CN107304476A

CN107304476A - The etch combination or the engraving method using the composition of monofilm or stacked film

Info

Publication number: CN107304476A
Application number: CN201710262809.5A
Authority: CN
Inventors: 高桥秀树
Original assignee: Kanto Chemical Co Inc
Current assignee: Kanto Chemical Co Inc
Priority date: 2016-04-21
Filing date: 2017-04-20
Publication date: 2017-10-31
Anticipated expiration: 2037-04-20
Also published as: CN107304476B; JP6777420B2; JP2017195311A; TW201809357A; KR102596773B1; TWI731962B; KR20220108017A; KR20170120504A

Abstract

The problem of the present invention is to provide the etch combination for etching metal monofilm or metal stacking film, said composition realizes more preferable etch-rate than ever, side etching, coning angle, section shape, pattern form are easily controlled, and there is longer bath life while retention property stability.A kind of etch combination, it is for etching the monofilm formed by the metal selected from copper, titanium, molybdenum and nickel or their nitride, by the monofilm formed containing the one kind or two or more alloy selected from copper, titanium, molybdenum and nickel, or the etch combination of the stacked film containing 1 layer or more than 2 layers of the monofilm, wherein, comprising azoles, nitric acid, peroxide and water-miscible organic solvent.

Description

The etch combination or the etching using the composition of monofilm or stacked film Method

Technical field

The present invention relates to the etch combination of the metal single layer film available for flat-panel monitor etc. or stacked film or make With the engraving method of the composition.

Background technology

For the wiring material of the display devices such as flat-panel monitor, the conjunction of the copper and cupric of low electrical resistant material is employed as Gold.However, adaptation of the copper originally with the substrate of glass etc. is just not enough, and copper has the property to silicon semiconductor membrane diffusion.Cause This, it is known that is in recent years by setting the barrier metal such as titanium layer or molybdenum layer layer to be used as barrier between the wiring material such as substrate and layers of copper Film, improves the adaptation of wiring material and glass substrate, prevents the diffusion to silicon semiconductor film.In addition, also existing in order to anti- Only the oxidation of layers of copper etc. and covering (Japanese is formed with the upper strata of layers of copper:キャップ) film 3 layers of stacked film.

As copper and titanium stacked film etching solution, proposition has for example comprising hydrogen peroxide, nitric acid, fluorine ion supply source, azoles Class, ammonium hydroxide, the etching solution (patent document 1) of pH1.5~2.5 of stabilizer of hydrogen peroxide and water, comprising ammonium persulfate, Organic acid, ammonium salt, fluorochemical, the glycol compound of powder, the etching solution (patent document 3) of azole compounds and water, Etching solution (patent document 3) comprising ammonium persulfate, azole compounds and water, includes fluorine ion supply source, hydrogen peroxide, sulfuric acid Salt, phosphate, the etching solution (patent document 4) of azole compounds and water.

In addition, as copper and molybdenum stacked film etching solution, proposition has for example comprising selected from neutral salt, inorganic acid and organic acid At least one of and hydrogen peroxide, the etching solution (patent document 5) of stabilizer of hydrogen peroxide, comprising hydrogen peroxide, no The etching solution (patent document 6) of inorganic acid, amines, azole, stabilizer of hydrogen peroxide containing fluorine atom, in aqueous medium In the etching composition (patent document 7) of compound, hydrogen peroxide and pH more than 8.5 containing ammonia, with amino etc..

Prior art literature

Patent document

Patent document 1:Japanese Patent No. 5685204

Patent document 2:Japanese Patent Laid-Open 2013-522901

Patent document 3:Japanese Patent Laid-Open 2008-227508

Patent document 4:Japanese Patent Laid-Open 2008-288575

Patent document 5:Japanese Patent No. 4282927

Patent document 6:International Publication No. 2011/099624

Patent document 7:Japanese Patent Laid-Open 2010-232486

The summary of invention

The technical problems to be solved by the invention

For the etching solution described in above-mentioned patent document 1,4~7, inner evenness is not enough, has at corrosion-resisting pattern end Portion produces a large amount of concavo-convex situations, if the corrosion further develops, may produce imaging mouse gnaw cheese vestige that The rat eaten (mouse bite) of the shape of sample and cause decrease in yield, or cause the fluctuating of section shape concave-convex surface.Separately Outside, for the etching composition described in citation 7, there is also bath life is short, storage stability in terms of usability Low problem.In addition, for the etching solution described in patent document 2 and 3, using persulfate, but if using persulfuric acid Salt, then compared with hydrogen peroxide, corrosion-resisting pattern end is more readily formed concavo-convex.It is whard to control, easy additionally, there are coning angle The problems such as step-down.

Therefore, the invention reside in for etching metal monofilm or metal stacking film for being used for of solving the above problems Etch combination is easily controlled side etching, coning angle, section shape, pattern form there is provided good etch-rate is realized, And there is the etch combination of longer bath life while retention property stability.

Solve the technical scheme that technical problem is used

The present inventor is conceived to the stabilization as peroxide during conscientiously being inquired into solve above-mentioned problem Organic acid and the chelating agent such as the phenylurea and phenolsulfonic acid of agent, the malonic acid of meltage for increasing copper, for obtaining pH's Neutral salt of cushioning effect etc. is the main cause this point for the decline for causing inner evenness, after constantly studying, and is found logical Crossing the etch combination for mixing water-miscible organic solvent in the etch combination containing peroxide and preparing can improve to metal The wellability of substrate, smoothly etches metal surface, suppresses local corrosion, after further being studied, as a result completes this hair It is bright.

That is, the present invention relates to herein below.

[1] a kind of etch combination, it is for etching by the metal selected from copper, titanium, molybdenum and nickel or their nitride The monofilm of formation, by the monofilm formed containing the one kind or two or more alloy selected from copper, titanium, molybdenum and nickel, or containing 1 layer Or the etch combination of the stacked film of more than 2 layers of the monofilm is comprising azoles, nitric acid, peroxide and water solubility have Machine solvent.

[2] etch combination as described above described in [1], wherein, vapour pressure at 25 DEG C of water-miscible organic solvent is Below 2kPa.

[3] etch combination as described above described in [1] or [2], wherein, water-miscible organic solvent is selected from alcohol, glycol, binary Alcohol, trihydroxylic alcohol, ketone, carbonic ester, sulfoxide.

[4] etch combination as described above described in any one of [1]~[3], wherein, water-miscible organic solvent is selected from second Glycol, diethylene glycol and DPG.

[5] etch combination as described above described in any one of [1]~[4], wherein, peroxide is selected from peroxidating Hydrogen, peroxosulphuric ammonium, peroxosulphuric sodium and potassium peroxide.

[6] etch combination as described in any one of [1]~[5], wherein, also comprising phosphoric acid or phosphate.

[7] etch combination as described above described in any one of [1]~[6], wherein, also comprising selected from ammonium hydroxide and The compound of ammoniacal liquor.

[8] etch combination as described in any one of [1]~[7], wherein, also comprising fluorine or fluorine compounds.

[9] etch combination as described in [8], wherein, fluorine compounds are selected from ammonium fluoride, acid ammonium fluoride and hydrofluoric acid.

[10] etch combination as described above described in any one of [1]~[9], wherein, also comprising carbamide compound.

[11] etch combination as described above described in [10], wherein, carbamide compound is selected from phenylurea, allylurea, 1,3- Dimethyl urea and thiocarbamide.

[12] etch combination as described above described in any one of [1]~[11], wherein, also comprising organic acid.

[13] etch combination as described above described in [12], wherein, organic acid is malonic acid or citric acid.

[14] as described above described in any one of [1]~[13] etch combination is comprising 1~15 mass % Peroxide, 1~10 mass % nitric acid, 0.005~0.2 mass % azole, 0.05~1.00 mass % fluorine compounds, 1~50 mass % water-miscible organic solvent.

[15] etch combination as described above described in any one of [1]~[14], it is the erosion for etching stacked film Composition is carved, wherein, stacked film is constituted for the layer of titanium/copper/titanium.

[16] etch combination as described above described in any one of [1]~[14], it is the erosion for etching stacked film Composition is carved, wherein, stacked film is that the layer of the alloy/copper/titanium formed by copper and mickel is constituted, and the titanium is located at substrate-side.

[17] etch combination as described above described in any one of [1]~[14], it is the erosion for etching stacked film Composition is carved, wherein, stacked film is constituted for the layer of the individual layer of individual layer/molybdenum of copper respectively, and the individual layer of the molybdenum is located at substrate-side.

[18] etch combination as described above described in any one of [1]~[17], wherein, pH is less than 7.0.

[19] a kind of engraving method, it is that etching is formed by the metal selected from copper, titanium, molybdenum and nickel or their nitride Monofilm, by the monofilm formed containing the one kind or two or more alloy selected from copper, titanium, molybdenum and nickel, or containing 1 layer or 2 layers The method of the stacked film of the monofilm above, wherein, including the use of the etching described in any one of above-mentioned [1]~[18] The process that composition is etched.

[20] method as described above described in [19], wherein, it is used for liquid crystal display, color film, contact panel, organic EL and shows Show device, Electronic Paper, MEMS or IC manufacturing process or packaging process.

The effect of invention

The etch combination of the present invention is because of the organic solvent contained by the etch combination, and the wellability to metal is improved, Monofilm or stacked film can disposably be etched.In addition, not only improve etch-rate, side etching, the control of coning angle System is easy, and inner evenness is high, and the etching of the smoothing of resist end and section shape can be achieved, and can etch complicated and essence The substrate of cause.In addition, the etch combination has good stability, it can use for a long time.In addition, by being combined to the etching The bulking liquor of the composition of etch combination of the supplement comprising one kind or two or more the present application in thing, can maintain above-mentioned performance In the case of extend bath life.Therefore, the security in the reduction and substrate manufacture of manufacturing cost is additionally aided.

Particularly the stacked film or cupric and the stacked film of molybdenum of cupric and titanium, can also easily suppress conventional incident titanium With the undercutting (under cut) of molybdenum.In addition, in the case of also there is upper strata in thickness 100nm or so titanium layer or molybdenum layer, it may have The effect for preventing the near interface on upper strata from extremely being etched.For monofilm, it may have prevent the flatness of corrosion-resisting pattern end The effect being deteriorated with section shape., also can be even if adding peroxide stabiliser, organic acid or chelating agent in addition, also having Suppress the decline of inner evenness in the case of not adding stabilizer or pH buffer further and corrosion-resisting pattern end produces mouse The effect nibbled.

The simple declaration of accompanying drawing

Fig. 1 is the ideograph of the section of the Cu/Ti substrates of etched processing.

Fig. 2 is the ideograph of the section for the Cu/Mo substrates that there occurs Mo undercutting.

Fig. 3 is the ideograph of the section for the CuNi/Cu/Ti substrates that copper alloy becomes eaves shape.

Fig. 4 is the ideograph of the section of the Ti substrates of etched processing.

Fig. 5 is the Ti ideograph of the sections of Ti substrates that is extremely etched of upper layer part.

Fig. 6 is SEM photograph of the section in the section of the Cu/Ti substrates of positive round taper.

Fig. 7 is the SEM photograph of the section for the Cu/Mo substrates that section there occurs Mo undercutting.

Fig. 8 is the SEM photograph of the section for the CuNi/Cu/Ti substrates that section upper layer part becomes eaves shape.

Fig. 9 is SEM photograph of the section in the section of the Ti substrates of positive round taper.

Figure 10 is the SEM photograph of Ti substrates.

The section shape of corrosion-resisting pattern end when Figure 11 is the CuNi/Cu/Ti substrates of the etched processing from oblique upper The ideograph of shape.

Section shape when Figure 12 is the CuNi/Cu/Ti substrates of corrosion-resisting pattern end concave-convex surface inequality from oblique upper The ideograph of shape.

The section shape of corrosion-resisting pattern end when Figure 13 is the CuNi/Cu/Ti substrates of the etched processing from oblique upper The SEM photograph of shape.

Section shape when Figure 14 is the CuNi/Cu/Ti substrates of corrosion-resisting pattern end concave-convex surface inequality from oblique upper The SEM photograph of shape.

The mode carried out an invention

Hereinafter, embodiments of the present invention are described in detail.

In this specification, make and being marked such as Cu/Ti, CuNi/Cu/Ti sometimes, Cu/Ti represents it is 2 layers of copper and titanium Film, CuNi/Cu/Ti represents 3 tunics of the alloy, copper, titanium of copper and mickel.In addition, for the order of layer, Cu/Ti represents the upper of titanium Copper is laminated with layer by layer, and CuNi/Cu/Ti represents that the upper strata of titanium is laminated with the alloy that nickel is laminated with above copper and copper.Therefore, in expression In the stacked film stated closest to real estate layer be titanium layer.

The etch combination of the present invention is the painting erosion resistant agent on the monofilm and/or stacked film on substrate, exposure Desired pattern mask is transferred, develops and is formed after corrosion-resisting pattern, etching monofilm and/or stacked film, finally on substrate Form the composition of wiring or electrode pattern.On this point, required performance in etching, as shown in figure 1, thin copper film end Etching face and lower floor substrate angulation (coning angle) be preferably in normal cone shape be less than 90 °, more preferably 20~ 60°.Particularly not in the case of the barrier metal layer of cupric, the monofilm such as Ti or Mo, thickness is small, even therefore 70 ° or 80 ° of high angle, the problem of actual substrate will not also produce particularly evident, so as normal cone shape, covering excellent In the range of choosing.

In addition, the distance (side etching) of Obstruct membrane of the resist layer end extremely under wiring is preferably the thickness of stacked film About 3 times within.Within more preferably from about 1.5 times.If for example, Cu/Ti thickness isPreferably 2.0 Within μm, within more preferably 0.9 μm.In addition, as shown in Fig. 2 the state that the barrier metal layer below layers of copper is etched claims Undercut for so-called barrier metal, undercut portions become cavity under said state, become off state, therefore can not be used as base Plate is used.Therefore, it is not preferred as etching.

In addition, as shown in figure 3, in layers of copper formed cover layer 3 layers of stacked film be etched when, the gold of cover layer In the case of category is more insoluble than copper, eaves shape may be formed.The state of eaves shape also turns into inverted cone, forms disconnected as described above Line state, therefore can not be used as substrate, so not preferred as etching.Preferred etching state such as Fig. 4 institutes of individual layer The sectional view of the Ti substrates shown.That is, coning angle is 20~60 ° of normal cone shape, and side etching is less than 0.9 μm.Will erosion State when liquid enters resist and Ti interface is carved to be represented with the ideograph of the section of Ti substrates as shown in Figure 5.Become Ti The state that is extremely etched of upper layer part, it is clear that be not preferred state.In addition, Figure 10 is by comprising hydrogen peroxide, ammoniacal liquor The SEM photograph of the Ti substrates handled with phosphatic general etch combination.The upper layer part for becoming Ti is extremely lost The state at quarter, is not preferred state.

In addition, Figure 11 and Figure 12 represent the shape of corrosion-resisting pattern end when from oblique upper.Figure 11 is represented after etching The high state of the flatness of end, Figure 12 represents the low state of flatness.The higher the better for the flatness of etching rearward end.That is, lose It is preferably to meet above-mentioned terms and conditions to carve composition.

The present invention etch combination as etch target be the metal formed on glass or silicon substrate monofilm Or stacked film.Furthermore it is possible to be the stacked film for including 1 layer or more than 2 layers of the above-mentioned monofilm formed by metal or alloy.

In a kind of form of the present invention, monofilm or stacked film include the nitride of the metal selected from copper, titanium, molybdenum and nickel. Preferably TiN or MoN monofilm or the stacked film comprising them.

Titanium alloy or molybdenum alloy used in monofilm or stacked film is using titanium or molybdenum as main component, but it is of course possible to contain aluminium Or other metals such as magnesium, calcium.In addition, titanium relative to weight alloy respectively containing more than 80 weight % of titanium alloy or molybdenum alloy or Molybdenum, preferably containing more than 90 weight %, more preferably containing more than 95 weight %.

Stacked film can be 2, the stacking of any of 3,4,5 layers numbers of plies, preferably 2,3 layers.2 layers of stacked film can example Cu/Ti, Cu/MoTi, Cu/TiN, Cu/Mo, Cu/MoN etc. are lifted, it is not limited to these.Can be by Ti or Mo or they Alloy-layer be film-made as barrier metal and be further formed on stacked film etc. obtained by the film of Cu or Cu alloys.

In addition, 3 layers of stacked film can enumerate Ti/Cu/Ti, Mo/Cu/Mo, Ti/Cu/TiN, Mo/Cu/MoN, CuNi/Cu/ Ti, CuNi/Cu/TiN, CuMgAl/Cu/CuMgAl, CuMgAlO/Cu/CuMgAl etc., it is not limited to these.By IGZO etc. Oxide semiconductor be used for channel layer in the case of, Cu electrodes be exposed to oxygen atmosphere under, therefore mostly using Ti, Mo or they Alloy etc. is used as diaphragm.But, if the upper layer part in copper forms these films, it is difficult to handled with a kind of solution or uniformly Section shape, so the copper alloy such as CuNi or CuMgAl is used as cover layer.

Plural layers particularly comprising layers of copper and molybdenum layer are largely used to the wiring of the display devices such as flat-panel monitor etc., The etch combination of the present invention is suitable for the multilayer film.In addition, being used mostly with monofilm for the film for forming electrode or wiring The alloy of titanium or molybdenum, nickel etc. is as barrier alloy, in order to suppress the diffusion to silicon etc., is also formed mostly on above-mentioned barrier metal Copper or copper alloy.The etch combination of the present invention is not only suitable for the monofilm of barrier metal, is also adapted on barrier metal Copper or tin-copper alloy film selective etch when.

In addition, flat-panel monitor by LCD Controlling light is TFT (thin film transistor (TFT)s:Thin Film Transistor).TFT has grid and source electrode, drain electrode, and grid is located at TFT orlop, and source electrode, drain electrode are located at upper strata.From electric From the point of view of in terms of characteristic, grid such as Cu/Ti or Cu/Mo stacked film are set to mostly it is relatively thick, and for source electrode, leakage Pole, is set to relatively thin sometimes.For example, the copper of grid isSource electrode, the copper of drain electrode areDeng, it is not limited to This.Therefore, the etch combination of the present application is preferably prepared in the way of it can tackle any thickness.

The thickness of stacked film is preferablyMore preferablyFilm for the copper of stacked film Thickness is preferablyMore preferablyThickness for the Ti or Mo of stacked film alloy is preferablyMore preferably

The etch combination of the present invention includes water-miscible organic solvent.Water-miscible organic solvent is conducive to etch-rate, side Control, the smoothing of corrosion-resisting pattern end, the control of section shape of facet etch, coning angle etc..Preferably with the erosion of the present invention Carve the liquid that water-miscible organic solvent used in composition, aqueous phase are held, vapour pressure at preferably 25 DEG C for below 2kPa with The water-miscible organic solvent that aqueous phase is held.Do not include the water-miscible organic solvent under normal temperature in solid state.Wherein more preferably alcohols, Glycols, ternary alcohols, ketone, amide-type, nitrogenous five-membered ring class, carbonates, sulfoxide type etc..These certain water solubilitys are organic Solvent can be used one kind or two or more in the etch combination of the present invention.

In addition, alcohols solvent used in the etch combination of the present invention is preferably methanol, ethanol, propyl alcohol, 2- propyl alcohol, 1- The monohydric alcohols such as butanol, the dihydric alcohol such as ethylene glycol, propane diols, butanediol etc..Wherein, preferably propyl alcohol, 2- propyl alcohol, n-butyl alcohol, more It is propyl alcohol, 2- propyl alcohol well.

Glycol used is preferably diethylene glycol, DPG, 1,3- propane diols, 1,3- in the etch combination of the present invention Butanediol, 2,3- butanediols, 1,4- butanediols, 1,5- pentanediols etc..Wherein, more preferably diethylene glycol, DPG, 1,3- third Glycol, 1,3-BDO, 2,3-butanediol, BDO, particularly preferably diethylene glycol, DPG, 1,3-BDO.

Trihydroxylic alcohol used is preferably glycerine etc. in the etch combination of the present invention.

In the etch combination of the present invention ketone used be preferably acetone, methyl ethyl ketone, diethyl ketone, methyl propyl ketone, Ethyl propyl ketone, two acetone etc..Wherein, more preferably acetone.

Acid amides used is preferably N,N-dimethylformamide, DMAC N,N' dimethyl acetamide in the etch combination of the present invention Deng.Wherein, more preferably DMF.

Nitrogenous five-membered ring used is preferably METHYLPYRROLIDONE, 2- pyrrolidines in the etch combination of the present invention Ketone, 1,3- dimethyl-2-imidazolinones etc..Wherein, more preferably DMI, N- methyl -2- pyrrolidines Ketone.

Carbonic ester used is preferably ethylene carbonate, propylene carbonate, carbonic acid two in the etch combination of the present invention Methyl esters, diethyl carbonate, methyl ethyl carbonate etc..Wherein, more preferably ethylene carbonate.

Sulfoxide used can enumerate dimethyl sulfoxide etc., preferably dimethyl sulfoxide in the etch combination of the present invention.

Ensure the control, the smoothing of corrosion-resisting pattern end, section of etch-rate, side etching, coning angle etc. from appropriateness From the perspective of the control of shape, the content of the water-miscible organic solvent in etch combination of the invention is preferably 1~50 matter Measure %, more preferably 5~30 mass %.

The etch combination of the present invention includes one kind or two or more peroxide.Peroxide, which has, is used as oxidant oxygen Change the function of thin copper film.There is the function of oxidation dissolution especially for molybdenum.Peroxide is preferably hydrogen peroxide, the burnt sulphur of peroxide Sour ammonium, peroxosulphuric ammonium, peroxosulphuric sodium, potassium peroxide, more preferably hydrogen peroxide, peroxide ammonium pyrosulfate.From hydrogen peroxide Management easily, also can ensure that appropriate etching speed from the perspective of, peroxide in etch combination of the invention Content is preferably easy 1~15 mass % of control of etch quantity, more preferably 3~6 mass %.

The etch combination of the present invention includes nitric acid.The dissolving of the copper that nitric acid has contributed to by peroxide oxidation etc.. From the perspective of obtaining appropriate etching speed, obtaining the wiring shape after good etching, etch combination of the invention In the content of nitric acid be preferably 1~10 mass %, more preferably 2~7 mass %.

The etch combination of the present invention includes one kind or two or more azoles.Azoles contributes to side etching, coning angle, section shape The control of shape.In the etch combination of the present invention azoles used be preferably 1,2,4-1H- triazoles, 1H- BTAs, 5- methyl- 1H- BTAs, 3- amino -1H- triazoles and 3- amino -1H-1, the triazole, 1H-TETRAZOLE, 5- methyl isophthalic acids H- tetra- such as 2,4- triazoles The tetrazoliums such as azoles, 5- phenyl -1H-TETRAZOLE and 5- amino -1H-TETRAZOLE, the imidazoles such as 1H- imidazoles and 1H- benzimidazoles, 1,3-thiazoles and Thiazoles such as 4- methylthiazols etc..Wherein, more preferably triazole and tetrazolium, particularly preferably 1,2,4-1H- triazoles, 3- amino -1H-1,2, 4- triazoles and 5- amino -1H-TETRAZOLE (ATZ).

From can suppress etching after side etching increase while etched after good wiring section shape From the perspective of, the content of the azoles in etch combination of the invention is preferably 0.005~0.2 mass %, more preferably 0.01~ 0.05 mass %.

The etch combination of the present invention can also include one kind or two or more phosphoric acid (phosphate) or phosphate cpd.By phosphorus The phosphate anion that sour (phosphate) or phosphate cpd are brought contributes to the etch-rate of copper, titanium, molybdenum, nickel or their alloy Control and coning angle control.From the perspective of the control of etch-rate and coning angle becomes easily, etching of the invention The content further comprising phosphoric acid (phosphate) or phosphate cpd in composition is preferably 0.1~30.0 mass %, more preferably It is 1.0~4.0 mass %.

For phosphate anion, as long as producing phosphate anion by etch combination, it is not particularly limited, preferably Phosphoric acid (phosphate), ammonium dihydrogen phosphate, diammonium hydrogen phosphate, sodium dihydrogen phosphate, disodium hydrogen phosphate, the hydrogen magnesium of phosphoric acid one, biphosphate Magnesium, potassium dihydrogen phosphate, dipotassium hydrogen phosphate, calcium monohydrogenphosphate, calcium dihydrogen phosphate etc..These may be used alone or in combination certainly makes With.Wherein, from from the perspective of being easily processed in liquid, more preferably phosphoric acid (phosphate).

The etch combination of the present invention can also include one kind or two or more alkali compounds.Alkali compounds contributes to pH Control, the wellability to fine portion are improved, inner evenness is improved.Alkali compounds is preferably ammonium hydroxide, ammoniacal liquor and hydrogen-oxygen Compound, more preferably tetramethyl-ammonium hydroxide, tetraethyl ammonium hydroxide, trimethyl (2- hydroxyethyls) ammonium hydroxide, hydrogen The alkali hydroxide metal class such as lithia, sodium hydroxide and potassium hydroxide, the hydroxide such as calcium hydroxide, strontium hydroxide and barium hydroxide Alkaline-earth metal class, the carbonate of the alkali metal such as ammonium carbonate, lithium carbonate, sodium carbonate and potassium carbonate, TMAH and courage The ammonium hydroxide class such as alkali, organic amine and the ammonia such as ethamine, diethylamine and ethylol amine.Wherein, particularly preferably tetramethyl hydroxide Ammonium (TMAH).

From the perspective of good wiring section shape after it can be etched, the alkali in etch combination of the invention The content of property compound is preferably 1~20 mass %, more preferably 1~7 mass %.

The etch combination of the present invention can also include one kind or two or more fluorine or fluorine compounds.By fluorine or fluorine compounds band The fluorine ion come especially contributes to the etching of the Obstruct membrane formed by titanium metalloid.For fluorine ion, as long as by etching group Compound produces fluorine ion, is not particularly limited, preferably hydrofluoric acid, ammonium fluoride, acid ammonium fluoride etc..Above-mentioned substance certainly may be used It is used singly or in combination.Wherein, from the perspective of the toxicity to animal is low, more preferably ammonium fluoride, acid ammonium fluoride and Hydrofluoric acid.

The content of fluorine or fluorine compounds in the etch combination of the present invention is preferably 0.05~1.00 mass %, more preferably 0.1~0.5 mass %.If the content of fluorine ion is within the above range, it can not increase in the corrosion rate of glass substrate In the case of, obtain the etching speed of the good Obstruct membrane formed by titanium metalloid.It is disposable to the layer of titaniferous for this point When being etched, etch combination of the invention preferably also includes one kind or two or more fluorine or fluorine compounds, the layer of titaniferous Do not etch titanium in folded film and only other layer of selective etch when, etch combination of the invention is preferably without one kind or two or more Fluorine or fluorine compounds.

The etch combination of the present invention can also include one kind or two or more ureas stabilizer of hydrogen peroxide.Ureas peroxidating Stabilized hydrogen agent contributes to the decomposition of peroxide to suppress.Ureas stabilizer of hydrogen peroxide is preferably phenylurea, allylurea, 1,3- Dimethyl urea, thiocarbamide etc., wherein more preferably phenylurea.Ureas stabilizer of hydrogen peroxide in the etch combination of the present invention contains Amount is preferably 0.1~2.0 mass %, from the perspective of the decomposition inhibition that can moderately obtain hydrogen peroxide, and more preferably 0.1 ~0.3 mass %.

The etch combination of the present invention can also include one kind or two or more organic acid.Organic acid has in etch combination Play the role of as the buffer adjusted for pH.Organic acid be preferably ammonium salt, citric acid, sodium citrate, Sodium citrate, Disodium citrate and potassium citrate, acetic acid and its salt (for example, ammonium acetate, calcium acetate, potassium acetate and sodium acetate), tartaric acid and its Salt (for example, sodium tartrate, sodium hydrogen tartrate and potassium sodium tartrate), three (methylol) aminomethanes (Tris) and its salt (for example, Three (methylol) aminomethane hydrochlorides), malonic acid, Triammonium citrate, ammonium dihydrogen citrate, ammonium lactate, diammonium hydrogen phosphate, phosphorus Acid dihydride ammonium etc..Wherein, more preferably citric acid, malonic acid, diammonium hydrogen phosphate, ammonium dihydrogen phosphate.

In addition to the above-mentioned components, etch combination of the invention can not also destroy the journey of the effect of etch combination Degree comprising water, other be generally used for the one kind or two or more various additives of etch combination.For water, preferably by steaming Evaporate, the processing of ion-exchange treatment, filter, various adsorption treatments etc. eliminate the water of metal ion and organic impurities, particle etc., special Not good is pure water, ultra-pure water.

In the preferred configuration of the etch combination of the present invention, etch combination of the invention includes peroxide, fluorine or fluorine Compound, nitric acid, azoles, water-miscible organic solvent and water, more preferably comprising peroxide, fluorine or fluorine compounds, nitric acid, azoles, alkali Property compound, water-miscible organic solvent and water, further more preferably include peroxide, fluorine or fluorine compounds, nitric acid, azoles, alkali Property compound, phosphoric acid, water-miscible organic solvent and water.

The present invention etch combination a side, preferably comprising peroxide, fluorine or fluorine compounds, nitric acid, Azoles, alkali compounds, ureas stabilizer of hydrogen peroxide, the etch combination of water-miscible organic solvent and water, comprising peroxide, Nitric acid, azoles, alkali compounds, phosphoric acid, ureas stabilizer of hydrogen peroxide, the etch combination of water-miscible organic solvent and water, or Person includes peroxide, fluorine or fluorine compounds, nitric acid, azoles, alkali compounds, phosphoric acid, ureas stabilizer of hydrogen peroxide, water solubility The etch combination of organic solvent and water.The etch combination of the present invention can be according to its composition of the membrane change as object.

If the etch combination pH of the present invention is more than 7, peroxide is easily decomposed, so preferably pH is less than 7.This Outside, in the case of being etched to the layer of titaniferous, from the perspective of titanium easily dissolves, pH is preferably less than 4.

Secondly, the monofilm that etching of the invention is formed by copper, titanium, molybdenum or nickel, the alloy containing copper, titanium, molybdenum or nickel The process being etched in the method for monofilm or stacked film containing the monofilm including the use of above-mentioned etch combination.Also The process contacted including the etch combination for making the present invention with etch target thing.Etch target thing is as described above.

In addition, the method for making etch combination be contacted with etch target thing generally can be using for example by being added dropwise, (monolithic revolves Turn processing) or the form such as spraying make the method or object is impregnated in etch combination that etch combination contacts with object The wet etch process such as method, the side that (monolithic rotation processing) contacts it in object preferably is added dropwise in etch combination Method, object is impregnated in the method that etch combination contacts it.

For the temperature in use of etch combination, if the temperature of etchant is more than 20 DEG C, etching speed Will not be too low, production efficiency will not be remarkably decreased；On the other hand, if less than the temperature of boiling point, then can composite inhibiting become Change, etching condition is kept certain.From the viewpoint of described, the temperature of etching process is preferably 15~60 DEG C, particularly preferably 30~50 DEG C.By improving the temperature of etch combination, etching speed rises；On the other hand, it can consider to suppress erosion further The composition for carving liquid composition changes after smaller grade, it is determined that appropriate treatment temperature.

In addition, it may include liquid crystal display, color film, contact panel, organic el display, Electronic Paper, MEMS or IC system Make process or packaging process.

If be etched, by the dissolving metal of the generations such as etching in etch combination.It is somebody's turn to do if continuing to use Etch combination, the then because decomposition of the amount of metal and peroxide of its dissolving, JET and S/E, T/A change.If these Performance change, then section shape also changes, therefore can not continue to manufacture the product of homotype.Then, generally for cost cutting etc., To use bulking liquor for the purpose of long-time use by increasing the meltage of the metals such as copper, bulking liquor is in order to feed because of the metal The increase of meltage and the organic acid that consumes are used added to etch combination.For this point, in the present invention, this can be sent out 1 in peroxide, nitric acid, fluorine and/or fluorine compounds, TMAH or water-miscible organic solvent used in bright etch combination Plant or two or more is as bulking liquor, added in the etch combination having been used of the present invention.Thus, with common to erosion Carve only to add organic acid or peroxide in composition or add both simultaneously and compared as the situation of bulking liquor, can be significantly Extend the life-span of solution.

Hereinafter, enumerating embodiment and comparative example, the present invention will be described in more detail, but the present invention is not by these Any restriction of embodiment etc..

1. the making of metal substrate

The making of Ti substrates

Using glass as substrate, sputtered titanium (Ti) forms the Obstruct membrane formed by titanium.Then, painting erosion resistant agent, by pattern After mask exposure transfer, the titanium single thin film for foring pattern is made in development.In addition, Ti thickness isFollowing reality Apply the Ti substrates used in example, comparative example and refer to the substrate.

The making of Cu/Ti substrates

Using glass as substrate, sputtered titanium (Ti) forms the Obstruct membrane formed by titanium.Then, sputter copper and form copper cloth Line.Then, painting erosion resistant agent, after pattern mask exposure transfer, the copper/titanium plural layers for foring pattern are made in development.This Outside, Cu/Ti thickness isThe Cu/Ti substrates used in following embodiment, comparative example refer to the substrate.

The making of CuNi/Cu/Ti substrates

Using glass as substrate, sputtered titanium (Ti) forms the Obstruct membrane formed by titanium.Then, sputter copper and form thin copper film, The cupro-nickel (CuNi) of copper alloy is sputtered again and forms the diaphragm of copper.Then, painting erosion resistant agent, after pattern mask exposure transfer, shows Shadow, is made the copper alloy/copper/titanium plural layers for foring pattern.In addition, CuNi/Cu/Ti thickness is The CuNi/Cu/Ti substrates used in following embodiment, comparative example refer to the substrate.

The making of Cu/Mo substrates

Using glass as substrate, sputtering molybdenum (Mo) forms the Obstruct membrane formed by molybdenum.Then, sputter copper and form copper cloth Line.Then, painting erosion resistant agent, after pattern mask exposure transfer, the copper/molybdenum plural layers for foring pattern are made in development.This Outside, Cu/Mo thickness isThe Cu/Mo substrates used in following embodiment, comparative example refer to the substrate.

2. etching test

2-1. uses the etching test that water-miscible organic solvent is added

By the mixing of (A) hydrogen peroxide, (B) acid ammonium fluoride, (C) nitric acid, (D) 5- amino -1H-TETRAZOLE (ATZ) and water The etch combination (table 1) obtained is added to beaker, makes temperature stabilization in 35 DEG C of thermostat is held in.Stirred by agitator While etchant, 1 × 1cm Cu/Ti substrates are impregnated, etching period is determined.By at the time point of copper and molybdenum disappearance The etching period of measure as the just etching time, using about 1.5 times of the just etching time as actual etching period (i.e., 50% excessive etching period, is denoted by 50%O.E.).Relative to the weight % of etch combination 100 described in table 1, it is made It with the addition of respectively in the etch combination described in the etch combination and table 1 of 10,20,30 weight % DPG (DPG) DPG etch combination is not added.

[table 1]

ATZ:5- amino -1H-TETRAZOLE

Then, above-mentioned etch combination is separately added into beaker, while stirring by agitator, impregnates each Cu/ Ti substrates, have carried out etching test.Using for each substrate of experiment as embodiment 1~3.Embodiment 1~3 is directed to table 10,20,30 weight %DPG are separately added into 1 etch combination and for the Cu/Ti substrates of etching test.During for etching Between, 1.5 times of the just etching time described in table 2 are etched as excessive etching period.Then, to for experiment Each Cu/Ti substrates carry out, using after washing, the processing of drying, section shape being confirmed by SEM, to the side etching of each substrate Each performances such as amount, coning angle, Ti residues, the flatness of corrosion-resisting pattern end, section shape are evaluated.Its result, which collects, to be shown In table 2.

[table 2]

Cu/Ti substrates50%O.E.

DPG:DPG

Each equal Ti residues of embodiment are good, in terms of the flatness of corrosion-resisting pattern end, the non-concave-convex surface in end, and section shape Shape is good.In addition, the SEM photograph of embodiment 1 is shown in Fig. 6.

Then, substrate is changed to Ti substrates, experiment is etched using etch combination similar to the above, carried out each The evaluation of substrate.Its result, which collects, is shown in table 3.Comparative example 1 refers to add DPG not into the etch combination of table 1 and for erosion The Ti substrates of experiment are carved, embodiment 4~6 is directed to be separately added into 10,20,30 weight %DPG in the etch combination of table 1 and supplied In the Ti substrates of etching test.As a result, in the substrate of comparative example 1, Ti section shape is in eaves shape as shown in Figure 3, Fail to determine T/A.But, the substrate of embodiment 4~6 is shown, by adding DPG and section shape is good, and end is smooth Property improve, also JET can be controlled by DPG addition concentration.In addition, the SEM photograph of embodiment 4 is shown in Fig. 9.

[table 3]

Ti substrates50%O.E.

DPG:DPG

For Ti residues, A represents good, and B represents bad.For the flatness of corrosion-resisting pattern end, A represents good, B tables Show bad.Bad is finger ends concave-convex surface.For section shape, A represents good, and B is represented bad (similarly hereinafter).

2-2. uses the etching test that water-miscible organic solvent is added

With to by (A) hydrogen peroxide, (B) acid ammonium fluoride, (C) nitric acid, (D) 5- amino -1H-TETRAZOLE (ATZ), (E) four DPG composition is added in the etch combination (table 4) that ammonium hydroxide (TMAH) and water are obtained by mixing and does not add DPG group Compound has carried out etching test.Respectively using Cu/Ti substrates, Ti substrates and Cu/Mo substrates with experimental condition similar to the above Etching test is carried out.

[table 4]

TMAH:TMAH

Obtained result is etched to Cu/Ti substrates collected and be shown in table 5.Comparative example 2 refers to etching not to table 4 DPG is added in composition and for the Cu/Ti substrates of etching test, embodiment 7~9 is directed to divide in the etch combination of table 4 Jia Ru not 10,20,30 weight %DPG and for the Cu/Ti substrates of etching test.As a result show in stacked film, also can be by adding Plus DPG control JET, T/A, the flatness of corrosion-resisting pattern end can be improved.

[table 5]

Cu/Ti substrates50%O.E.

DPG:DPG

Obtained result is etched to Ti substrates collected and be shown in table 6.Comparative example 3 refers to etching group not to table 4 DPG is added in compound and for the Ti substrates of etching test, embodiment 10~12 is directed in the etch combination of table 4 add respectively Enter 10,20,30 weight %DPG and for the Ti substrates of etching test.As a result display can control JET, Neng Gougai by adding DPG The flatness and section shape of kind corrosion-resisting pattern end.

[table 6]

Ti substrates50%O.E.

DPG:DPG

Obtained result is etched to Cu/Mo substrates collected and be shown in table 7.Comparative example 4 refers to etching not to table 4 DPG is added in composition and for the Cu/Mo substrates of etching test, embodiment 13 and 14 is directed in the etch combination of table 4 It is separately added into 10,20 weight %DPG and for the Cu/Mo substrates of etching test.As a result show as described above, in monofilm JET, T/A can be controlled by adding DPG.The flatness of the end of each embodiment, section shape are good.

[table 7]

Cu/Mo substrates50%O.E.

DPG:DPG

2-3. uses the etching test that water-miscible organic solvent is added

With to by (A) hydrogen peroxide, (B) acid ammonium fluoride, (C) nitric acid, (D) 5- amino -1H-TETRAZOLE (ATZ), (E) four DPG composition and not is added in etch combination (table 8) that ammonium hydroxide (TMAH), (F) phosphoric acid and water are obtained by mixing Plus DPG composition has carried out etching test.Etching test has been carried out using CuNi/Cu/Ti substrates.Except O.E. is set to 50% Or beyond 100%, etching test has been carried out with experimental condition similar to the above.

[table 8]

The result of the CuNi/Cu/Ti substrates handled with 50%O.E., which collects, is shown in table 9.Comparative example 5 refers to not to table 8 Etch combination in add DPG and for the CuNi/Cu/Ti substrates of etching test, embodiment 15~17 is directed to the erosion of table 8 Carve in composition and be separately added into 10,20,30 weight %DPG and for the CuNi/Cu/Ti substrates of etching test.As a result display can JET is controlled by adding DPG.In addition, each equal Ti residues of embodiment are good, in terms of the flatness of corrosion-resisting pattern end, end is not Concave-convex surface, and section shape is good.

[table 9]

CuNi/Cu/Ti substrates50%O.E.

DPG:DPG

The result of the CuNi/Cu/Ti substrates handled with 100%O.E., which collects, is shown in table 10.Comparative example 6 refers to not to table DPG is added in 8 etch combination and for the CuNi/Cu/Ti substrates of etching test, embodiment 18~20 is directed to table 8 10,20,30 weight %DPG are separately added into etch combination and for the CuNi/Cu/Ti substrates of etching test.As a result show JET can be controlled by adding DPG, can also improve the flatness of corrosion-resisting pattern end.

[table 10]

CuNi/Cu/Ti substrates100%O.E.

DPG:DPG

2-4. uses the etching test that water-miscible organic solvent is added

With to by (A) hydrogen peroxide, (B) acid ammonium fluoride, (C) nitric acid, (D) 5- amino -1H-TETRAZOLE (ATZ), (E) four Add DPG's in the etch combination (table 11) that ammonium hydroxide (TMAH), (F) phosphoric acid, (G) phenylurea and water are obtained by mixing Composition and not plus DPG composition has carried out etching test.Use CuNi/Cu/Ti substrates, Cu/Ti substrates and Cu/Mo substrates Etching test is carried out.O.E. is changed to 50% or 100%, etching test has been carried out with experimental condition similar to the above.

[table 11]

The result of the CuNi/Cu/Ti substrates handled with 50%O.E., which collects, is shown in table 12.Comparative example 7 refers to not to table DPG is added in 11 etch combination and for the CuNi/Cu/Ti substrates of etching test, embodiment 21~23 is directed to table 11 Etch combination in be separately added into 10,20,30 weight %DPG and for the CuNi/Cu/Ti substrates of etching test.As a result show JET, S/E, T/A can be controlled by adding DPG by showing, can also improve the flatness of corrosion-resisting pattern end and section shape.In addition, The SEM photograph of comparative example 7 is shown in Fig. 8,14, and the SEM photograph of embodiment 23 is shown in Figure 13.

[table 12]

CuNi/Cu/Ti substrates50%O.E.

DPG:DPG

In addition, comparative example 8 makes the etch combination of unmixed phosphoric acid in addition when referring to prepare the etch combination of table 11 (that is, by (A) hydrogen peroxide, (B) acid ammonium fluoride, (C) nitric acid, (D) 5- amino -1H-TETRAZOLE (ATZ), (E) tetramethyl hydrogen-oxygen Change ammonium (TMAH), the etch combination that is obtained by mixing of (G) phenylurea and water), added not into the etch combination DPG and for The CuNi/Cu/Ti substrates of etching test.The result of comparative example 7 and comparative example 8 is shown if without phosphoric acid, inner evenness is big Width declines, and S/E becomes big, and the flatness and section shape of end are deteriorated.This is presumably because with the addition of phenylurea.But, such as Fruit with the addition of into the composition further adds as water-miscible organic solvent in composition, the i.e. etch combination of table 11 of phosphoric acid DPG, S/E and T/A control easily, the flatness and section shape of corrosion-resisting pattern end can be greatly improved.Thus speculate Water-miscible organic solvent, which has, makes the effect that the effect of phosphoric acid is further improved.

The result of the CuNi/Cu/Ti substrates handled with 100%O.E., which collects, is shown in table 13.Comparative example 9 refers to not to table DPG is added in 11 etch combination and for the CuNi/Cu/Ti substrates of etching test, embodiment 24~26 is directed to table 11 Etch combination in be separately added into 10,20,30 weight %DPG and for the CuNi/Cu/Ti substrates of etching test.As a result show JET, S/E, T/A can be controlled by adding DPG by showing, can also improve the flatness of corrosion-resisting pattern end and section shape.

[table 13]

CuNi/Cu/Ti substrates100%O.E.

DPG:DPG

The result of the Cu/Ti substrates handled with 50%O.E., which collects, is shown in table 14.Comparative example 10 refers to not to table 11 DPG is added in etch combination and for the Cu/Ti substrates of etching test, embodiment 27~29 is directed to the etching combination of table 11 10,20,30 weight %DPG are separately added into thing and for the Cu/Ti substrates of etching test.As a result display can be by adding DPG Control JET, S/E, T/A.Each equal Ti residues of embodiment are good, in terms of the flatness of corrosion-resisting pattern end, the non-concave-convex surface in end, And section shape is good.

[table 14]

Cu/Ti substrates50%O.E.

DPG:DPG

In addition, comparative example 11 makes the etch combination of unmixed phosphoric acid in addition when referring to prepare the etch combination of table 11 (that is, by (A) hydrogen peroxide, (B) acid ammonium fluoride, (C) nitric acid, (D) 5- amino -1H-TETRAZOLE (ATZ), (E) tetramethyl hydrogen-oxygen Change ammonium (TMAH), the etch combination that is obtained by mixing of (G) phenylurea and water), added not into the etch combination DPG and for The Cu/Ti substrates of etching test.The result of comparative example 10 and comparative example 11 is shown, due to not phosphoric acid, therefore corrosion-resisting pattern end Portion and section shape are deteriorated.It is because with the addition of phenylurea as described above that this, which is speculated,.But, if added into the composition Further addition is used as DPG, S/E and the T/A's of water-miscible organic solvent in the composition of phosphoric acid, the i.e. etch combination of table 11 Control is easy, can greatly improve the flatness and section shape of corrosion-resisting pattern end.Thus speculate water-soluble as described above Organic solvent, which has, makes the effect that the effect of phosphoric acid is further improved.

The result of the Cu/Mo substrates handled with 50%O.E., which collects, is shown in table 15.Comparative example 12 refers to not to table 11 DPG is added in etch combination and for the Cu/Mo substrates of etching test, embodiment 30~32 is directed to the etching combination of table 11 10,20,30 weight %DPG are separately added into thing and for the Cu/Mo substrates of etching test.Being understood by result can be by addition DPG controls JET, T/A.

[table 15]

Cu/Mo substrates50%O.E.

DPG:DPG

2-5. uses the etching test that water-miscible organic solvent is added

With to by (A) hydrogen peroxide, (C) nitric acid, (D) 5- amino -1H-TETRAZOLE (ATZ), (E) TMAH (TMAH) DPG composition, is added in the etch combination (table 16) that (F) phosphoric acid, (G) phenylurea and water are obtained by mixing and is not added DPG composition has carried out etching test.Etching test has been carried out using Cu/Ti substrates.O.E. is set to 50%, with it is above-mentioned Same experimental condition has carried out etching test.

[table 16]

The result of Cu/Ti substrates, which collects, is shown in table 17.Comparative example 13 refers to not add DPG into the etch combination of table 16 And for the Cu/Ti substrates of etching test, embodiment 33 is directed to add 30 weight %DPG in the etch combination of table 16 and supplied In the Cu/Ti substrates of etching test.As a result display can control JET, S/E, T/A by adding DPG, suppress disappearing for corrosion-resisting pattern Lose, smooth the end of corrosion-resisting pattern, it is in normal cone that can make section shape.Thus it can confirm to Cu monofilms also with water-soluble The additive effect of property organic solvent.

As described above, barrier metal used in Cu stacked films typically mainly uses Mo and Ti, according to its purposes, make sometimes With alloy using Ta or other metals or various metals etc..Under such circumstances, if display uses etching of the invention Composition, then for the stacked film, optionally only etch Cu monofilm.This point prompting barrier metal layer wishes other When etch combination is handled, if the selectivity for only dissolving Cu can be realized as the etch combination of the present invention Etching, then can be combined other etch combinations, using two kinds of easy two-stage etchings, thus can be processed into stacked film S/E or T/A in prescribed limit.Also show when being disposably etched to the substrate of titaniferous, can be closed by including fluorine or fluorination The etch combination of thing is carried out, and when carrying out selective etch to the substrate of titaniferous, can pass through not fluorine-containing or fluorine compounds erosions Composition is carved to carry out.

[table 17]

Cu/Ti substrates50%O.E.

Cu selection etching (only etching Cu, do not etch Ti)

DPG:DPG

2-6. uses additive etching test

Mixed with to by (A) hydrogen peroxide, (B) acid ammonium fluoride, (C) nitric acid, (D) 5- amino -1H-TETRAZOLE (ATZ) and water Etch combination obtained by conjunction (table 18) and by (A) hydrogen peroxide, (B) acid ammonium fluoride, (C) nitric acid, (D) 5- amino -1H- The composition of additive is added in the etch combination (table 19) that tetrazolium (ATZ), (H) DPG and water are obtained by mixing and is not attached The composition of agent has carried out etching test.Etching test has been carried out using Cu/Ti substrates, Cu/Mo substrates.O.E. is set to 50%, etching test has been carried out with experimental condition similar to the above.The malonic acid used as additive is for solution Cushioning effect and Cu or Mo dissolubility are improved and added, and TMAH (TMAH) is used to control pH.

[table 18]

The investigation of pH scopes

[table 19]

The investigation of pH scopes

DPG:DPG

The result of Cu/Ti substrates, which collects, is shown in table 20 and table 21.Comparative example 14~18 is directed to the etch combination of table 18 In be separately added into 0/2,2/2,2/3,2/4,2/5 weight % malonic acid/TMAH and for the Cu/Ti substrate (tables of etching test 20).Embodiment 34~36 is directed to be separately added into 0/0,2/2,2/3 weight % malonic acid/TMAH in the etch combination of table 19 And for the Cu/Ti substrates (table 21) of etching test.As a result show that, by adding DPG, the flatness of corrosion-resisting pattern end is obtained Improve.Ti dissolubility declines to a great extent during more than pH5, therefore Cu/Ti substrates are preferably below pH4.

[table 20]

Cu/Ti substrates50%O.E.

TMAH:TMAH

[table 21]

Cu/Ti substrates50%O.E.

TMAH:TMAH

The result of Cu/Mo substrates, which collects, is shown in table 22, table 23.Comparative example 19~24 is directed in the etch combination of table 18 It is separately added into 0/2,2/2,2/3,2/4,2/5,2/6 weight % malonic acid/TMAH and for the Cu/Mo substrate (tables of etching test 22).Embodiment 37~39 is directed to be separately added into 2/2,2/3,2/4 weight % malonic acid/TMAH in the etch combination of table 19 And for the Cu/Mo substrates (table 23) of etching test.As a result display with the addition of DPG composition suppression Mo undercutting, therefore pH Scope is wider than the composition for being not added with DPG, S/E, the improvement of section shape.When can confirm below pH4 by table 23, not Occurs Mo undercutting.But, table 22 and table 23 are shown, if with pH4 ratio of components compared with the substrate of addition DPG etchings is not with adding Plus substrate compare, S/E is very small, so by adjusting proportion of composing, even pH can also suppress for pH5 or pH6 composition Mo is undercut.The decomposition of hydrogen peroxide may be promoted during more than pH7, so it is effective to speculate that the pH of composition is less than pH7. In addition, the SEM photograph of comparative example 21 is shown in Fig. 7, the SEM photograph of comparative example 22 is shown in Figure 13.

[table 22]

Cu/Mo substrates50%O.E.

TMAH:TMAH

[table 23]

Cu/Mo substrates50%O.E.

TMAH:TMAH

Then, unmixed acid is made in addition when comparative example 25~30 as shown below refers to prepare the etch combination of table 18 Property ammonium fluoride etch combination (that is, by (A) hydrogen peroxide, (C) nitric acid, (D) 5- amino -1H-TETRAZOLE (ATZ) and water mix Obtained by shown in etch combination), 0/2,2/2,2/3,2/4,2/4.5,2/5.5 weight is separately added into the etch combination Measure % malonic acid/TMAH and for the Cu/Mo substrates (table 24) of etching test.The result of comparative example 25~30 is only in pH2~pH3 Preferable section shape is obtained, Cu or Mo is undissolved during other pH or occurs Mo undercutting.If in addition, also display with including acid Property ammonium fluoride the comparative example 19~24 that is handled of etch combination compare, acid ammonium fluoride has the undercutting that suppresses Mo Effect, and by adding the DPG as water-miscible organic solvent, the inhibition of Mo undercutting is further improved.

[table 24]

Cu/Mo substrates50%O.E.

TMAH:TMAH

The etching test that 2-7. is relied on based on pH

Mixed with by (A) hydrogen peroxide, (B) acid ammonium fluoride, (C) nitric acid, (D) 5- amino -1H-TETRAZOLE (ATZ) and water Obtained by etch combination (table 25) and by (A) hydrogen peroxide, (B) acid ammonium fluoride, (C) nitric acid, (D) 5- amino -1H- four The etch combination (table 26) that azoles (ATZ), (H) DPG and water are obtained by mixing has carried out etching test.Carried out using Cu/Ti substrates Etching test.O.E. is set to 50%, etching test has been carried out with experimental condition similar to the above.Used as additive Malonic acid be in order to solution cushioning effect and Cu or Ti dissolubility improve and add, TMAH is made to control pH With.

[table 25]

[table 26]

The result of Cu/Ti substrates, which collects, is shown in table 27, table 28.Comparative example 31~33 is directed in the etch combination of table 25 It is separately added into 10/2,10/3,10/8 weight % citric acids/TMAH and for the Cu/Ti substrates (table 27) of etching test, embodiment 40~42 are directed to be separately added into 10/2,10/3,10/8 weight % citric acids/TMAH in the etch combination of table 26 and for erosion Carve the Cu/Ti substrates (table 28) of experiment.Result is the rising with pH, and S/E becomes big.But, DPG substrate is with the addition of with not adding Plus DPG substrate is compared, it can more suppress S/E rising.In addition, being not added with the corrosion-resisting pattern end of DPG substrate in bumps Shape, with the addition of DPG substrate can form smooth end.

[table 27]

Cu/Ti substrates50%O.E.

TMAH:TMAH

[table 28]

Cu/Ti substrates50%O.E.

TMAH:TMAH

The result of Cu/Mo substrates, which collects, is shown in table 29, table 30.Comparative example 36~39 is directed in the etch combination of table 25 It is separately added into 10/2,10/3,10/8,10/10 weight % citric acids/TMAH and for the Cu/Ti substrates (table 29) of etching test, Embodiment 43~46 be directed to be separately added into the etch combination of table 26 10/2,10/3,10/8,10/10 weight % citric acids/ TMAH and for the Cu/Mo substrates (table 30) of etching test.Result is that occur Mo by the substrate of the compositions-treated of table 25 Undercutting.But, if be compared with S/E, DPG substrate is not added with pH rising, S/E is greatly improved, and is added The S/E of DPG substrate has been added to be inhibited.In addition, being not added with the corrosion-resisting pattern end concave-convex surface of DPG substrate, it with the addition of DPG substrate can be smoothened.Mo undercutting occurs for the substrate of table 29.But, it is same when pointing out with using malonic acid, it can lead to Toning whole group is proportional to be suppressed to it.In addition, also prompting can suppress S/E by adding DPG.With replacing lemon using malonic acid Same when lemon is sour, the decomposition of hydrogen peroxide may be promoted during more than pH7, so pH scopes are effective less than pH7.

[table 29]

Cu/Mo substrates50%O.E.

TMAH:TMAH

[table 30]

Cu/Mo substrates50%O.E.

TMAH:TMAH

2-8. uses the etching test that water-miscible organic solvent is added

With to by (A) hydrogen peroxide, (B) acid ammonium fluoride, (C) nitric acid, (D) 5- amino -1H-TETRAZOLE (ATZ), (E) four 2- propyl alcohol is separately added into the etch combination (table 31) that ammonium hydroxide (TMAH), (G) phenylurea and water are obtained by mixing (IPA), diethylene glycol (DEG), dimethyl sulfoxide (DMSO), 1,3 butylene glycol (BD), 1,3- dimethyl-2-imidazolinones (DMI), METHYLPYRROLIDONE (NMP), glycerine (Gly), the composition of DMAC N,N' dimethyl acetamide (DMAc) and the composition not added Etching test is carried out.Etching test has been carried out using CuNi/Cu/Ti substrates.O.E. is set to 50%, with similar to the above Experimental condition has carried out etching test.

[table 31]

Use IPA to be etched obtained result to CuNi/Cu/Ti substrates and collect as water-miscible organic solvent to show In table 32.Comparative example 40 refers to add IPA not into the etch combination of table 31 and for the CuNi/Cu/Ti bases of etching test Plate, embodiment 47~49 is directed to be separately added into 10,20,30 weight %IPA in the etch combination of table 31 and for etching examination The CuNi/Cu/Ti substrates tested.As a result show that IPA also can control JET, S/E, T/A compared with un-added substrate, make resist pattern Case end is smooth, and it is in normal cone that can make section shape.

[table 32]

CuNi/Cu/Ti substrates50%O.E.

IPA:2- propyl alcohol

DEG, DMSO is used to be etched obtained result to CuNi/Cu/Ti substrates as water-miscible organic solvent Collect and be shown in table 33.Embodiment 50~52 is directed to be separately added into 10,20,30 weight %DEG in the etch combination of table 31 simultaneously For the CuNi/Cu/Ti substrates of etching test, embodiment 53~55 is directed to be separately added into 10 in the etch combination of table 31, 20th, 30 weight %DMSO and for the CuNi/Cu/Ti substrates of etching test.As a result show DEG and DMSO also with un-added base Plate compares controllable JET, S/E, T/A, makes corrosion-resisting pattern end smooth, and it is in normal cone that can make section shape.

[table 33]

CuNi/Cu/Ti substrates50%O.E.

DEG:Diethylene glycol, DMSO:Dimethyl sulfoxide

BD, DMI is used to be etched obtained result remittance to CuNi/Cu/Ti substrates as water-miscible organic solvent Always it is shown in table 34.Embodiment 56~58 be directed to be separately added into the etch combination of table 31 10,20,30 weight %BD and for The CuNi/Cu/Ti substrates of etching test, embodiment 59~61 is directed in the etch combination of table 31 be separately added into 10,20,30 Weight %DMI and for the CuNi/Cu/Ti substrates of etching test.As a result show that BD and DMI also can compared with un-added substrate JET, S/E, T/A are controlled, makes corrosion-resisting pattern end smooth, it is in normal cone that can make section shape.

[table 34]

CuNi/Cu/Ti substrates50%O.E.

BD:1,3-BDO, DMI:1,3- dimethyl-2-imidazolinones

NMP, Gly is used to be etched obtained result remittance to CuNi/Cu/Ti substrates as water-miscible organic solvent Always it is shown in table 35.Embodiment 62~64 is directed to be separately added into 10,20,30 weight %NMP in the etch combination of table 31 and supplied In the CuNi/Cu/Ti substrates of etching test, embodiment 65~67 is directed to be separately added into 10 in the etch combination of table 31,20, 30 weight %Gly and for the CuNi/Cu/Ti substrates of etching test.As a result show NMP and Gly also with un-added substrate phase Than controllable JET, S/E, T/A, make corrosion-resisting pattern end smooth, it is in normal cone that can make section shape.

[table 35]

CuNi/Cu/Ti substrates50%O.E.

NMP:METHYLPYRROLIDONE, Gly:Glycerine

Use DMAc to be etched obtained result to CuNi/Cu/Ti substrates as water-miscible organic solvent to collect It is shown in table 36.Embodiment 68~70 be directed to be separately added into the etch combination of table 31 10,20,30 weight %DMAc and for The CuNi/Cu/Ti substrates of etching test.Understand that DMAc also can control JET, S/E, T/A compared with un-added substrate by result, Make corrosion-resisting pattern end smooth, it is in normal cone that can make section shape.

[table 36]

CuNi/Cu/Ti substrates50%O.E.

DMAc:DMAC N,N' dimethyl acetamide

The above results are shown by using water-miscible organic solvent, can control JET, S/E, T/A, and make corrosion-resisting pattern end Smoothly, it is in normal cone that can make section shape.

2-9. uses the etching test of peroxide

With by (A) peroxide ammonium pyrosulfate, (B) acid ammonium fluoride, (C) nitric acid, (D) 5- amino -1H-TETRAZOLE (ATZ), (G) The etch combination (table 37) that phenylurea and water are obtained by mixing has carried out etching test.Lost using CuNi/Cu/Ti substrates Carve experiment.O.E. is set to 50%, etching test has been carried out with experimental condition similar to the above.

[table 37]

The result of CuNi/Cu/Ti substrates, which collects, is shown in table 38.Comparative example 41 refers to add not into the etch combination of table 37 Enter DPG and for the CuNi/Cu/Ti substrates of etching test, embodiment 71 and 72 is directed in the etch combination of table 37 respectively Add 10,20 weight %DPG and for the CuNi/Cu/Ti substrates of etching test.As a result display with the addition of DPG substrate with not The substrate for adding DPG compares controllable JET, S/E, T/A, additionally it is possible to which it is in positive round taper to make section shape.Even it has thus been shown that The peroxide such as peroxide ammonium pyrosulfate, can also obtain with the basic identical effect of hydrogen peroxide, so peroxide ammonium pyrosulfate can generation For hydrogen peroxide.

[table 38]

Cu/Ti substrates50%O.E.

DPG:DPG

3. bath life and supply are tested

3-1. bath life evaluation tests

With by (A) hydrogen peroxide, (B) hydrofluoric acid, (C) nitric acid, (D) 5- amino -1H-TETRAZOLE (ATZ), (E) TMAH, (G) The etch combination (table 39) that phenylurea, (H) DPG and water are obtained by mixing has carried out etching test.Bath life evaluation test is The experiment of performance change during the meltage increase of confirmation copper.In addition, for the dissolving of copper, dissolving copper powders are entered instead of copper base Experiment is gone.Substrate for experiment has carried out etching test using CuNi/Cu/Ti substrates.O.E. is set to 50%, with it is upper State same experimental condition and carry out etching test.

[table 39]

DPG:DPG

The result of CuNi/Cu/Ti substrates, which collects, is shown in table 40.Embodiment 74 refers to use not into the etch combination of table 39 The CuNi/Cu/Ti substrates that the etch combination of addition copper is handled, embodiment 75~77 refers to the etching group to table 39 The CuNi/Cu/Ti substrates that 1000,2000 and 3000ppm etch combination is handled have been dissolved in compound respectively.With molten The display performance of comparative example 75~77 that the etch combination of 0ppm~2000ppm copper handled has been solved slowly to decline.In addition, The display performance of comparative example 77 handled with the etch combination for having dissolved 3000ppm copper declines to a great extent, and generates Ti residual Slag.Not shown in following table, if adding up to 4000ppm copper, copper is not completely dissolved in etch combination in itself.

[table 40]

CuNi/Cu/Ti substrates50%O.E.

The supply experiment of 3-2. bath lifes

Then, added in the etch combination to table 39 as bulking liquor by (A) hydrogen peroxide, (B) hydrofluoric acid, (C) While etch combination (table 41) that nitric acid, (D) TMAH and water are obtained by mixing, the supply experiment of bath life has been carried out.Mend Adding method to liquid uses the volume relative to etch combination, per 1000ppm copper dissolutions amount addition 1.8 volume % or 2.0 Solution obtained by volume % is used as etch combination.Substrate for experiment has carried out etching examination using CuNi/Cu/Ti substrates Test.O.E. is set to 50%, etching test has been carried out with experimental condition similar to the above.

[table 41]

Bulking liquor

DPG:DPG

The result of CuNi/Cu/Ti substrates, which collects, is shown in table 42.Embodiment 78 refers to use not into the etch combination of table 39 The CuNi/Cu/Ti substrates that the etch combination of the copper powder and bulking liquor that add addition is handled, embodiment 79~82 refers to With with the addition of 8000 in the etch combination to table 39 respectively, 16000,24000,32000ppm copper powders and add respectively 14.4th, the CuNi/Cu/Ti substrates that the etch combination of the bulking liquor of 32.0,46.8 and 62.4 volume % tables 14 is handled. As a result show in embodiment 77, Ti residues are produced in copper dissolution amount 3000ppm, and in embodiment 82, even if dissolving 32000ppm copper does not produce Ti residues yet.In addition, on performance, display that and maintain and the performance at initial stage equal property substantially Energy.Thereby confirm that the composition by peroxide, nitric acid, fluorine and/or fluorine compounds, TMAH or water-miscible organic solvent etc. are included As bulking liquor, added in the etch combination having been used of the present invention, bath life can be extended.

[table 42]

CuNi/Cu/Ti substrates50%O.E.

The possibility industrially utilized

If be etched using the etch combination of the present invention, monofilm and/or stacked film can disposably be lost Carve, the complicated exquisite substrate of manufacture, and high productivity can be realized.In addition, by using the etching side of the etch combination The substrate that method is made can be used for flat-panel monitor of higher performance etc..In addition, by using bulking liquor, bath life extends, from And contribute to the cost cutting of substrate production, and security can be improved.

Claims

1. a kind of etch combination, it is to be formed for etching by the metal selected from copper, titanium, molybdenum and nickel or their nitride Monofilm, by the monofilm formed containing the one kind or two or more alloy selected from copper, titanium, molybdenum and nickel, or containing 1 layer or 2 layers The etch combination of the stacked film of the monofilm above is comprising azoles, nitric acid, peroxide and water solubility are organic molten Agent.

2. etch combination as claimed in claim 1, wherein, vapour pressure at 25 DEG C of water-miscible organic solvent for 2kPa with Under.

3. etch combination as claimed in claim 1 or 2, wherein, water-miscible organic solvent is selected from alcohol, glycol, dihydric alcohol, three First alcohol, ketone, carbonic ester, sulfoxide.

4. the etch combination as described in any one of claims 1 to 3, wherein, water-miscible organic solvent be selected from ethylene glycol, Diethylene glycol and DPG.

5. the etch combination as described in any one of Claims 1 to 4, wherein, peroxide is selected from hydrogen peroxide, peroxide Ammonium sulfate, peroxosulphuric sodium and potassium peroxide.

6. the etch combination as described in any one of Claims 1 to 5, wherein, also comprising phosphoric acid or phosphate.

7. the etch combination as described in any one of claim 1~6, wherein, also comprising selected from ammonium hydroxide and ammoniacal liquor Compound.

8. the etch combination as described in any one of claim 1~7, wherein, also comprising fluorine or fluorine compounds.

9. etch combination as claimed in claim 8, wherein, fluorine compounds are selected from ammonium fluoride, acid ammonium fluoride and hydrofluoric acid.

10. the etch combination as described in any one of claim 1~9, wherein, also comprising carbamide compound.

11. etch combination as claimed in claim 10, wherein, carbamide compound is selected from phenylurea, allylurea, 1,3- diformazans Base urea and thiocarbamide.

12. the etch combination as described in any one of claim 1~11, wherein, also comprising organic acid.

13. etch combination as claimed in claim 12, wherein, organic acid is malonic acid or citric acid.

14. the etch combination as described in any one of claim 1~13 is comprising 1~15 mass % peroxidating Thing, 1~10 mass % nitric acid, 0.005~0.2 mass % azole, 0.05~1.00 mass % fluorine compounds, 1~50 Quality % water-miscible organic solvent.

15. the etch combination as described in any one of claim 1~14, it is combined for etching the etching of stacked film Thing, wherein, stacked film is constituted for the layer of titanium/copper/titanium.

16. the etch combination as described in any one of claim 1~14, it is combined for etching the etching of stacked film Thing, wherein, stacked film is that the layer of the alloy/copper/titanium formed by copper and mickel is constituted, and the titanium is located at substrate-side.

17. the etch combination as described in any one of claim 1~14, it is combined for etching the etching of stacked film Thing, wherein, stacked film is constituted for the layer of the individual layer of individual layer/molybdenum of copper respectively, and the individual layer of the molybdenum is located at substrate-side.

18. the etchant as described in any one of claim 1~17, wherein, pH is less than 7.0.

19. a kind of engraving method, it is the individual layer that etching is formed by the metal selected from copper, titanium, molybdenum and nickel or their nitride Film, by the monofilm formed containing the one kind or two or more alloy selected from copper, titanium, molybdenum and nickel, or containing 1 layer or more than 2 layers The monofilm stacked film method, wherein, including the use of described in any one of claim 1~18 etching combination The process that thing is etched.

20. method as claimed in claim 19, wherein, it is used for liquid crystal display, color film, contact panel, organic EL and shows Device, Electronic Paper, MEMS or IC manufacturing process or packaging process.