CN105648439A - Liquid composition and etching method therewith - Google Patents
Liquid composition and etching method therewith Download PDFInfo
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- CN105648439A CN105648439A CN201510845502.9A CN201510845502A CN105648439A CN 105648439 A CN105648439 A CN 105648439A CN 201510845502 A CN201510845502 A CN 201510845502A CN 105648439 A CN105648439 A CN 105648439A
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/16—Acidic compositions
- C23F1/18—Acidic compositions for etching copper or alloys thereof
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- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K13/00—Etching, surface-brightening or pickling compositions
- C09K13/04—Etching, surface-brightening or pickling compositions containing an inorganic acid
- C09K13/06—Etching, surface-brightening or pickling compositions containing an inorganic acid with organic material
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Abstract
The invention relates to a liquid composition and an etching method therewith, wherein the liquid composition is used for etching copper contianing indium, gallium or zinc oxides or metal compounds with copper as main components. The etching method is cahracterized by contacting the liquid composition with the metal compound having copper or with copper as main components. The liquid composition includes A) H2O2; B) acid without fluorine atom; C) more than one from phosphonic acid, phsophates, 1H-tetrazole-1-acetic acid, 1H-tetrazole-5-acetic acid and 4-amino-1,2,4-triazole; and D) water, pH of hte composition is lwoer than 5. THe liquid composition can inhibit damage on teh indium, gallium or zinc oxides and etch copper on the oxides or the metal compounds with copper as main components.
Description
Technical field
The substrate that the present invention relates to liquid composition and use its engraving method and utilize the method to manufacture, described liquid composition is used for the copper being formed on the oxide compound containing indium, gallium, zinc and oxygen (IGZO) or etches using copper as the metallic compound of main component, it suppresses the damage to IGZO, and etches to copper or using copper as the metallic compound of main component.
Background technology
In recent years, in the process of the miniaturization of electronics, lightweight and low consumpting powerization development, especially in the field of the display unit such as liquid-crystal display, electroluminescent display, as the material of semiconductor layer, the exploitation of various oxide semiconductor material is carried out.
Oxide semiconductor material is formed primarily of indium, gallium, zinc and tin etc., have studied the various compositions such as indium gallium zinc oxide (IGZO), indium gallium oxide (IGO), indium tin zinc oxide (ITZO), indium gallium zinc tin oxide (IGZTO), gallium zinc oxide (GZO), zinc tin oxide (ZTO). Wherein, particularly research about IGZO carries out actively.
Use aforementioned IGZO as such as thin film transistor (TFT; Etc. ThinFilmTransistor), during electronic component, IGZO uses the film-forming process such as sputtering method to be formed on the substrates such as glass. Then, etch as mask using resist etc., thus form electrode pattern. And then thereon, it may also be useful to the film-forming process such as sputtering method form copper (Cu), molybdenum (Mo) etc., then, etch using resist etc. as mask, thus form source/drain wiring. This carries out etching method wet (wet) method and dry (dry) method, uses etching solution in wet method.
Usual known IGZO is easily by acid, alkaline etching, it may also be useful to these etching solutions form the tendency that there is the IGZO as substrate when source/drain connects up and easily corrode. Due to the corrosion of this IGZO, there is the situation of the electrical characteristic deterioration of TFT. Therefore, being typically employed on IGZO and form etching barrier type (etchstoptype) structure (with reference to Fig. 1) forming source/drain wiring after protective layer, but manufacture and become numerous and diverse, its result causes cost to increase.Therefore, back of the body channel-etch type (backchanneletchtype) structure (with reference to Fig. 2) not needing protective layer to adopt, it is desirable to suppress the damage to IGZO and various wiring material can be carried out etching solution for etching.
Patent documentation 1 (No. 2011/021860th, International Publication) discloses and uses etching solution that the metallic membrane using copper as main component is carried out etching method, and described etching solution comprises: more than a kind compound 0.1��10.0 weight % that (A) hydrogen peroxide 5.0��25.0 weight %, (B) fluorine cpd 0.01��1.0 weight %, (C) azole compounds 0.1��5.0 weight %, (D) are selected from the group being made up of phosphonate derivative or its salt, (E) water.
But, etching solution disclosed in patent documentation 1 comprises hydrogen peroxide, fluorine cpd, azole compounds and phosphonate derivative or its salt, but phosphonate derivative or its salt add in order to the stabilization of hydrogen peroxide, it does not have mention about the damage to the oxide compound (IGZO) containing indium, gallium, zinc and oxygen. Hydrogen peroxide, fluorine cpd, azole compounds and 1-hydroxy ethylidene-1 is had about compounding, the liquid composition of 1-di 2 ethylhexyl phosphonic acid, confirming the damage to IGZO (with reference to comparative example 13), as suppressing, the liquid composition damaging and being etched by metallic compound to IGZO is insufficient.
Patent documentation 2 (No. 2009/066750th, International Publication) describes: with the use of the etchant of the alkalescence formed by the aqueous solution containing alkali, comprising amorphous oxide film and by being selected from aluminium (Al), in the etching of stacked film that Al alloy, copper (Cu), Cu close at least a kind of metallic membrane formed in gold and silver (Ag) and the group that forms of Ag alloy, it is possible to optionally etched by this metallic membrane.
But, etchant disclosed in patent documentation 2 is the etchant of the alkalescence formed by the aqueous solution containing alkali, but having the liquid composition of hydrogen peroxide and ammonia to confirm the damage to IGZO (with reference to comparative example 14) about compounding, as suppressing, the liquid composition damaging and being etched by metallic compound to IGZO is insufficient.
Patent documentation 3 (No. 2013/015322nd, International Publication) describes: with the use of the etching solution comprising the pyroles such as the amine compound such as the organic acid such as mineral acid, succsinic acid, thanomin such as hydrogen peroxide, sulfuric acid or nitric acid and 5-amino-1H-TETRAZOLE, it is possible to reduce the damage to semiconductor layer and optionally copper/molybdenum multi layer film is etched.
But, owing to the semiconductor layers such as IGZO being caused damage in low pH region, therefore etching solution disclosed in patent documentation 3 needs the scope being adjusted to pH2.5��5 to use.
Prior art literature
Patent documentation
Patent documentation 1: No. 2011/021860th, International Publication
Patent documentation 2: No. 2009/066750th, International Publication
Patent documentation 3: No. 2013/015322nd, International Publication
Summary of the invention
The problem that invention to be solved
The problem of the present invention be to provide suppress the damage to IGZO and to the copper being formed on IGZO or the liquid composition that etches using copper as the metallic compound of main component be characterised in that the engraving method using this liquid composition and the copper being formed on IGZO or contact using copper as the metallic compound of main component and the substrate applied this engraving method and manufacture.
For the scheme dealt with problems
The present inventor etc. have studied to solve the problem, found that following liquid composition can solve the problem, described liquid composition is characterised in that, comprise: (A) hydrogen peroxide, (B) not acid of contain fluorine atoms, (C) are selected from by phosphonic acid based, phosphoric acid ester, 1H-TETRAZOLE-1-acetic acid, 1H-TETRAZOLE-5-acetic acid and 4-amino-1,2, more than a kind compound in the group of 4-triazole composition and (D) water, and the pH value of described liquid composition is less than 5.
The present invention completes based on above-mentioned discovery. That is, described in the present invention as follows.
[1] a kind of liquid composition, it is characterized in that, it is for being formed in containing indium, gallium, copper on the oxide compound of zinc and oxygen or etch using copper as the metallic compound of main component, described liquid composition comprises: (A) hydrogen peroxide, (B) acid of not contain fluorine atoms, (C) it is selected from by phosphonic acid based, phosphoric acid ester, 1H-TETRAZOLE-1-acetic acid, 1H-TETRAZOLE-5-acetic acid and 4-amino-1, 2, more than a kind compound in the group of 4-triazole composition, and (D) water, the acid of described (B) not contain fluorine atoms does not comprise described (C) composition, and the pH value of described liquid composition is less than 5.
[2] liquid composition according to the 1st, it is characterized in that, to the copper being formed on the oxide compound containing indium, gallium, zinc and oxygen or using copper as the metallic compound of main component and the molybdenum being formed on the oxide compound containing indium, gallium, zinc and oxygen or etch using molybdenum as the metallic compound of main component.
[3] liquid composition according to the 1st, wherein, more than a kind compound in the group that the acid of (B) not contain fluorine atoms is made up of nitric acid, sulfuric acid, phosphoric acid, hydrochloric acid, methylsulfonic acid, thionamic acid, acetic acid, oxyacetic acid, lactic acid, propanedioic acid, toxilic acid, succsinic acid, oxysuccinic acid, tartrate and citric acid for being selected from.
[4] liquid composition according to the 1st, wherein, (C) phosphonic acid based is for being selected from by aminomethylphosphonic acid, just own base phosphonic acids, 1-octyl phosphonic acid, amino three (methylene phosphonic acid), hydroxy ethylidene-1,1-di 2 ethylhexyl phosphonic acid, N, N, N ', more than a kind compound in the group that N '-EDTMP, 1,2-propylene diamine four (methylene phosphonic acid), diethylene triamine penta(methylene phosphonic acid), two (hexa-methylene) triamine five (methylene phosphonic acid) and penten eight (methylene phosphonic acid) form.
[5] liquid composition according to the 1st, wherein, (C) phosphoric acid ester is more than the a kind compound being selected from the group being made up of monoethyl phosphate, diethyl phosphoric acid and ethylene glycol phosphoric acid ester.
[6] liquid composition according to the 1st, its also comprise as stabilizer of hydrogen peroxide, more than the a kind stabilizer of hydrogen peroxide with phenyl being selected from the group being made up of phenylurea, ethyleneglycol monophenylether, phenylglycol, sulfocarbolic acid, Acetanilide, phenacetin, acetoamidophenol, hydroxy-benzoic acid, para-amino benzoic acid, p-aminophenol, 3,5-diaminobenzoic acid, Sulphanilic Acid, aniline, methylphenylamine, oxine, N-acetyl Ortho Toluidine, N-acetyl meta-aminotoluene, pentanoic, phenol, methyl-phenoxide.
[7] a kind of engraving method, it makes the liquid composition according to any one of the 1st��the 6th and the copper being formed on the oxide compound containing indium, gallium, zinc and oxygen or contacts using copper as the metallic compound of main component, etches to copper or using copper as the metallic compound of main component.
[8] a kind of engraving method, it makes the liquid composition according to any one of the 1st��the 6th and the copper being formed on the oxide compound containing indium, gallium, zinc and oxygen or using copper as the metallic compound of main component and the molybdenum being formed on the oxide compound containing indium, gallium, zinc and oxygen or contact using molybdenum as the metallic compound of main component, to copper or using copper as the metallic compound of main component and molybdenum or etch using molybdenum as the metallic compound of main component.
[9] a kind of substrate, by applying, the engraving method described in the 7th to the copper being formed on the oxide compound containing indium, gallium, zinc and oxygen or etches and manufacture using copper as the metallic compound of main component for it.
[10] a kind of substrate, it is by applying the engraving method described in the 8th to the copper being formed on the oxide compound containing indium, gallium, zinc and oxygen or using copper as the metallic compound of main component and the molybdenum being formed on the oxide compound containing indium, gallium, zinc and oxygen or etch using molybdenum as the metallic compound of main component.
The preferred version of the present invention as follows described in.
[1] a kind of liquid composition, it is characterized in that, it is for being formed in containing indium, gallium, copper on the oxide compound of zinc and oxygen or etch using copper as the metallic compound of main component, described liquid composition comprises: (A) hydrogen peroxide, (B) acid of not contain fluorine atoms, (C) it is selected from by phosphonic acid based, phosphoric acid ester, 1H-TETRAZOLE-1-acetic acid, 1H-TETRAZOLE-5-acetic acid and 4-amino-1, 2, more than a kind compound in the group of 4-triazole composition, and (D) water, the acid of described (B) not contain fluorine atoms does not comprise described (C) composition, and the pH value of described liquid composition is less than 5.
[2] liquid composition Gen Ju [1], wherein, the acid of (B) not contain fluorine atoms is more than the a kind compound that (B1) is selected from the group being made up of nitric acid, sulfuric acid, phosphoric acid and hydrochloric acid.
[3] liquid composition Gen Ju [1], wherein, the acid of (B) not contain fluorine atoms is the combination of more than the a kind compound that more than the a kind compound that (B1) is selected from the group being made up of nitric acid, sulfuric acid, phosphoric acid and hydrochloric acid is selected from the group being made up of methylsulfonic acid, thionamic acid, acetic acid, oxyacetic acid, lactic acid, propanedioic acid, toxilic acid, succsinic acid, oxysuccinic acid, tartrate and citric acid with (B2).
[4] according to the liquid composition according to any one of [1]��[3], wherein, (C) in aforementioned liquids composition is selected from by phosphonic acid based, phosphoric acid ester, 1H-TETRAZOLE-1-acetic acid, 1H-TETRAZOLE-5-acetic acid and 4-amino-1, the content of more than a kind compound in the group of 2,4-triazole composition is in the scope of 0.001 quality %��0.1 quality %.
[5] according to the liquid composition according to any one of [1]��[4], wherein, the content of (A) hydrogen peroxide in aforementioned liquids composition is in the scope of 2 quality %��10 quality %.
[6] according to the liquid composition according to any one of [1]��[5], wherein, the content of the not acid of contain fluorine atoms of (B) in aforementioned liquids composition is in the scope of 1 quality %��10 quality %, and the acid of described (B) not contain fluorine atoms does not comprise described (C) composition.
[7] according to the liquid composition according to any one of [1]��[6], wherein, (C) phosphonic acid based is for being selected from by aminomethylphosphonic acid, just own base phosphonic acids, 1-octyl phosphonic acid, amino three (methylene phosphonic acid), hydroxy ethylidene-1, 1-di 2 ethylhexyl phosphonic acid, N, N, N ', N '-EDTMP, 1, 2-propylene diamine four (methylene phosphonic acid), diethylene triamine penta(methylene phosphonic acid), more than a kind compound in the group that two (hexa-methylene) triamine five (methylene phosphonic acid) and penten eight (methylene phosphonic acid) form.
[8] according to the liquid composition according to any one of [1]��[7], wherein, (C) phosphoric acid ester is more than the a kind compound being selected from the group being made up of monoethyl phosphate, diethyl phosphoric acid and ethylene glycol phosphoric acid ester.
[9] according to the liquid composition according to any one of [1]��[8], it also comprises as stabilizer of hydrogen peroxide, it is selected from by phenylurea, ethyleneglycol monophenylether, phenylglycol, sulfocarbolic acid, Acetanilide, phenacetin, acetoamidophenol, hydroxy-benzoic acid, para-amino benzoic acid, p-aminophenol, 3, 5-diaminobenzoic acid, Sulphanilic Acid, aniline, methylphenylamine, oxine, N-acetyl Ortho Toluidine, N-acetyl meta-aminotoluene, pentanoic, phenol, more than the a kind stabilizer of hydrogen peroxide with phenyl in the group of methyl-phenoxide composition.
[10] according to liquid composition according to any one of [1]��[9], it is for the copper being formed on the oxide compound containing indium, gallium, zinc and oxygen or using copper as the metallic compound of main component and the molybdenum being formed on the oxide compound containing indium, gallium, zinc and oxygen or etch using molybdenum as the metallic compound of main component.
[11] a kind of engraving method, it is to being formed in containing indium, gallium, copper on the oxide compound of zinc and oxygen or carry out etching method using copper as the metallic compound of main component, described method makes following liquid composition and is formed in containing indium, gallium, copper on the oxide compound of zinc and oxygen or contact using copper as the metallic compound of main component, etch to copper or using copper as the metallic compound of main component, described liquid composition comprises: (A) hydrogen peroxide, (B) acid of not contain fluorine atoms, (C) it is selected from by phosphonic acid based, phosphoric acid ester, 1H-TETRAZOLE-1-acetic acid, 1H-TETRAZOLE-5-acetic acid and 4-amino-1, 2, more than a kind compound in the group of 4-triazole composition, and (D) water, the acid of described (B) not contain fluorine atoms does not comprise described (C) composition, and the pH value of described liquid composition is less than 5.
[12] method Gen Ju [11], it is to the copper being formed on the oxide compound containing indium, gallium, zinc and oxygen in the way of non-sandwiched protective layer or etches using copper as the metallic compound of main component.
[13] a kind of engraving method, it is to being formed in containing indium, gallium, copper on the oxide compound of zinc and oxygen or using copper as the metallic compound of main component, and it is formed in containing indium, gallium, molybdenum on the oxide compound of zinc and oxygen or carry out etching method using molybdenum as the metallic compound of main component, described method makes following liquid composition and is formed in containing indium, gallium, copper on the oxide compound of zinc and oxygen or using copper as the metallic compound of main component, and it is formed in containing indium, gallium, molybdenum on the oxide compound of zinc and oxygen or contact using molybdenum as the metallic compound of main component, to copper or using copper as the metallic compound of main component, and molybdenum or etch using molybdenum as the metallic compound of main component, described liquid composition comprises: (A) hydrogen peroxide, (B) acid of not contain fluorine atoms, (C) it is selected from by phosphonic acid based, phosphoric acid ester, 1H-TETRAZOLE-1-acetic acid, more than a kind compound in the group of 1H-TETRAZOLE-5-acetic acid and 4-amino-1,2,4-triazole composition, and (D) water, the acid of described (B) not contain fluorine atoms does not comprise described (C) composition, and the pH value of described liquid composition is less than 5.
[14] method Gen Ju [13], it is to the copper to be formed on the oxide compound containing indium, gallium, zinc and oxygen in the way of non-sandwiched protective layer or using copper as the metallic compound of main component and with the molybdenum that is formed on the oxide compound containing indium, gallium, zinc and oxygen in the way of non-sandwiched protective layer or etch using molybdenum as the metallic compound of main component.
According to liquid composition according to any one of [11]��[14], wherein, [15] acid of (B) not contain fluorine atoms is more than the a kind compound that (B1) is selected from the group being made up of nitric acid, sulfuric acid, phosphoric acid and hydrochloric acid.
[16] according to the liquid composition according to any one of [11]��[14], wherein, the acid of (B) not contain fluorine atoms is the combination of more than the a kind compound that more than the a kind compound that (B1) is selected from the group being made up of nitric acid, sulfuric acid, phosphoric acid and hydrochloric acid is selected from the group being made up of methylsulfonic acid, thionamic acid, acetic acid, oxyacetic acid, lactic acid, propanedioic acid, toxilic acid, succsinic acid, oxysuccinic acid, tartrate and citric acid with (B2).
[17] according to the liquid composition according to any one of [11]��[16], wherein, (C) in aforementioned liquids composition is selected from by phosphonic acid based, phosphoric acid ester, 1H-TETRAZOLE-1-acetic acid, 1H-TETRAZOLE-5-acetic acid and 4-amino-1, the content of more than a kind compound in the group of 2,4-triazole composition is in the scope of 0.001 quality %��0.1 quality %.
[18] according to the liquid composition according to any one of [11]��[17], wherein, the content of (A) hydrogen peroxide in aforementioned liquids composition is in the scope of 2 quality %��10 quality %.
[19] according to the liquid composition according to any one of [11]��[18], wherein, the content of the not acid of contain fluorine atoms of (B) in aforementioned liquids composition is in the scope of 1 quality %��10 quality %, and the acid of described (B) not contain fluorine atoms does not comprise described (C) composition.
[20] according to the liquid composition according to any one of [11]��[19], wherein, (C) phosphonic acid based is for being selected from by aminomethylphosphonic acid, just own base phosphonic acids, 1-octyl phosphonic acid, amino three (methylene phosphonic acid), hydroxy ethylidene-1, 1-di 2 ethylhexyl phosphonic acid, N, N, N ', N '-EDTMP, 1, 2-propylene diamine four (methylene phosphonic acid), diethylene triamine penta(methylene phosphonic acid), more than a kind compound in the group that two (hexa-methylene) triamine five (methylene phosphonic acid) and penten eight (methylene phosphonic acid) form.
[21] according to the liquid composition according to any one of [11]��[20], wherein, (C) phosphoric acid ester is more than the a kind compound being selected from the group being made up of monoethyl phosphate, diethyl phosphoric acid and ethylene glycol phosphoric acid ester.
[22] according to the liquid composition according to any one of [11]��[21], it also comprises as stabilizer of hydrogen peroxide, it is selected from by phenylurea, ethyleneglycol monophenylether, phenylglycol, sulfocarbolic acid, Acetanilide, phenacetin, acetoamidophenol, hydroxy-benzoic acid, para-amino benzoic acid, p-aminophenol, 3, 5-diaminobenzoic acid, Sulphanilic Acid, aniline, methylphenylamine, oxine, N-acetyl Ortho Toluidine, N-acetyl meta-aminotoluene, pentanoic, phenol, more than the a kind stabilizer of hydrogen peroxide with phenyl in the group of methyl-phenoxide composition.
The effect of invention
According to the present invention, the substrate that can provide a kind of liquid composition, engraving method and apply this engraving method and manufacture, described liquid composition suppresses the damage of the oxide compound (IGZO) containing indium, gallium, zinc and oxygen and etches to the copper being formed on IGZO or using copper as the metallic compound of main component, described engraving method is characterised in that, this liquid composition is contacted with the copper being formed on IGZO or using copper as the metallic compound of main component. In addition, owing to this engraving method can suppress the damage to IGZO, so not needing to be formed protective layer on IGZO, therefore can simplify manufacturing process and significantly reducing manufacturing cost, it is possible to realizing high productivity. Even if the liquid composition of the present invention also can suppress the damage to IGZO low pH region (pH value is less than 5, it is preferable to 0��5), and can etch to the copper being formed on IGZO or using copper as the metallic compound of main component. When using the liquid composition of the present invention in low pH region, it is possible to expect that the dissolving power height of copper, the life-span of chemical solution extend further.
Accompanying drawing explanation
Fig. 1 is the schematic diagram of etching barrier type TFT cross section structure. In Fig. 1, glass substrate 1 is formed with gate electrode 2 and gate insulating film 3, it is formed with IGZO semiconductor layer 9, etch stop layer 10, source electrode 6a and drain electrode 6b thereon, be formed with protective layer 7 and transparency electrode 8 further thereon.
Fig. 2 is the schematic diagram of back of the body channel-etch type TFT cross section structure. In Fig. 2, glass substrate 1 is formed with gate electrode 2 and gate insulating film 3, it is formed with IGZO semiconductor layer 9, source electrode 6a and drain electrode 6b thereon, and then be formed with protective layer 7 and transparency electrode 8 thereon. , in the way of the protective layers such as non-sandwiched etch stop layer, on IGZO semiconductor layer 9, form wiring material herein, form source electrode 6a and drain electrode 6b by etch processes.
Description of reference numerals
1: glass
2: gate electrode
3: gate insulating film
6a: source electrode
6b: drain electrode
7: protective layer
8: transparency electrode
9:IGZO semiconductor layer
10: etch stop layer
Embodiment
<liquid composition>
The liquid composition of the present invention is characterised in that, comprise: (A) hydrogen peroxide, (B) not acid (not comprising C composition) of contain fluorine atoms, (C) are selected from by phosphonic acid based, phosphoric acid ester, 1H-TETRAZOLE-1-acetic acid, 1H-TETRAZOLE-5-acetic acid and 4-amino-1,2, more than a kind compound in the group of 4-triazole composition and (D) water, and the pH value of described liquid composition is less than 5.
(A) hydrogen peroxide
In the liquid composition of the present invention, hydrogen peroxide (hereinafter sometimes referred to A composition) has the function that copper is oxidized as oxygenant, in addition, molybdenum is had to the function of oxidation dissolution. The content of the hydrogen peroxide in this liquid composition is preferably more than 1 quality %, is more preferably more than 2 quality %, more preferably more than 3 quality %, it is preferable to below 30 quality %, be more preferably below 20 quality %, more preferably below 10 quality %, be particularly preferably below 8 quality %. Such as, the content of the hydrogen peroxide in this liquid composition be preferably 1��30 quality %, be more preferably 2��20 quality %, more preferably 2��10 quality %, be particularly preferably 3��8 quality %. If the content of hydrogen peroxide is in above-mentioned scope, then can guaranteeing the good etch-rate for the metallic compound containing copper and molybdenum etc., the control of the etch quantity of metallic compound becomes easy, it is preferred to.
(B) acid of not contain fluorine atoms
In the liquid composition of the present invention, the acid of contain fluorine atoms is not (hereinafter sometimes referred to B component. But, do not comprise C composition) and the copper dissolution that made by (A) hydrogen peroxide oxidation.
As B component, can preferably enumerate nitric acid, sulfuric acid, phosphoric acid, hydrochloric acid, methylsulfonic acid, thionamic acid, acetic acid, oxyacetic acid, lactic acid, propanedioic acid, toxilic acid, succsinic acid, oxysuccinic acid, tartrate, citric acid etc., more preferably nitric acid, sulfuric acid, methylsulfonic acid, thionamic acid, acetic acid, wherein particularly preferably nitric acid, sulfuric acid.
Above-mentioned acid can be used alone or mixes multiple use.
Wherein, in the present invention, the acid of (B) not contain fluorine atoms preferably comprises more than the a kind compound that (B1) is selected from the group being made up of nitric acid, sulfuric acid, phosphoric acid and hydrochloric acid. In addition, (B) not acid more than the a kind compound that preferably (B1) is selected from the group being made up of nitric acid, sulfuric acid, phosphoric acid and hydrochloric acid of contain fluorine atoms and the combination of more than the a kind compound that (B2) is selected from the group being made up of methylsulfonic acid, thionamic acid, acetic acid, oxyacetic acid, lactic acid, propanedioic acid, toxilic acid, succsinic acid, oxysuccinic acid, tartrate and citric acid.
The content of the B component in this liquid composition be preferably more than 0.01 quality %, be more preferably more than 0.1 quality %, more preferably more than 0.5 quality %, be particularly preferably more than 1 quality %, be preferably below 30 quality %, be more preferably below 20 quality %, more preferably below 15 quality %, be particularly preferably below 10 quality %.Such as, the content of the B component in this liquid composition be preferably 0.01��30 quality %, be more preferably 0.1��20 quality %, more preferably 0.5��15 quality %, be particularly preferably 1��10 quality %. When the content of B component is in above-mentioned scope, it is possible to obtain the good etch-rate for metal and the solvability of good copper.
(C) compound being selected from the group being made up of phosphonic acid based, phosphoric acid ester, 1H-TETRAZOLE-1-acetic acid, 1H-TETRAZOLE-5-acetic acid and 4-amino-1,2,4-triazole
In the liquid composition of the present invention, it is selected from by phosphonic acid based, phosphoric acid ester, 1H-TETRAZOLE-1-acetic acid, 1H-TETRAZOLE-5-acetic acid and 4-amino-1, compound (hereinafter sometimes referred to C composition) in the group of 2,4-triazole composition has the effect of the etch-rate suppressing IGZO. Therefore, it may also be useful to this liquid composition is to the copper being formed on IGZO or when etching using copper as the metallic compound of main component, it is possible to suppress the damage to IGZO.
Wherein, in the present invention, as (C) composition, it is preferred to use phosphonic acid based and phosphoric acid ester, it is particularly preferred to use phosphonic acid based. Typically, it is known that easily corrode at low pH region IGZO, but with the use of phosphonic acid based, even if being the low pH region of less than 2.5 at pH, the damage to IGZO also can effectively be suppressed.
In C composition, as phosphonic acid based, can preferably enumerate aminomethylphosphonic acid, just own base phosphonic acids, 1-octyl phosphonic acid, amino three (methylene phosphonic acid), hydroxy ethylidene-1,1-two banks, N, N, N ', N '-EDTMP, 1,2-propylene diamine four (methylene phosphonic acid), diethylene triamine penta(methylene phosphonic acid), two (hexa-methylene) triamine five (methylene phosphonic acid), penten eight (methylene phosphonic acid) etc.
In C composition, as phosphoric acid ester, it is possible to preferably enumerate monoethyl phosphate, diethyl phosphoric acid, ethylene glycol phosphoric acid ester etc.
The compound being selected from the group being made up of phosphonic acid based, phosphoric acid ester, 1H-TETRAZOLE-1-acetic acid, 1H-TETRAZOLE-5-acetic acid, 4-amino-1,2,4-triazole can be used alone, or mixes multiple use. It is preferably amino three (methylene phosphonic acid), 1,2-propylene diamine four (methylene phosphonic acid), diethylene triamine penta(methylene phosphonic acid), two (hexa-methylene) triamine five (methylene phosphonic acid), it is particularly preferred to amino three (methylene phosphonic acid), diethylene triamine penta(methylene phosphonic acid).
The content of the C composition in this liquid composition be preferably more than 0.001 quality %, be more preferably more than 0.01 quality %, more preferably more than 0.02 quality %, be particularly preferably more than 0.05 quality %. When the content of C composition is above-mentioned, it is possible to suppress the damage to the oxide compound containing indium, gallium, zinc and oxygen. And on the other hand, from the view point of economy, the content of C composition is preferably below 5 quality %, is more preferably below 1 quality %, more preferably below 0.5 quality %, be particularly preferably below 0.1 quality %.
(D) water
As the water used in the liquid composition of the present invention, it is not particularly limited, the water removing metal ion, organic impurity, fine-grained particles etc. preferably by distillation, ion exchange treatment, filter process, various adsorption treatment etc. and obtain, it is particularly preferred to pure water or ultrapure water.
The liquid composition of the present invention can contain stabilizer of hydrogen peroxide as required. As stabilizer of hydrogen peroxide, usually, as long as the material that can use as the stablizer of hydrogen peroxide, so that it may not use with limitation, it is preferable that have the stabilizer of hydrogen peroxide of phenyl.
As the stabilizer of hydrogen peroxide with phenyl, can preferably enumerate phenylurea, ethyleneglycol monophenylether, phenylglycol, sulfocarbolic acid, Acetanilide, phenacetin, acetoamidophenol, hydroxy-benzoic acid, para-amino benzoic acid, p-aminophenol, 3, 5-diaminobenzoic acid, Sulphanilic Acid, aniline, methylphenylamine, oxine, N-acetyl Ortho Toluidine, N-acetyl meta-aminotoluene, pentanoic, phenol, methyl-phenoxide, more preferably phenylurea, ethyleneglycol monophenylether, phenylglycol, sulfocarbolic acid, wherein particularly preferably phenylurea, ethyleneglycol monophenylether.
They can be used alone or mix multiple use.
About the content of stabilizer of hydrogen peroxide, as long as its additive effect can fully be obtained, it is not particularly limited, be preferably more than 0.01 quality %, be more preferably more than 0.02 quality %, more preferably more than 0.03 quality %, it is preferable to below 0.5 quality %, be more preferably below 0.3 quality %, more preferably below 0.1 quality %. Such as, the content of stabilizer of hydrogen peroxide is preferably 0.01��0.5 quality %, is more preferably 0.02��0.3 quality %, more preferably 0.03��0.1 quality %.
Liquid composition for the present invention, in order to obtain the pH value expected, can contain pH adjusting agent as required. As pH adjusting agent, it is possible to preferably enumerating ammoniacal liquor, sodium hydroxide, potassium hydroxide, tetramethyl ammonium hydroxide etc., they can be used alone or mix multiple use.
The upper limit of the pH value of the liquid composition of the present invention is less than 5. When pH value is more than 5, the decline of the stability of hydrogen peroxide, and copper or decline using copper as the etch-rate of the metallic compound of main component, therefore not preferred. In addition, the lower limit of the pH value of the liquid composition of the present invention is not limited, from the view point of suppress the damage to device material, surrounding member, it is preferable that pH value is more than 0, is more preferably more than 1. When pH value is above-mentioned situation, it is possible to obtain for copper or using copper as the metallic compound of main component, molybdenum or using molybdenum as the good etch-rate of the metallic compound of main component.
Etching solution for the present invention, except mentioned component, it is also possible to contain normally used various additive in etching solution not damage the scope of the effect of etching solution. Such as, it is possible to use azole compounds, pH buffer reagent etc.
<engraving method>
The copper that etch target thing in the engraving method of the present invention is formed on IGZO or using copper as the metallic compound of main component. Engraving method according to the present invention, it is possible to suppress the damage to IGZO, and etch to copper or using copper as the metallic compound of main component with good etch-rate.
In addition, the etch target thing in the engraving method of the present invention is formed on IGZO molybdenum or using molybdenum as the metallic compound of main component. Engraving method according to the present invention, it is possible to suppress the damage to IGZO, and etch to molybdenum or using molybdenum as the metallic compound of main component with good etch-rate.
It should be noted that, in this specification sheets, " using copper as the metallic compound of main component " refers to the metallic compound containing more than 50 quality %, preferably more than 60 quality %, the more preferably copper of more than 70 quality % in metallic compound. In addition, the metallic compound containing more than 50 quality %, preferably more than 60 quality %, the more preferably molybdenum of more than 70 quality % in metallic compound is referred to " using molybdenum as the metallic compound of main component ".
The engraving method of the present invention has the operation that the liquid composition of the present invention is contacted with etch target thing, described liquid composition is characterised in that, comprise: (A) hydrogen peroxide, (B) not acid of contain fluorine atoms, (C) are selected from by phosphonic acid based, phosphoric acid ester, 1H-TETRAZOLE-1-acetic acid, 1H-TETRAZOLE-5-acetic acid and 4-amino-1,2, more than a kind and (D) water in the group of 4-triazole composition, and the pH value of described liquid composition is less than 5. About the liquid composition of the present invention, as in<liquid composition>describe.
As copper or using copper as the metallic compound of main component, it is possible to enumerate copper (metal), copper alloy or cupric oxide, nitrogenize copper etc. As molybdenum or using molybdenum as the metallic compound of main component, it is possible to enumerate molybdenum (metal), molybdenum alloy or molybdenum oxide, molybdenum nitride etc.
In the engraving method of the present invention, as etch target thing, it is possible to etch to copper or using copper as the metallic compound of main component separately, it is also possible to etch to molybdenum or using molybdenum as the metallic compound of main component separately. In addition, it is also possible in the lump simultaneously to copper or using copper as the metallic compound of main component and molybdenum or etch using molybdenum as the metallic compound of main component. Engraving method according to the present invention, it is possible to suppress the damage of IGZO, with good etch-rate in the lump to copper or using copper as the metallic compound of main component and molybdenum or etch using molybdenum as the metallic compound of main component.
In the engraving method of the present invention, about the copper as etch target thing or using copper as the metallic compound of main component, molybdenum or using molybdenum as the metallic compound of main component, its shape is not limited, use copper or during using copper as wiring material on the metallic compound of main component, molybdenum or the tft array panel using molybdenum as the metallic compound of main component as flat-panel monitor, it is preferable to film shape. Such as by after IGZO patterning on the insulating films such as silicon oxide, form copper or using copper as the film of the metallic compound of main component, painting erosion resistant agent thereon, the pattern mask exposure transfer that will expect, develop, using be thus formed with the resist pattern of expectation metallic compound as etch target thing. In addition, etch target thing can be by copper or using copper as the film of the metallic compound of main component and molybdenum or the stepped construction that formed as the film of the metallic compound of main component using molybdenum. In this situation, it is possible to etch by copper or using copper as the film of the metallic compound of main component and molybdenum or the stepped construction that formed as the film of the metallic compound of main component using molybdenum in the lump simultaneously.
About the IGZO in the present invention, as long as being essentially the oxide compound containing indium, gallium, zinc and oxygen, just it is not particularly limited. The atomic ratio of indium, gallium, zinc is also not particularly limited, is generally the scope of In/ (In+Ga+Zn)=0.2��0.8, Ga/ (In+Ga+Zn)=0.05��0.6, Zn/ (In+Ga+Zn)=0.05��0.6. In addition, it is possible to containing the trace element (representing for M) except indium, gallium, zinc and oxygen, it is preferable that the atomic ratio of trace element is M/ (In+Ga+Zn+M) < 0.05. In addition, oxide compound can be amorphous structure, it is also possible to have crystallinity.
The Contact Temperature of etch target thing and liquid composition is preferably the temperature of 10��70 DEG C, is more preferably 20��60 DEG C, is particularly preferably 20��50 DEG C.During the temperature range of 10��70 DEG C, it is possible to obtain good etch-rate. And then, the etching operation within the scope of said temperature can suppress the corrosion of device. By improving the temperature of liquid composition, etch-rate rises, but the change that forms of the liquid composition caused by water evaporation etc. becomes big, is also considering on these basis, is suitably determining the most applicable treatment temp.
The method that liquid composition is contacted with etch target thing is not particularly limited, such as, can adopt and add, by dripping, method that the form such as (monolithic rotation treatment), spraying makes liquid composition contact with object, make object flood the common wet etch process such as method in liquid composition.
Embodiment
Below by way of embodiments of the invention and comparative example, its enforcement mode and effect are specifically described, but the present invention is not limited to these embodiments.
1. the mensuration of the etch-rate of various metal (wiring material)
Use copper (Cu)/molybdenum (Mo) stacked film and the whole facial mask of Mo individual layer that utilize sputtering film-forming on the glass substrate, measure the etch-rate of Cu, Mo of utilizing the liquid composition shown in table 1 and table 2. Aforesaid substrate is left standstill the method being immersed in the liquid composition remaining 35 DEG C and etches by employing. Thickness before and after etching uses fluorescent x-ray analyzer SEA1200VX (SeikoInstrumentsInc. manufactures) mensuration, by calculating etch-rate divided by etching period with its film thickness difference. Evaluation result is stated according to following master meter.
E: etch-rate is 100nm/ minute��it is less than 1000nm/ minute
G: etch-rate is 30nm/ minute��be less than 100nm/ minute or for 1000nm/ minute��be less than 5000nm/ minute
F: etch-rate is 5nm/ minute��be less than 30nm/ minute or for 5000nm/ minute��be less than 10000nm/ minute
P: etch-rate is less than 5nm/ minute or is more than 10000nm/ minute
It should be noted that, herein qualified is E, G and F.
The mensuration of the etch-rate of 2.IGZO
Utilize sputtering method with thickness on the glass substrateFormed indium (In), gallium (Ga), zinc (Zn) and oxygen (O) element than the IGZO film for 1:1:1:4, then, it may also be useful to the liquid composition shown in table 1 and table 2 is implemented etch-rate and measured. Aforesaid substrate is left standstill the method flooded in remaining in the liquid composition of 35 DEG C and etches by employing. Optical profile type film characteristics determinator n&kAnalyzer1280 (n&kTechnologyInc. manufacture) is utilized to measure the thickness before and after etching, by calculating etch-rate divided by etching period with its film thickness difference. And then, calculating interpolation is selected from by phosphonic acid based, phosphoric acid ester, 1H-TETRAZOLE-1-acetic acid, 1H-TETRAZOLE-5-acetic acid and 4-amino-1, more than a kind compound in the group of 2,4-triazole composition as etch-rate during C composition, with the ratio of etch-rate when not adding C composition. Evaluation result is stated according to following master meter.
E: etch-rate ratio (have C composition/without C composition)=be less than 0.1
G: etch-rate ratio (have C composition/without C composition)=0.1��be less than 0.2
F: etch-rate ratio (have C composition/without C composition)=0.2��be less than 0.5
P: etch-rate ratio (have C composition/without C composition)=more than 0.5
It should be noted that, herein qualified is E, G and F.
Embodiment 1
The polypropylene container of capacity 100ml drops into 79.99g pure water and 2.86g70% nitric acid (manufacturing with Guang Chun medicine Industrial Co., Ltd). And then, add 0.10g aminomethylphosphonic acid (MPBiomedicals, Inc. manufacture), then add 14.29g35% hydrogen peroxide (Mitsubishi Gas Chemical Co., Ltd's manufacture), it is carried out stirring and makes each composition Homogeneous phase mixing.Finally, add 2.76g48% potassium hydroxide (Northeast chemistry Co., Ltd. manufactures) and make pH value become 1.0, prepare liquid composition. The compounding amount of the hydrogen peroxide of gained liquid composition is 5 quality %, and the compounding amount of nitric acid is 2 quality %, and the compounding amount of aminomethylphosphonic acid is 0.10 quality %, and the compounding amount of potassium hydroxide is 1.33 quality %.
Use the liquid composition obtained to implement above-mentioned evaluation, gained result is shown in table 1.
Embodiment 2��13
In embodiment 1, except the kind and pH value except making C composition is as shown in table 1, operates similarly to Example 1, prepare liquid composition, it may also be useful to this liquid composition implements above-mentioned evaluation. The obtained results are shown in table 1.
Embodiment 14��18
In embodiment 1, make the kind of concentration of hydrogen peroxide, concentration of nitric acid, C composition and concentration as shown in table 1, in addition, operate similarly to Example 1, prepare liquid composition, it may also be useful to this liquid composition implements above-mentioned evaluation. Gained result is shown in table 1.
Embodiment 19,20
In embodiment 1, make the kind of C composition and pH value as shown in table 1, add acetic acid further, in addition, operate similarly to Example 1, prepare liquid composition, it may also be useful to this liquid composition implements above-mentioned evaluation. Gained result is shown in table 1.
Embodiment 21��26
In embodiment 1, make B component be sulfuric acid, make the kind of C composition and pH value as shown in table 1, in addition, operate similarly to Example 1, prepare liquid composition, it may also be useful to this liquid composition implements above-mentioned evaluation. Gained result is shown in table 1.
Embodiment 27,28
In embodiment 1, make B component be sulfuric acid and acetic acid, make the kind of C composition and pH value as shown in table 1, in addition, operate similarly to Example 1, prepare liquid composition, it may also be useful to this liquid composition implements above-mentioned evaluation. Gained result is shown in table 1.
Embodiment 29��31
In embodiment 1, make B component be hydrochloric acid, make the kind of C composition as shown in table 1, in addition, operate similarly to Example 1, prepare liquid composition, it may also be useful to this liquid composition implements above-mentioned evaluation. Gained result is shown in table 1.
Embodiment 32
In embodiment 1, make concentration of hydrogen peroxide, B component and C composition as shown in table 3, N is added as other compositions, N-diethyl-1,3-propylene diamine, 5-amino-1H-TETRAZOLE and phenylurea, in addition, operate similarly to Example 1, prepare liquid composition, it may also be useful to this liquid composition implements above-mentioned evaluation.
Comparative example 1��12
In embodiment 1, make the composition of liquid composition and pH value be the composition shown in table 2, in addition, operate similarly to Example 1, prepare liquid composition, it may also be useful to this liquid composition implements above-mentioned evaluation. Gained result is shown in table 2.
Comparative example 13
In embodiment 1, make concentration of hydrogen peroxide, C composition and pH value as shown in table 2, not containing B component, add Neutral ammonium fluoride and 5-amino-1H-TETRAZOLE, in addition, operate similarly to Example 1, prepare liquid composition, it may also be useful to this liquid composition implements above-mentioned evaluation. Gained result is shown in table 2.
Comparative example 14
In embodiment 1, make concentration of hydrogen peroxide and pH value as shown in table 2, not containing B component and C composition, add ammoniacal liquor, in addition, operate similarly to Example 1, prepare liquid composition, it may also be useful to this liquid composition implements above-mentioned evaluation. Gained result is shown in table 2.
Comparative example 15
Do not add C composition, add 5-amino-1H-TETRAZOLE, in addition, operate similarly to Example 1, prepare liquid composition, it may also be useful to this liquid composition implements above-mentioned evaluation.Gained result is shown in table 2.
Comparative example 16
Do not add C composition, in addition, prepare liquid composition, it may also be useful to this liquid composition implements above-mentioned evaluation samely with embodiment 32. Gained result is shown in table 2.
From above-described embodiment 1��32, the liquid composition of the present invention can suppress the damage to the oxide compound containing indium, gallium, zinc and oxygen, it is possible to good etch-rate to the copper being formed on the oxide compound containing indium, gallium, zinc and oxygen or using copper as the metallic compound of main component and the molybdenum being formed on the oxide compound containing indium, gallium, zinc and oxygen or etch using molybdenum as the metallic compound of main component.
On the other hand, by above-mentioned comparative example 1��12 it will be seen that liquid composition containing C composition time, cannot fully suppress the damage to the oxide compound containing indium, gallium, zinc and oxygen. In addition, even if by above-mentioned comparative example 13 it will be seen that liquid composition is containing C composition, when containing Neutral ammonium fluoride and 5-amino-1H-TETRAZOLE, also cannot fully suppress the damage to the oxide compound containing indium, gallium, zinc and oxygen. And then, by above-mentioned comparative example 14 it will be seen that liquid composition containing C composition, containing ammonia, pH value height time, cannot fully suppress the damage to the oxide compound containing indium, gallium, zinc and oxygen. And then, by above-mentioned comparative example 15 and 16 it will be seen that liquid composition containing C composition, containing 5-amino-1H-TETRAZOLE time, cannot fully suppress the damage to the oxide compound containing indium, gallium, zinc and oxygen.
Utilizability in industry
The liquid composition of the present invention can suppress the damage to IGZO; and can etch to the copper being formed on IGZO or using copper as the metallic compound of main component with good etch-rate; therefore; in TFT manufacturing process; can from the existing etching barrier type structure arranging protective membrane on IGZO to the back of the body channel-etch type structural transformation not needing protective layer; accordingly, it may be possible to make manufacturing process simplify and significantly reduce manufacturing cost, it is possible to realize high productivity.
Claims (14)
1. a liquid composition, it is characterized in that, it is for being formed in containing indium, gallium, copper on the oxide compound of zinc and oxygen or etch using copper as the metallic compound of main component, described liquid composition comprises: (A) hydrogen peroxide, (B) acid of not contain fluorine atoms, (C) it is selected from by phosphonic acid based, phosphoric acid ester, 1H-TETRAZOLE-1-acetic acid, 1H-TETRAZOLE-5-acetic acid and 4-amino-1, 2, 4-triazole composition group in more than a kind compound and (D) water, the acid of described (B) not contain fluorine atoms does not comprise described (C) composition, and the pH value of described liquid composition is less than 5.
2. liquid composition according to claim 1, wherein, the acid of (B) not contain fluorine atoms is more than the a kind compound that (B1) is selected from the group being made up of nitric acid, sulfuric acid, phosphoric acid and hydrochloric acid.
3. liquid composition according to claim 1, wherein, the acid of (B) not contain fluorine atoms is the combination of more than the a kind compound that more than the a kind compound that (B1) is selected from the group being made up of nitric acid, sulfuric acid, phosphoric acid and hydrochloric acid is selected from the group being made up of methylsulfonic acid, thionamic acid, acetic acid, oxyacetic acid, lactic acid, propanedioic acid, toxilic acid, succsinic acid, oxysuccinic acid, tartrate and citric acid with (B2).
4. liquid composition according to any one of claims 1 to 3, wherein, (C) in described liquid composition is selected from by phosphonic acid based, phosphoric acid ester, 1H-TETRAZOLE-1-acetic acid, 1H-TETRAZOLE-5-acetic acid and 4-amino-1, the content of more than a kind compound in the group of 2,4-triazole composition is in the scope of 0.001 quality %��0.1 quality %.
5. liquid composition according to any one of Claims 1 to 4, wherein, the content of (A) hydrogen peroxide in described liquid composition is in the scope of 2 quality %��10 quality %.
6. liquid composition according to any one of Claims 1 to 5, wherein, the content of the not acid of contain fluorine atoms of (B) in described liquid composition is in the scope of 1 quality %��10 quality %, and the acid of described (B) not contain fluorine atoms does not comprise described (C) composition.
7. liquid composition according to any one of claim 1��6, wherein, (C) phosphonic acid based is for being selected from by aminomethylphosphonic acid, just own base phosphonic acids, 1-octyl phosphonic acid, amino three (methylene phosphonic acid), hydroxy ethylidene-1, 1-di 2 ethylhexyl phosphonic acid, N, N, N ', N '-EDTMP, 1, 2-propylene diamine four (methylene phosphonic acid), diethylene triamine penta(methylene phosphonic acid), more than a kind compound in the group that two (hexa-methylene) triamine five (methylene phosphonic acid) and penten eight (methylene phosphonic acid) form.
8. liquid composition according to any one of claim 1��7, wherein, (C) phosphoric acid ester is more than the a kind compound being selected from the group being made up of monoethyl phosphate, diethyl phosphoric acid and ethylene glycol phosphoric acid ester.
9. liquid composition according to any one of claim 1��8, it also comprises as stabilizer of hydrogen peroxide, it is selected from by phenylurea, ethyleneglycol monophenylether, phenylglycol, sulfocarbolic acid, Acetanilide, phenacetin, acetoamidophenol, hydroxy-benzoic acid, para-amino benzoic acid, p-aminophenol, 3, 5-diaminobenzoic acid, Sulphanilic Acid, aniline, methylphenylamine, oxine, N-acetyl Ortho Toluidine, N-acetyl meta-aminotoluene, pentanoic, phenol, more than the a kind stabilizer of hydrogen peroxide with phenyl in the group of methyl-phenoxide composition.
10. liquid composition according to any one of claim 1��9, it is for the copper being formed on the oxide compound containing indium, gallium, zinc and oxygen or using copper as the metallic compound of main component and the molybdenum being formed on the oxide compound containing indium, gallium, zinc and oxygen or etch using molybdenum as the metallic compound of main component.
11. 1 kinds of engraving methods, it makes the liquid composition according to any one of claim 1��10 and the copper being formed on the oxide compound containing indium, gallium, zinc and oxygen or contacts using copper as the metallic compound of main component, etches to copper or using copper as the metallic compound of main component.
12. methods according to claim 11, it is to the copper being formed on the oxide compound containing indium, gallium, zinc and oxygen in the way of non-sandwiched protective layer or etches using copper as the metallic compound of main component.
13. 1 kinds of engraving methods, it makes the liquid composition according to any one of claim 1��10 and the copper being formed on the oxide compound containing indium, gallium, zinc and oxygen or using copper as the metallic compound of main component and the molybdenum being formed on the oxide compound containing indium, gallium, zinc and oxygen or contact using molybdenum as the metallic compound of main component, to copper or using copper as the metallic compound of main component and molybdenum or etch using molybdenum as the metallic compound of main component.
14. methods according to claim 13, it is to the copper to be formed on the oxide compound containing indium, gallium, zinc and oxygen in the way of non-sandwiched protective layer or using copper as the metallic compound of main component and with the molybdenum that is formed on the oxide compound containing indium, gallium, zinc and oxygen in the way of non-sandwiched protective layer or etch using molybdenum as the metallic compound of main component.
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| CN107978607B (en) * | 2017-11-21 | 2020-04-28 | 深圳市华星光电半导体显示技术有限公司 | Manufacturing method of back channel etching type oxide semiconductor TFT substrate |
| KR102562490B1 (en) * | 2018-10-29 | 2023-08-03 | 솔브레인 주식회사 | Etchant composition and method for methal layer etching method using the same |
| JP6485587B1 (en) * | 2018-12-25 | 2019-03-20 | 三菱瓦斯化学株式会社 | Etching solution |
| CN114032548A (en) * | 2021-11-11 | 2022-02-11 | 河南慧泽生物工程有限公司 | Copper foil etching solution for printed circuit board |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4378270A (en) * | 1981-10-29 | 1983-03-29 | Learonal, Inc. | Method of etching circuit boards and recovering copper from the spent etch solutions |
| CN102696097A (en) * | 2009-12-25 | 2012-09-26 | 三菱瓦斯化学株式会社 | Etchant and method for manufacturing semiconductor device using same |
| CN103717787A (en) * | 2011-07-26 | 2014-04-09 | 三菱瓦斯化学株式会社 | Etchant for copper/molybdenum-based multilayer thin film |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102005038414A1 (en) * | 2005-08-12 | 2007-02-15 | Basf Aktiengesellschaft | Stabilized etching solutions for etching Cu and Cu / Ni layers |
| CN101952485A (en) | 2007-11-22 | 2011-01-19 | 出光兴产株式会社 | Etching liquid composition |
| JP5403922B2 (en) * | 2008-02-26 | 2014-01-29 | 富士フイルム株式会社 | Polishing liquid and polishing method |
| CN102576170B (en) | 2009-08-20 | 2014-12-17 | 东友精细化工有限公司 | Method of fabricating array substrate for liquid crystal display |
| JP2014032998A (en) * | 2012-08-01 | 2014-02-20 | Panasonic Liquid Crystal Display Co Ltd | Method of manufacturing thin film transistor |
| KR20140118492A (en) * | 2013-03-29 | 2014-10-08 | 동우 화인켐 주식회사 | Etching composition for copper-based metal layer and method of preparing metal line |
| JP6531612B2 (en) * | 2014-11-27 | 2019-06-19 | 三菱瓦斯化学株式会社 | Liquid composition and etching method using the same |
-
2015
- 2015-10-23 JP JP2015208989A patent/JP6657770B2/en active Active
- 2015-11-20 TW TW104138367A patent/TWI667373B/en active
- 2015-11-25 KR KR1020150165660A patent/KR102328443B1/en active IP Right Grant
- 2015-11-26 CN CN201510845502.9A patent/CN105648439A/en active Pending
- 2015-11-26 CN CN202210705026.0A patent/CN115125536A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4378270A (en) * | 1981-10-29 | 1983-03-29 | Learonal, Inc. | Method of etching circuit boards and recovering copper from the spent etch solutions |
| CN102696097A (en) * | 2009-12-25 | 2012-09-26 | 三菱瓦斯化学株式会社 | Etchant and method for manufacturing semiconductor device using same |
| CN103717787A (en) * | 2011-07-26 | 2014-04-09 | 三菱瓦斯化学株式会社 | Etchant for copper/molybdenum-based multilayer thin film |
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| CN111902569A (en) * | 2018-03-26 | 2020-11-06 | 三菱瓦斯化学株式会社 | Etching solution |
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Also Published As
| Publication number | Publication date |
|---|---|
| JP2016108659A (en) | 2016-06-20 |
| KR20160064013A (en) | 2016-06-07 |
| JP6657770B2 (en) | 2020-03-04 |
| CN115125536A (en) | 2022-09-30 |
| TW201627533A (en) | 2016-08-01 |
| KR102328443B1 (en) | 2021-11-18 |
| TWI667373B (en) | 2019-08-01 |
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