film.Above-mentioned copper Indium sesquioxide base alloy film refers to the multilayer film that comprises the copper base metal film that forms on Indium sesquioxide base alloy film and the above-mentioned Indium sesquioxide alloy film.Above-mentioned copper gallium oxide zinc film (IGZO) refers to the multilayer film that comprises gallium oxide zinc film (IGZO) and the upper copper base metal film that forms of above-mentioned gallium oxide zinc film (IGZO).The lamination order of above-mentioned copper base metal film and metal oxide film can be exchanged.
1. etchant
The A that comprises in the etchant of the present invention) hydrogen peroxide (H
2O
2) be the principal constituent of etch copper Base Metal film, with respect to composition total weight, its content is 5.0～25.0wt%, is preferably 15.0～23.0wt%.If its content is lower than above-mentioned scope, the copper base metal film can't obtain etching or etching speed becomes very slow.If its content surpasses above-mentioned scope, because etching speed accelerates the technology controlling and process difficult on the whole.
The above-mentioned B that comprises in the etchant of the present invention) azoles (azole) compound plays the etching speed of regulating copper base metal, reduces the live width loss (CD Loss) of pattern, to improve the effect of technologic allowance.
With respect to composition total weight, above-mentioned B) content of azole compounds is 0.1～5.0wt%, is preferably 0.5～1.5wt%.If its content is lower than above-mentioned scope, etching speed accelerates and live width loss may be crossed greatly and occured.If its content surpasses above-mentioned scope, the etching speed of copper base metal film became slow, may have problems on the performance.
Above-mentioned B) azole compounds preferably from the group that is consisted of by amino tetrazole (aminotetrazole), benzotriazole (benzotriazole), tolyl-triazole (tolyltriazole), pyrazoles (pyrazole), pyrroles (pyrrole), imidazoles (imidazole), glyoxal ethyline, 2-ethyl imidazol(e), 2-propyl imidazole, 2-aminooimidazole, 4-methylimidazole, 4-ethyl imidazol(e) and 4-propyl imidazole, select one or more.
The C that comprises in the etchant of the present invention) there is no particular limitation for water, but deionized water preferably.More preferably, making the ratio resistance value (that is, the removed degree of the ion in the water) of water is the above deionized water of 18M Ω cm.Above-mentioned C) water is included in the etchant of the present invention according to surplus, makes its gross weight reach 100wt%.
Can also comprise D in the etchant of the present invention) additive.
Above-mentioned additive is more than one that select from the group that is made of sulfonic acid, organic peracid and phosphonate derivative and salt thereof.
Above-mentioned sulfonic acid is to have-SO
3The general name of the compound of H, it uses inorganic sulfonic acid or organic sulfonic acid (RSO
3H) all can, but preferably use organic sulfonic acid.Above-mentioned sulfonic acid (the RSO that in the aqueous solution, dissociates
3H →-RSO
3 -+ H
+) and show the character of acid.The acidity of above-mentioned sulfonic acid (Acidity) far is better than the carboxylic acids such as acetic acid, and almost similar with sulfuric acid, therefore, play by the pH that regulates etching solution and improve the activity of hydrogen peroxide with the effect of the etching speed of adjusting copper base metal film, simultaneously, may play the effect of the angle of taper that reduces etching face.And above-mentioned sulfonic acid suppresses the activity of cupric ion by reducing pH, to suppress the decomposition reaction of hydrogen peroxide.When reducing as mentioned above cupric ion active, in the process of using etching solution, can stably carry out technique.And, by above-mentioned sulfonic acid is included in the etchant of the present invention, when carrying out etching, make soft etching (S/E) excellence, and make angle of taper, the grazing excellence of etched metallic membrane.
With respect to composition total weight, above-mentioned sulfonic acid content is 0.5～5.0wt%, is preferably 1.0～3.0wt%.If its content is lower than above-mentioned scope, etching speed can reduce.If its content surpasses above-mentioned scope, the problem that the etching appropriateness becomes too fast can occur.
Above-mentioned sulfonic acid is preferably from by sulphonyl amino acid (Amidosulfonic acid), methylsulfonic acid (Methanesulfonic acid), ethyl sulfonic acid (Ethanesulfonic acid), tosic acid (p-Toluenesulfonic acid), trifluoromethanesulfonic acid (Trifiuoromethanesulfonic acid), Phenylsulfonic acid (Benzenesulfonic acid), one or more that select in the group that sulfanilic acid (sulfamic acid) and polystyrolsulfon acid (Polystyrene sulfonic acid) consist of.
Above-mentioned organic peracid (Organic Peroxyacid) improves the activity of hydrogen peroxide to play the effect of the etching speed of regulating copper by the pH that regulates etching solution, play simultaneously the secondary oxidizer effect to copper film.And, suppress the activity of Cu ion by reducing pH, to suppress the decomposition reaction of hydrogen peroxide.Above-mentioned organic peracid preferably comprises according to 1～5wt% with respect to composition total weight, more preferably comprises according to 1～3wt%.If the content of above-mentioned organic peracid (Organic Peroxyacid) is below the 1wt%, because the pH regulator effect is little, and not etching of Cu (Unetch) phenomenon may occur, if surpass 5wt%, since too fast etching speed, the technology controlling and process difficult.
Above-mentioned organic peracid (Organic Peroxyacid) can use peracetic acid (Peracetic Acid), peroxybenzoic acid (Perbenzoic acid) or its mixture, but is not to be defined in this.
Above-mentioned phosphonic acids (phosphonic acid) derivative and salt thereof carry out chelating (chelating) to the cupric ion that dissolves in the etching solution when etching, with the activity of inhibition cupric ion, thus the decomposition reaction of inhibition hydrogen peroxide.When reducing as mentioned above cupric ion active, in the process of using etching solution, can stably carry out technique.Above-mentioned phosphonate derivative and salt thereof preferably comprise according to 3～15wt% with respect to composition total weight, more preferably comprise according to 5～10wt%.
If the content of above-mentioned phosphonate derivative and salt thereof according to comprising below the 3wt%, the problem of the decomposition accelerationization of etch uniformity reduction and hydrogen peroxide will occur with respect to composition total weight, handling property (Capa) is little.If the content of above-mentioned phosphonate derivative and salt thereof comprises according to surpassing 15.0wt% with respect to composition total weight, the too fast problem of etching speed of copper film will occur, cause the technology controlling and process difficult, the needs that exist the increase of viscosity to cause improve the shortcoming of etching system suction capacity.
Above-mentioned phosphonate derivative and salt thereof are so long as usually use in this area, it can use any, for example, preferably use from by 2-amino-ethyl phosphonic acids (2-Aminoethylphosphonic acid, 2-AEP), dimethyl methyl phosphonate (Dimethyl methylphosphonate, DMMP), 1-hydroxy ethylene-1,1-di 2 ethylhexyl phosphonic acid (1-Hydroxy Ethylidene-1,1-Diphosphonic Acid, HEDP), amino three (methylene phosphonic acids) (Amino tris (methylene phosphonic acid), ATMP), EDTMP (Ethylenediamine tetra (methylene phosphonic acid), EDTMP), tetramethylene-diamine four (methylene phosphonic acid) (Tetramethylenediamine tetra (methylene phosphonic acid), TDTMP), hexanediamine four (methylene phosphonic acid) (Hexamethylenediamine tetra (methylene phosphonic acid), HDTMP), diethylene triamine penta(methylene phosphonic acid) (Diethylenetriamine penta (methylene phosphonic acid), DTPMP), phosphonic acids butane-tricarboxylic acid (Phosphonobutane-tricarboxylic acid, PBTC), N-((phosphonomethyl)) iminodiethanoic acid (N-(phosphonomethyl) iminodiacetic acid, PMIDA), 2-propyloic phosphonic acids (2-carboxyethyl phosphonic acid, CEPA), 2-hydroxy phosphinylidyne yl carboxylic acid (2-Hydroxyphosphonocarboxylic acid, HPAA) and amino-three-(methylene phosphonic acid) (Amino-tris-(methylene-phosphonic acid), AMP); And one or more the mixture of selecting in the group that consists of of salt, above-mentioned salt is sodium salt or sylvite preferably.More preferably, above-mentioned phosphonate derivative salt can use sodium salt or the sylvite of HEDP.
Etchant of the present invention also can comprise tensio-active agent.Above-mentioned tensio-active agent plays the reduction surface tension, to increase etched inhomogeneity effect.Above-mentioned tensio-active agent is so long as can bear etchant and have commerciality, there is no particular limitation for it, one or more that still preferably select from the group that is made of anion surfactant, cats product, zwitterionics, nonionogenic tenside and polyvalent alcohol tensio-active agent.
And, except aforesaid composition, also can add common additive, can enumerate metal ion chelation agent (sequestering agent) and inhibiter etc. as additive.
Hydrogen peroxide (the H that uses among the present invention
2O
2), azole compounds, sulfonic acid, organic peracid and phosphonate derivative and salt thereof can be prepared by generally well-known method, etchant of the present invention preferably has the purity that semiconductor technology is used.
Etchant of the present invention in the situation that metal oxide film is not consisted of erosion, can be realized the taper profile of etch uniformity and grazing excellence when etch copper Base Metal film.Etchant of the present invention does not produce residue when carrying out etching, therefore, be conducive to solve the problems such as minimizing of bad, the brightness of electrical short or distribution.Therefore, etchant of the present invention can very usefully use when the manufacturing of the array substrate for liquid crystal display device of the circuit of realizing large picture, high brightness.
2. method for forming wiring
Method for forming wiring of the present invention comprises step:
I) form metal oxide film at substrate;
II) on above-mentioned metal oxide film, form the copper base metal film;
III) on above-mentioned copper base metal film, optionally stay the photoresponse material; And
IV) the above-mentioned copper base metal film on a use etchant of the present invention etching top.
In method for forming wiring of the present invention, above-mentioned photoresponse material is preferably common resist material, and it can optionally be stayed by common exposure and developing process.
Below, the present invention will be described in detail by embodiment etc.But it only is to provide in order in further detail the present invention to be described that following embodiment waits, and scope of the present invention is limited by it.
Embodiment 1 to embodiment 7, and comparative example 1 is to comparative example 3: the etchant that contains sulfonic acid
Preparation
Prepare embodiment 1 to embodiment 7 according to the composition shown in the following table 1, and comparative example 1 is to the etchant 180kg of comparative example 3.
[table 1]
PTSA: tosic acid
SFA: sulfanilic acid
Embodiment 8 to embodiment 14, and comparative example 4 is to comparative example 6: order has the etching solution of organic peracid
The preparation of composition
Prepare embodiment 8 to embodiment 14 according to the composition shown in the following table 2, and comparative example 4 is to the etchant 180kg of comparative example 6.
[table 2]
Embodiment 15 to embodiment 21, and comparative example 7 is to comparative example 9: contain the etching of phosphonate derivative
The preparation of fluid composition
Prepare embodiment 15 to embodiment 21 according to the composition shown in the following table 3, and comparative example 7 is to the etchant 180kg of comparative example 9.
[table 3]
Test example 1 to 7 and comparison test example 1 to 3: the evaluating characteristics that contains the etchant of sulfonic acid
The etching of test 1:Cu/ITO and Cu/IGZOx
At glass substrate (the upper vacuum evaporation ITO of 100mm * 100mm) or IGZO
X, and at above-mentioned ITO or IGZO
XBehind the upper vacuum evaporation copper film, form the photoresist material with predetermined pattern at substrate by photoetching (photolithography) technique.Subsequently, use respectively embodiment 1 to embodiment 7, and comparative example 1 is to the etchant of comparative example 3, to Cu/ITO duplicature or Cu/IGZO
XDuplicature is implemented etch process.
Utilized the experimental installation (model name: ETCHER (TFT), SEMES company) of jet-type etching mode, when carrying out etch process, the Temperature Setting of etchant is approximately about 30 ℃.Etching period approximately 100 seconds.For the section of etched copper base metal film in the above-mentioned etch process, use section S EM (Hitachi company product, model name S-4700) to detect, and its result is recorded in following table 4.
[table 4]
(notes) zero: good, Δ: general, X: poor
With reference to table 4, the etchant of embodiment 1 to embodiment 7 all shows good etching characteristic.And, also almost not to the erosion of ITO film.
Therefore as can be known, etchant of the present invention is very suitable for the etching of copper base metal film, metal oxide film, and is very suitable for its batch etching.
Simultaneously, in the situation of the etchant of the comparative example 1 that does not have sulfonic acid, confirm to carry out etching to copper film.And, the content of the sulfonic acid of pointing out out in being equivalent to the present invention is to be lower than in the situation of etchant of comparative example 2 of 0.3wt% of 0.5wt%, the oxidation-resistance of ITO of resulting from is large, so that etching speed is slack-off significantly, causes section good and residue occured.But, do not have generation to erosion (Attack) phenomenon of ITO film.And, the content of the sulfonic acid of pointing out out in being equivalent to the present invention is higher than in the situation of etchant of comparative example 3 of 7.0wt% of 5.0wt%, although residue does not occur and to the erosion of ITO film, but because because of fast etching speed and PR (photoresistance) perk phenomenon, cause occuring pattern deformation (Pattern out) phenomenon, be not suitable as can be known etchant.
In addition, Fig. 1 is the photo that the etching section of the etched Cu/ITO duplicature of the etchant that utilizes embodiment 4 is shown.
With reference to Fig. 1, utilize the etched Cu/ITO duplicature of etchant of embodiment 4 to show good taper profile and excellent grazing.
Test example 8 to 14 and comparison test example 4 to 6: the characteristic that contains the etchant of organic peracid
Estimate
The etching of test 1:Cu/ITO and Cu/IGZOx
At glass substrate (the upper vacuum evaporation ITO of 100mm * 100mm) or IGZO
X, and at above-mentioned ITO or IGZO
XBehind the upper vacuum evaporation copper film, form the photoresist material with predetermined pattern at substrate by photoetching (photolithography) technique.Subsequently, use respectively embodiment 8 to embodiment 14, and comparative example 4 is to the etchant of comparative example 6, to Cu/ITO duplicature or Cu/IGZO
XDuplicature is implemented etch process.
Utilized the experimental installation (model name: ETCHER (TFT), SEMES company) of jet-type etching mode, when carrying out etch process, the Temperature Setting of etchant is approximately about 30 ℃.Etching period approximately 100 seconds.For the section of etched copper base metal film in the above-mentioned etch process, use section S EM (Hitachi company product, model name S-4700) to detect, and its result is recorded in following table 5.
[table 5]
(zero: good, Δ: general, X: poor)
As shown in Table 5 above, the etching solution of embodiment 8 to embodiment 14 does not consist of erosion (Attack) to bottom ITO film and the IGZOx film of copper layer.And, as confirming among Fig. 2, in the situation of the etched copper base metal film of the etchant that utilizes embodiment 11, show excellent etching section (Profile) and grazing, and do not stay etch residue.Simultaneously, in the situation of the etching solution of the comparative example 4 that does not have peracetic acid, not etched (Unetch) phenomenon of Cu occurs and can't carry out etching.In addition, shown in comparative example 5,6, at the excessively low (peracetic acid of content of organic peracid (Organic Peroxyacid), 0.5wt%) or too high (peracetic acid, in situation 7.0wt%), because etching characteristic is bad, can't guarantee the use possibility of etching solution.
Test example 15 to 21 and comparison test example 7 to 9: contain the etchant of phosphonate derivative
Evaluating characteristics
The etching of test 1:Cu/ITO and Cu/IGZOx
At glass substrate (the upper vacuum evaporation ITO of 100mm * 100mm) or IGZO
X, and at above-mentioned ITO or IGZO
XBehind the upper vacuum evaporation copper film, form the photoresist material with predetermined pattern at substrate by photoetching (photolithography) technique.Subsequently, use respectively embodiment 15 to embodiment 21, and comparative example 7 is to the etchant of comparative example 9, to Cu/ITO duplicature or Cu/IGZO
XDuplicature is implemented etch process.
Utilized the experimental installation (model name: ETCHER (TFT), SEMES company) of jet-type etching mode, when carrying out etch process, the Temperature Setting of etchant is approximately about 30 ℃.Etching period is approximately 100 seconds.For the section of etched copper base metal film in the above-mentioned etch process, use section S EM (Hitachi company product, model name S-4700) to detect, and its result is recorded in following table 6.
And, when having metal ion (particularly cupric ion), in order to estimate the degree of superheat based on the chain decomposition reaction of hydrogen peroxide, with above-described embodiment 15 to embodiment 21 and comparative example 7 etchant corresponding to comparative example 9 in behind the suitable Cu powder of stripping 3000ppm, placed 24 hours and detected temperatures, its result is recorded in following table 6.At this moment, below the maximum temperature of record in the table 6 represents is when Cu stripping 3000ppm, based on the highest numerical value in the temperature variation of the etchant of the chain decomposition reaction of hydrogen peroxide.
[table 6]
As shown in Table 6 above, the etchant of embodiment 15 to embodiment 21 all shows good etching characteristic, and the lower metal oxide film of copper layer is not consisted of and corrode (Attack).And, as confirming among Fig. 3, in the situation of the etchant etch copper Base Metal film that utilizes embodiment 18, show good taper profile, the etching grazing is excellent, and does not have etch residue and metal oxide film to corrode (Attack) phenomenon.
And as shown in Table 6 above, the etchant of embodiment 15 to embodiment 21 is when Cu stripping 3000ppm, and temperature also only rises to maximum 34.2 ℃, shows overheated stability characteristic and obtains large raising.Simultaneously, in the situation of the etching solution of the comparative example 7 that does not comprise HEDP (HEDP), show Cu not etched (Unetch) phenomenon, the Cu powder is not dissolved yet, and therefore can confirm, HEDP is essential key element in the copper film etching.In addition, in the situation of the etchant etch copper Base Metal film that utilizes comparative example 8, although show good taper profile, when Cu stripping 3000ppm, can't guarantee thermostability.And, in the situation of the etchant etch copper Base Metal film that utilizes comparative example 9, because because too fast etching speed (Etch Rate) causes etching characteristic bad, but confirmed that thermostability was guaranteed.
Test 2: the processing number based on the etchant of Cu concentration is estimated
Stripping Cu powder in turn in the etchant of embodiments of the invention 17 is with the Cu concentration that reaches record in the table 7 (0～7000ppm), and carry out etching characteristic and the estimation of stability of etchant.
Thus, to temperature variation, residue based on Cu concentration whether occur, etching section (Profile), etching grazing, metal oxide film corrode (Attack) with/without etc. estimate, and its result is illustrated in the table 7.Below maximum temperature in the table 7 represents is along with Cu concentration increases, based on the highest numerical value in the temperature variation of the etching solution of the chain decomposition reaction of hydrogen peroxide.In this evaluation, guaranteed thermostability can satisfying, do not occur in the situation of the good condition of residue and etching section, be defined as and etchant can be continued to be used in etch process and implement experiment.
[table 7]
As shown in Table 7 above, superheating phenomenon does not occur in the etchant of embodiment 17 yet when Cu stripping 7000ppm, and residue and metal oxide film do not occur corrode (Attack), showing good characteristic aspect etching section (Profile) and the grazing.Therefore can confirm, the etchant of embodiment 17 can use to Cu stripping 7000ppm.
Claims (16)
1. method for forming wiring, described method for forming wiring is the method for forming wiring of copper base metal film, comprises step:
I) form metal oxide film at substrate;
II) form the copper base metal film at described metal oxide film;
III) on described copper base metal film, optionally stay the photoresponse material; And
IV) the described copper base metal film on a use etchant etching top,
It is characterized in that, with respect to described etchant gross weight, described etchant comprises A) hydrogen peroxide (H of 5～25wt%
2O
2), B) azole compounds and the C of 0.1～5wt%) water of surplus, described etchant also comprises additive.
2. method for forming wiring according to claim 1 is characterized in that, described metal oxide film is the film that is made of the ternary of following formula 1 expression or quaternary oxide compound,
[formula 1] AxByCzO
In formula 1, A, B and C are respectively Zn, Cd, Ga, In, Sn, Hf, Zr or Ta independently, and x, y and z are respectively the rational number more than or equal to 0 independently.
3. method for forming wiring according to claim 1 is characterized in that, described additive is the sulfonic acid of 0.5～5.0wt%.
4. method for forming wiring according to claim 1 is characterized in that, described additive is the organic peracid of 1～5wt%.
5. method for forming wiring according to claim 1 is characterized in that, described additive is phosphonate derivative and the salt thereof of 3～15wt%.
6. method for forming wiring according to claim 1 is characterized in that, described copper base metal film is select from the group that the oxide compound by the nitride of fine copper, copper, copper consists of a kind of; Or from the group that the oxide compound by the nitride of fine copper, copper, copper consists of, select a kind of, with more than one the alloy of metal of from the group that is consisted of by aluminium (Al), magnesium (Mg), calcium (Ca), titanium (Ti), silver (Ag), chromium (Cr), manganese (Mn), iron (Fe), zirconium (Zr), niobium (Nb), molybdenum (Mo), palladium (Pd), hafnium (Hf), tantalum (Ta) and tungsten (W), selecting.
7. a copper base metal film etchant is characterized in that, based on described etchant gross weight, described etchant comprises:
A) hydrogen peroxide (H of 5.0～25.0wt%
2O
2);
B) azole compounds of 0.1～5.0wt%; And
C) water of surplus,
Described etchant also comprises additive.
8. copper base metal film etchant according to claim 7, it is characterized in that, B) described azole compounds is one or more that select from the group that is made of amino tetrazole (aminotetrazole), benzotriazole (benzotriazole), tolyl-triazole (tolyltriazole), pyrazoles (pyrazole), pyrroles (pyrrole), imidazoles, glyoxal ethyline, 2-ethyl imidazol(e), 2-propyl imidazole, 2-aminooimidazole, 4-methylimidazole, 4-ethyl imidazol(e) and 4-propyl imidazole.
9. copper base metal film etchant according to claim 7 is characterized in that, described additive is the sulfonic acid of 0.5～5.0wt%.
10. copper base metal film etchant according to claim 9, it is characterized in that, described sulfonic acid is from by sulphonyl amino acid (Amidosulfonic acid), methylsulfonic acid (Methanesulfonic acid), ethyl sulfonic acid (Ethanesulfonic acid), tosic acid (p-Toluenesulfonic acid), trifluoromethanesulfonic acid (Trifluoromethanesulfonic acid), Phenylsulfonic acid (Benzenesulfonic acid), one or more that select in the group that sulfanilic acid (sulfamic acid) and polystyrolsulfon acid (Polystyrene sulfonic acid) consist of.
11. copper base metal film etchant according to claim 7 is characterized in that described additive is the organic peracid of 1～5wt%.
12. copper base metal film etchant according to claim 11, it is characterized in that, described organic peracid is more than one that select from the group that is made of peracetic acid (Peracetic Acid) and peroxybenzoic acid (Perbenzoic acid).
13. copper base metal film etchant according to claim 7 is characterized in that, described additive is phosphonate derivative and the salt thereof of 3～15wt%.
14. copper base metal film etchant according to claim 13, it is characterized in that, described phosphonate derivative and salt thereof are from by 2-amino-ethyl phosphonic acids (2-AEP), dimethyl methyl phosphonate (DMMP), HEDP (HEDP), amino three (methylene phosphonic acids) (ATMP), EDTMP (EDTMP), tetramethylene-diamine four (methylene phosphonic acid) (TDTMP), hexanediamine four (methylene phosphonic acid) (HDTMP), diethylene triamine penta(methylene phosphonic acid) (DTPMP), phosphonic acid butane-tricarboxylic acid (PBTC), N-((phosphonomethyl)) iminodiethanoic acid (PMIDA), 2-propyloic phosphonic acids (CEPA), 2-hydroxy phosphinylidyne yl carboxylic acid (HPAA) and amino-three-(methylene phosphonic acid) (AMP); And one or more the mixture of selecting in the group that consists of of their salt.
15. copper base metal film etchant according to claim 7 is characterized in that, described etchant also comprises surfactant.
16. copper base metal film etchant according to claim 7 is characterized in that, described copper base metal film is select from the group that the oxide compound by the nitride of fine copper, copper, copper consists of a kind of; Or from the group that the oxide compound by the nitride of fine copper, copper, copper consists of, select a kind of, with more than one the alloy of metal of from the group that is consisted of by aluminium (Al), magnesium (Mg), calcium (Ca), titanium (Ti), silver (Ag), chromium (Cr), manganese (Mn), iron (Fe), zirconium (Zr), niobium (Nb), molybdenum (Mo), palladium (Pd), hafnium (Hf), tantalum (Ta) and tungsten (W), selecting.
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| KR20110083265 | 2011-08-22 | ||
| KR20110083264 | 2011-08-22 | ||
| KR10-2011-0083264 | 2011-08-22 | ||
| KR10-2011-0083266 | 2011-08-22 | ||
| KR20110083266 | 2011-08-22 | ||
| KR10-2011-0083265 | 2011-08-22 | ||
| KR10-2012-0080783 | 2012-07-24 | ||
| KR1020120080798A KR20130021321A (en) | 2011-08-22 | 2012-07-24 | Method for forming metal line |
| KR10-2012-0080798 | 2012-07-24 | ||
| KR1020120080783A KR101939841B1 (en) | 2011-08-22 | 2012-07-24 | Method for forming metal line |
| KR10-2012-0081099 | 2012-07-25 | ||
| KR1020120081099A KR101939842B1 (en) | 2011-08-22 | 2012-07-25 | Method for forming metal line |
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| CN103060805B CN103060805B (en) | 2014-12-17 |
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| CN105297015A (en) * | 2014-06-30 | 2016-02-03 | 东友精细化工有限公司 | Etching liquid composition and method for using the same to manufacture array substrate for liquid crystal display |
| CN106521502A (en) * | 2016-10-27 | 2017-03-22 | 宜昌南玻显示器件有限公司 | Etching solution for manufacturing of fine copper wire flexible touch screen and preparation method thereof |
| CN107587135A (en) * | 2016-07-08 | 2018-01-16 | 深圳新宙邦科技股份有限公司 | A kind of molybdenum aluminium-molybdenum etching liquid |
| JP6458913B1 (en) * | 2018-03-26 | 2019-01-30 | 三菱瓦斯化学株式会社 | Etching solution |
| JP6485587B1 (en) * | 2018-12-25 | 2019-03-20 | 三菱瓦斯化学株式会社 | Etching solution |
| CN111849486A (en) * | 2019-04-24 | 2020-10-30 | 易安爱富科技有限公司 | Etching composition and etching method using the same |
| CN115011963A (en) * | 2022-05-11 | 2022-09-06 | 江苏和达电子科技有限公司 | Copper metal etching liquid composition and use method thereof |
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| CN105297015A (en) * | 2014-06-30 | 2016-02-03 | 东友精细化工有限公司 | Etching liquid composition and method for using the same to manufacture array substrate for liquid crystal display |
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| CN111849486A (en) * | 2019-04-24 | 2020-10-30 | 易安爱富科技有限公司 | Etching composition and etching method using the same |
| CN111849486B (en) * | 2019-04-24 | 2022-08-16 | 易安爱富科技有限公司 | Etching composition and etching method using the same |
| CN115011963A (en) * | 2022-05-11 | 2022-09-06 | 江苏和达电子科技有限公司 | Copper metal etching liquid composition and use method thereof |
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