CN106400017B

CN106400017B - Etching solution and the engraving method using it and the substrate that is obtained using the engraving method

Info

Publication number: CN106400017B
Application number: CN201610619512.5A
Authority: CN
Inventors: 山田洋三; 本望圭纮; 后藤敏之
Original assignee: Mitsubishi Gas Chemical Co Inc
Current assignee: Mitsubishi Gas Chemical Co Inc
Priority date: 2015-08-03
Filing date: 2016-07-29
Publication date: 2019-07-09
Anticipated expiration: 2036-07-29
Also published as: CN106400017A; JP2017031502A; KR20170016279A; TWI677561B; KR102291351B1; TW201706395A; JP6337922B2

Abstract

There is provided: for etching the etching solution for the plural layers being laminated on substrate, the substrate is used selected from one or more of glass, silica and silicon nitride, and the plural layers include with copper layers of copper as main component and with titanium titanium layer as main component；With the engraving method for the plural layers comprising layers of copper and titanium layer for using it；And the substrate obtained using the engraving method.A kind of etching solution, is the aqueous solution comprising following ingredient and pH value is 1.5~2.5:(A) concentration of hydrogen peroxide is 4.5~7.5 mass %；(B) concentration of nitric acid is 0.8~6 mass %；(C) concentration of fluorine compounds is 0.2~0.5 mass %；(D) concentration of azole is 0.14~0.3 mass %；(E) concentration of specific amine compounds is 0.4~10 mass %；The concentration of (F) stabilizer of hydrogen peroxide is 0.005~0.1 mass %.

Description

Etching solution and the engraving method using it and the substrate that is obtained using the engraving method

Technical field

This technology is related to: for etching the etching for the plural layers being laminated on glass, silica or silicon nitride board Liquid, the plural layers include with copper layers of copper as main component and with titanium titanium layer as main component；With use its etching Method.Etching solution of the invention is equipped with the etching of the plural layers of layers of copper particularly suitable for titanium layer.

Background technique

All the time, the wiring material of equipment is shown as flat-panel monitor etc., generally uses aluminium or aluminium alloy.So And along with the enlargement and high resolution of display, the wiring material of such aluminium system is generated because of characteristics such as routing resistances And the problem of signal delay occurs, have the tendency that uniform picture is shown and becomes difficult.

Therefore, it as the lower material of resistance, uses copper or is gradually increased with the example of copper metal line as main component Add.However, copper has the advantages that resistance is low, on the other hand, there are the following problems: making in grid wiring (gate wiring) In the case where copper, the adaptation of the substrates such as glass and copper is insufficient, and source/drain wiring in use copper the case where Under, the diffusion to organic silicon semiconductor film as its substrate is generated sometimes.Such problems in order to prevent is configured with The stacking of the barrier layer of metal, the adaptations of the substrates such as the metal and glass is high and also has both and is not likely to produce to organosilicon half The barrier property of conductor membrane diffusion, as the metal, mostly using titanium series metal as titanium, titanium nitride.

However, being layered in glass, two by film-forming process such as sputtering methods with copper or copper alloy stacked film as main component On silicon oxide or silicon nitride etc. (being denoted as glass etc. sometimes) substrate, then via the etching being etched with protective layer etc. for mask Process and form electrode pattern.Moreover, the mode of the etching work procedure have wet type (wet process) method using etching solution and use etc. from Dry type (dry method) method of the etching gas such as daughter.Herein, etching solution used in wet type (wet process) method requires following feature:

(i) high manufacturing accuracy,

(II) etch residue is few,

(III) etching is uneven less,

The dissolution of (IV) for the wiring metal material comprising the copper as etch target, etching performance are stablized,

And in order to cope with the enlargement of display and high resolution, it is desirable that:

(v) wiring shape after being etched is the good wiring shape of desired range.

More specifically, as shown in Figure 1, be strongly required following feature: the etching face of copper wiring layer (2) end is under The positive cone shape that substrate (4) angulation (cone angle (5)) of layer is 20 °~60 °；From protective layer (1) end to protection Distance ((top CD loss), a × 2 is lost in top CD) until wiring layer (2) end that layer is in contact is 2.5 μm or less；From (bottom at a distance from until protective layer (1) end to wiring layer (2) end being in contact with the barrier layer (3) being set under wiring CD be lost (bottom CD loss), b × 2) be 1.5 μm hereinafter, and barrier layer trail (tailing) (c × 2) be 0.4 μm with Under.

As comprising copper, with etching solution used in the etching work procedure of the stacked film of copper copper alloy as main component, example As described a kind of etching solution in patent document 1 (Japanese Unexamined Patent Publication 2002-302780 bulletin), it includes: it is selected from neutral salt, nothing At least one kind of and hydrogen peroxide, stabilizer of hydrogen peroxide in machine acid and organic acid.

It proposes in patent document 2 (No. 2003/0107023 specification of U.S. Patent Application Publication No.) comprising peroxidating Hydrogen, organic acid, fluorine etching solution.

It proposes in patent document 3 (International Publication No. 2011/021860) comprising hydrogen peroxide, fluorine, organic phosphine chemical combination The etching solution etc. of object.

However, for etching solution disclosed in patent document 1 and 2, and insufficient wiring shape met after etching, as As a result, the enlargement and high resolution of display can not be coped with sometimes.In turn, although patent document 2, which contains, is used as organic acid Acetic acid, but have the shortcomings that the dissolution of titanium is extremely slow (referring to table 11, comparative example 24).

In patent document 3, in order to etch molybdenum alloy, titanium, it is compounded the fluorochemical of 0.01~1.0 mass %, but fluorine makes The multi-purpose glass for making substrate and silica or silicon nitride etch, as a result, the baneful influences such as changes in optical properties are generated, Therefore, it is desirable to the etching solution that the damage to glass etc. is small.

In addition, Patent Documents 1 to 3 are known that larger amount of hydrogen peroxide is contained in ingredient (such as patent document It is 5.0~25 mass % in 3), but increase with the metal ion in the etching solution is dissolved in due to repetition etching operation, mistake The stability of hydrogen oxide reduces.When the concentration of hydrogen peroxide in the etching solution is reduced sharply, desired etching can not be obtained Can, and the supplement quantitative change of hydrogen peroxide is more, and it is unfavorable economically to become.

Existing technical literature

Patent document

Patent document 1: Japanese Unexamined Patent Publication 2002-302780 bulletin

Patent document 2: No. 2003/0107023 specification of U.S. Patent Application Publication No.

Patent document 3: International Publication No. 2011/021860

Summary of the invention

Problems to be solved by the invention

In the prior art, it is mostly used for including layers of copper and titanium layer compounded with the etching solution of hydrogen peroxide, acid, fluorine compounds The etching of plural layers, but the substrates such as fluorine compounds meeting etching glass.For the etching solution comprising fluorine compounds, it is strongly required Have the effect of comprising fluorine compounds will not the substrates such as etching glass etching solution.

In turn, in order to control the etching speed of the etching solution, the adjusting of pH value is usually carried out.PH, which is adjusted, uses alkali composition, It is but big to the corrosion of the substrates such as glass when using ammonia, potassium hydroxide, it is difficult to which that efficiency is good and steadily production has target property Panel.

Also there is the case where quaternary ammonium hydroxide as other alkali compositions is adjusted for pH, but tetramethylammonium hydroxide belongs to Violent in toxicity bans method poisonous substance, high to the harmfulness of human body, and use is restricted, and it is not preferable.

The present invention completes in this case, provides: for etching glass, silica with plural layers Or the etching solution of silicon nitride board, the plural layers include with copper layers of copper as main component and with titanium titanium as main component Layer；With the engraving method for the plural layers comprising layers of copper and titanium layer for using it；And the substrate obtained using the engraving method. More specifically, it provides: although can be greatly decreased for the etching solution comprising hydrogen peroxide and fluorine compounds to glass, dioxy The etching solution of the corrosion of SiClx or silicon nitride board；With the engraving method for the plural layers comprising layers of copper and titanium layer for using it； And the substrate obtained using the engraving method.

The solution to the problem

Present inventors etc. are furtherd investigate repeatedly in order to reach foregoing purpose, as a result, it has been found that: although being closed to contain fluorination The etching solution of object, but by adding specific amine compounds in the etching solution, so as to include layers of copper and titanium to having The wiring of the plural layers of layer is etched together, at this point, it is small to the corrosion of glass, silica or silicon nitride board, thus Complete the present invention.

More it is surprising that know will not destroying hydrogen peroxide the metal ion increase being dissolved in etching solution Stability, and high productivity is kept by the engraving method and keeps good wiring shape after etching.

That is, the present application is related to following technology:

The wiring with the plural layers comprising layers of copper and titanium layer is etched by etching solution, the etching solution is such as Lower aqueous solution and pH value are 1.5~2.5: comprising 4.5~7.5 mass % of (A) hydrogen peroxide, 0.8~6 mass % of (B) nitric acid, (C) 0.2~0.5 mass % of fluorine compounds, 0.14~0.3 mass % of (D) azole, 0.4~10 matter of (E) specific amine compounds % and 0.01~0.10 mass % of (F) stabilizer of hydrogen peroxide is measured, surplus is made of water.

[1] a kind of etching solution, for the etching solution for etching the plural layers being laminated on substrate, the substrate is used Selected from one or more of glass, silica and silicon nitride, the plural layers include with copper layers of copper as main component and with Titanium titanium layer as main component, the etching solution is the aqueous solution comprising following ingredient and pH value is 1.5~2.5:(A) peroxidating The concentration of hydrogen is 4.5~7.5 mass %, the concentration of (B) nitric acid is 0.8~6 mass %, the concentration of (C) fluorine compounds be 0.2~ 0.5 mass %, (D) azole concentration be 0.14~0.3 mass %, the concentration of (E) amine compounds be 0.4~10 mass % and (F) concentration of stabilizer of hydrogen peroxide is 0.005~0.1 mass %.Aforementioned (E) amine compounds be preferably selected from 1 with On optionally the alkanamine (E1) of the alkyl of the carbon number 2~5 of the straight-chain replaced methoxyl group or branched, have 1 or 2 it is straight The hydroxy alkyl of chain or the carbon number of branched 2~5 and any carbon number 2~5 with 1 or 2 straight-chains or branched The alkanolamine (E2) of alkyl, carbon number 2~5 with straight-chain or branched alkylidene diamines (E3) and cyclohexylamine One or more of (E4).Herein, refer to " using copper as main component ", comprising 50 mass % or more, preferably 60 mass % or more, The copper of more preferable 70 mass % or more." using titanium as main component " refers to, comprising 50 mass % or more, preferably 60 mass % with The titanium of upper, more preferable 70 mass % or more.

[2] etching solution according to the 1st, wherein (C) fluorine compounds are selected from hydrofluoric acid, ammonium fluoride and acid fluorine Change one or more of ammonium.

[3] etching solution according to the 1st, wherein (D) azole is 5- amino -1H-TETRAZOLE.

[4] etching solution according to the 1st, wherein (E) amine compounds are selected from the carbon with straight-chain or branched Alkanamine, alkanolamine, diamines and the cyclic amine of the alkyl (wherein, excluding the hexyl of the chain other than cyclic annular hexyl) of number 1~6 One or more of.

[5] etching solution according to the 1st or the 4th, wherein (E) amine compounds are selected from isopropanolamine, 3- ammonia Base -1- propyl alcohol, N- butylethanolamine, N, N- dimethylamino -2- propyl alcohol, 2- methoxyethyl amine, cyclohexylamine, n-butylamine, two fourths Amine, tert-butylamine, N- methyl-n-butylamine, 1,4- diaminobutane, 2- amino-n-butyl alcohol, 5- amino -1- amylalcohol, 3- methoxy propyl One or more of amine, 2-dimethylaminoethanol and 2- ethylaminoethanol.

[6] etching solution according to the 1st, wherein (F) stabilizer of hydrogen peroxide is selected from phenylurea and phenolsulfonic acid One or more of.

[7] etching solution according to the 1st, wherein CD loss in top is for 2.5 μm hereinafter, CD loss in bottom is 1.5 μm It is below 0.4 μm or less with hangover.

[8] etching solution according to the 1st, wherein the corrosion rate of glass is 60nm/ minutes or less.

[9] etching solution according to the 1st, wherein the corrosion rate of silica and silicon nitride is/ minute with Under.

[10] etching solution according to the 1st comprising with copper layers of copper as main component and with titanium be mainly at The appropriate etching period of the plural layers of the titanium layer divided is 80 seconds~140 seconds.

[11] etching solution according to the 1st, wherein in the etching solution add copper 4000ppm and titanium 360ppm and The stability of the hydrogen peroxide in etching solution when saving 2 hours for 50 DEG C is 0.075%/hour or less.

[12] etching solution according to the 1st, wherein be laminated in use in glass, silica and silicon nitride 1 kind or more of substrate on plural layers be with stacking on titanium titanium layer as main component with copper layers of copper as main component Made of.

[13] a kind of comprising with copper layers of copper as main component and with the erosion of the plural layers of titanium titanium layer as main component Carving method, which is characterized in that make etching solution described in the plural layers being laminated on substrate and the 1st~any one of the 12nd Contact, the substrate are used selected from one or more of glass, silica and silicon nitride, and the plural layers include to be with copper The layers of copper of main component and with titanium titanium layer as main component.

The effect of invention

Preferred embodiment according to the present invention, by (being denoted as glass sometimes being laminated in glass, silica or silicon nitride Deng) etching solution that the present application is used in the etching work procedures of plural layers on substrate, thus the bath service life (bath of etching solution Life) length, machining accuracy height, etch residue, it is uneven less and the good wiring shape after being etched, it is possible thereby to provide Cope with the substrates such as the enlargement of display and the glass of high resolution, wherein the plural layers include based on copper Want the layers of copper of ingredient and with titanium titanium layer as main component.

Detailed description of the invention

Fig. 1 is that having when being etched using etching solution of the invention is laminated in glass, silica or nitridation silicon substrate The schematic diagram in the wiring section of the plural layers on plate, the plural layers include with copper layers of copper as main component and based on titanium Want the titanium layer of ingredient.

Description of symbols

1. protective layer

2. wiring layer

3. barrier layer

4. substrate

5. cone angle

A: top CD loss (a)

B: bottom CD loss (b)

C: hangover (c)

Specific embodiment

For etching the plural layers comprising layers of copper and titanium layer being laminated on glass, silica or silicon nitride board Etching solution

Etching solution of the invention is characterized in that, is used to be laminated in the multilayer comprising layers of copper and titanium layer on glass substrate The etching of film, the etching solution is following aqueous solution and pH value is 1.5~2.5:

Concentration comprising (A) hydrogen peroxide is 4.5~7.5 mass %, the concentration of (B) nitric acid be 0.8~6.0 mass %, (C) concentration of fluorine compounds is 0.2~0.5 mass %, the concentration of (D) azole is 0.14~0.30 mass %, (E) amine compounds Concentration be the concentration of 0.4~10 mass % and (F) stabilizer of hydrogen peroxide be 0.005~0.1 mass %, surplus is by water structure At.

(A) hydrogen peroxide

Hydrogen peroxide used in etching solution of the invention has the function of making copper metal oxidation, the etching as oxidant Content in liquid be preferably 4.5 mass % or more, more preferably 5.0 mass % or more, additionally, it is preferred that for 7.5 mass % or less, More preferably 7.0 mass % or less, further preferably 6.5 mass % or less.Wherein, the peroxidating in etching solution of the invention The content of hydrogen is preferably 4.5~7.5 mass %, more preferably 4.5~7.0 mass %, particularly preferably 5.0~6.5 mass %. For the content of hydrogen peroxide if it is in above range, may insure etching speed appropriate, the control transfiguration of etch quantity is easy, and It will not generate the local corrosion of thin copper film, therefore it is preferred that.

(B) nitric acid

Nitric acid used in etching solution of the invention promotes the dissolution of the copper aoxidized by (A) hydrogen peroxide, the etching solution In the content of nitric acid be preferably 0.8~6 mass %, more preferably 2~6 mass %, particularly preferably 3.5~6 mass %.Nitre The content of acid is if it is in above range, available etching speed appropriate, and the cloth after available good etching Wire shaped.

(C) fluorine compounds

Fluorine compounds used in etching solution of the invention facilitate the etching of the barrier layer formed by titanium series metal, the erosion The content carved in liquid is preferably 0.2~0.5 mass %, more preferably 0.2~0.4 mass %, particularly preferably 0.2~0.3 matter Measure %.The content of fluorine compounds if it is in above range, the available barrier layer formed by titanium series metal it is good Etching speed.

As fluorine compounds, it is not particularly limited, can preferably enumerates: hydrogen fluorine as long as generating fluorine ion in etching solution Acid, ammonium fluoride, ammonium acid fluoride etc., they can be used alone or combine a variety of uses.Wherein, go out from the viewpoint of hypotoxicity Hair, more preferable ammonium fluoride and ammonium acid fluoride.

(D) azole

It as azole used in etching solution of the invention, can preferably enumerate: 1,2,4- triazole, 1H- benzotriazole, 5- The triazole types such as methyl-1 H- benzotriazole, 3- amino -1H- triazole, 1H-TETRAZOLE, 5- methyl-1 H- tetrazolium, 5- phenyl -1H- four Thiazoles such as four azoles, 1,3- thiazole, the 4- methylthiazols such as azoles, 5- amino -1H-TETRAZOLE etc..Wherein, preferably four azoles, especially It is preferred that 5- amino -1H-TETRAZOLE.

The content of azole in etching solution is preferably 0.14 mass % or more, is more preferably 0.15 mass % or more, in addition, Preferably 0.3 mass % or less, more preferably 0.25 mass % or less.Wherein, the content of the azole in etching solution of the invention Preferably 0.14~0.3 mass %, particularly preferably 0.15~0.25 mass %.The content of azole if it is in above range, It then can wiring shape with the etching speed of suitable control thin copper film, after available good etching.

(E) amine compounds

Think, amine compounds used in etching solution of the invention have caused by reducing by fluorine compounds to using glass The function of the corrosion of the substrate of glass, silica or silicon nitride.As effectively with the amine compounds of these functions, Ke Yiyou Elect: the alkyl with straight-chain or branched or cricoid carbon number 1~6 (wherein, excludes the chain other than cyclic annular hexyl Hexyl) alkanamine, alkanolamine, diamines and cyclic amine.With carbon number be 7 or more alkyl amine solubility in water it is low, Accordingly, it is difficult to be dissolved in etching solution, apparent foaming is generated part of it can be made to dissolve, is difficult to sometimes as erosion It is practical to carve liquid.

It as amine compounds used in etching solution of the invention, can enumerate: with 1 or more optionally by methoxyl group institute The alkanamine (E1) of the alkyl of the carbon number 2~5 of substituted straight-chain or branched；Carbon with 1 or 2 straight-chains or branched The hydroxy alkyl of number 2~5 and any alkanolamine with 1 or the alkyl of the carbon number 2~5 of 2 straight-chains or branched (E2)；The diamines (E3) of the alkylidene of carbon number 2~5 with straight-chain or branched；With cyclohexylamine (E4).Hereinafter, to each amine Compound is illustrated.

< alkanamine (E1) >

Alkanamine (E1) can be shown below:

[in formula, R¹For the alkyl of the optionally carbon number 2~5 of the straight-chain replaced methoxyl group or branched, m 1,2 or 3。]。

Specifically, can be enumerated as alkanamine (E1): ethamine, 2- methoxyethyl amine, n-propylamine, isopropylamine, 3- methoxy Base propylamine, n-butylamine, sec-butylamine, isobutyl amine, tert-butylamine, amylamine, 2- aminopentane, 3- aminopentane, 1- amino-2-methyl fourth Alkane, 2- amino-2-methyl butane, 3- amino-2-methyl butane, 4- amino-2-methyl butane, 5- amino-2-methyl pentane etc. Primary alkylamine；Di-n-propylamine, diisopropylamine, dibutyl amine, di-sec-butylamine, two tert-butylamines, diamylamine, methyl ethyl-amine, methyl propylamine, methyl Isopropylamine, methylbutylamine, methyl tert-butyl amine, methyl-sec-butylamine, methyl-tertbutylamine, dimethylpentylamine, methyl iso-amylamine, ethyl third Amine, ethyl isopropylamine, ethyl butyl amine, ethyl isobutyl amine, ethyl-sec-butylamine, ethyl amylamine, ethyl iso penlyl amine, propyl butylamine, third The secondary alkylamines such as base isobutyl amine；Trimethylamine, triethylamine, tripropyl amine (TPA), tri-n-butylamine, triamylamine, dimethyl amine, methyl-diethyl-amine, first Tertiary alkanamines such as base di-n-propylamine etc..

< alkanolamine (E2) >

Alkanolamine (E2) can be shown below:

[in formula, R²OH is the hydroxy alkyl of the carbon number 2~5 of straight-chain or branched, R³For the carbon of straight-chain or branched The alkyl of number 2~5, p are 1 or 2, q 0,1 or 2, p+q 1,2 or 3.].

Specifically, can be enumerated as alkanolamine (E2): ethanol amine, N- methylethanolamine, N, N- dimethyl ethanol Amine, N- ehtylethanolamine, N, N- diethyl ethylene diamine, N- Propanolamine, N- propyl ethanol amine, N- butylethanolamine, diethanol amine, Isopropanolamine, N- methyl isopropyl hydramine, N- ethylisopropanolamine, N- propyl isopropanolamine, 2- amino -1- propyl alcohol, 3- amino -1- Propyl alcohol, N- methyl-2-amino -1- propyl alcohol, N, N- dimethylamino -2- propyl alcohol, N- ethyl -2- amino -1- propyl alcohol, 1- amino - 2- butanol, N- methyl-1-amino-2- butanol, N- ethyl-1- amino-2- butanol, 2- amino-n-butyl alcohol, N- methyl-2-amino- N-butyl alcohol, N- ethyl -2- amino-n-butyl alcohol, 3- amino-n-butyl alcohol, N- ethyl -3- amino-n-butyl alcohol, 1- amino -4- butanol, 1- amino-2-methyl -2- propyl alcohol, 2-amino-2-methyl-1-propanol, 1- amino -4- amylalcohol, 2- amino -4- methyl-1-pentene alcohol, 5- amino -1- amylalcohol, 1- aminopropane -2,3- glycol, 2- aminopropane -1,3- glycol, three (oxygroup methyl) aminomethanes and 1,2- diamino -2- propyl alcohol etc..It is not limited to these.In addition, they can be used alone or combine a variety of make in the present invention With.

As diamines (E3), can enumerate: ethylenediamine, 1,2- propane diamine, 1,3- propane diamine, diethyl -1,3- propane diamine, 1,4- diaminobutane, 1,3- diaminobutane, 2,3- diaminobutane, five methylene diamine, 2,4- 1,5-DAP etc..

In addition, cyclohexylamine (E4) can be enumerated as amine compounds.

In the present invention, these amine compounds can be used alone or combine a variety of uses.

It in these amine compounds, can preferably enumerate: isopropanolamine, 3- amino -1- propyl alcohol, N- butylethanolamine, N, N- Dimethylamino -2- propyl alcohol, 2- methoxyethyl amine, cyclohexylamine, n-butylamine, dibutyl amine, tert-butylamine, N- methyl-n-butylamine, 1,4- Diaminobutane, 2- amino-n-butyl alcohol, 5- amino -1- amylalcohol, 3 methoxypropyl amine, 2-dimethylaminoethanol, 2- amino second Alcohol, particularly preferably 3 methoxypropyl amine, N- methyl-n-butylamine, n-butylamine, 2- amino-n-butyl alcohol, cyclohexylamine, N- butyl second Hydramine, 5- amino -1- amylalcohol.

The content of amine compounds in etching solution is preferably 0.4 mass % or more, more preferably 1 mass % or more, into one Step is preferably 2 mass % or more, additionally, it is preferred that for 10 mass % or less, more preferably 9 mass % or less, further preferably 8 Quality % or less.Wherein, the content of the amine compounds in etching solution is preferably 0.4~10 mass %, more preferably 1~9 matter Measure %, further preferably 1~8 mass %, particularly preferably 2~8 mass %.The content of amine compounds is if it is above range Interior, even if the metal concentration then in liquid rises, the decomposition of hydrogen peroxide is also slow, and the available damage to glass substrate is small Etching solution.

(F) stabilizer of hydrogen peroxide

Etching solution of the invention preferably comprises stabilizer of hydrogen peroxide.As stabilizer of hydrogen peroxide, as long as usually to use The substance for making stabilizer of hydrogen peroxide can use without limitation, in addition to phenylurea, allylurea, 1,3- dimethyl urea, Except the ureas such as thiocarbamide system stabilizer of hydrogen peroxide, can also preferably it enumerate: phenyl-acetamides, styrene glycol, phenolsulfonic acid etc., Particularly preferred phenylurea, phenolsulfonic acid.In addition, they can be used alone or combine a variety of uses in the present invention.

The content of stabilizer of hydrogen peroxide in etching solution of the invention from the viewpoint of sufficiently obtaining its additive effect, Preferably 0.005 mass % or more, more preferably 0.01 mass % or more, additionally, it is preferred that being 0.1 mass % or less, more preferable For 0.09 mass % or less, further preferably 0.08 mass % or less.Wherein, the hydrogen peroxide in etching solution of the invention is steady The content for determining agent is preferably 0.005~0.1 mass %, particularly preferably 0.01~0.09 mass %, particularly preferably 0.01~ 0.08 mass %.

PH value

It is 1.5~2.5 range that etching solution of the invention, which needs pH value,.When pH value is less than 1.5, etching speed became Fastly, therefore, the local corrosion of thin copper film is generated, is generated in thin copper film sometimes and etches uneven (unevenness).In addition, pH value is higher than When 2.5, the stability of hydrogen peroxide is reduced, and is caused heat release, is decomposed, and the concentration of hydrogen peroxide reduces, as a result, drawing sometimes Rise thin copper film etching speed reduce, can not steady production a problem that.

PH, which is adjusted, usually to be carried out by addition (E) amine compounds, but as long as the effect for not damaging the present application can also To add other pH adjusting agents.It can be used for example: usually used inorganic acid, organic acid, inorganic base and organic base etc..

Water

Use water as diluent, water of the invention preferably passes through distillation, ion-exchange treatment, filtration treatment, various suctions Attached processing etc. eliminates water obtained from metal ion, organic impurities, granule particles etc., particularly preferred pure water or ultrapure water.

Other compositions

Other than above-mentioned (A)~(F) ingredient, etching solution of the invention can be in the range of not interfering etching solution effect Include various additives usually used in etching solution, surfactant, colorant, defoaming agent etc..

It is laminated in the engraving method of the plural layers comprising layers of copper and titanium layer on glass, silica or silicon nitride board

Engraving method of the invention is to lose to the plural layers comprising layers of copper and titanium layer being laminated on glass substrate The method at quarter, the method be characterized in that using etching solution of the invention, and this method has and makes etch target object and the present invention Etching solution contact process, wherein etching solution of the invention be include (A) hydrogen peroxide concentration be 4.5~7.5 matter Measure %, the concentration of (B) nitric acid is 0.8~6 mass %, the concentration of (C) fluorine compounds is 0.2~0.5 mass %, (D) azole Concentration is 0.14~0.3 mass %, the concentration of (E) amine compounds is the dense of 0.4~10 mass % and (F) stabilizer of hydrogen peroxide The aqueous solution that degree is 0.005~0.1 mass %, surplus is made of water, and the etching solution that pH value is 1.5~2.5.

The method for contacting etch target object with etching solution is not particularly limited, such as can be used: is (single by dropwise addition Piece rotation processing), the forms such as the spraying method that contacts etching solution with object；The method etc. for making object be impregnated in etching solution Wet type (wet process) engraving method.In the present invention, it is preferred to use: object is impregnated in etching solution or carries out spraying and makes it The method of contact.

As the use temperature of etching solution, preferably 10~70 DEG C, particularly preferably 20~50 DEG C.The temperature of etching solution is such as Fruit is 10 DEG C or more, then etching speed will not become too slow, and therefore, production efficiency will not be substantially reduced.On the other hand, if it is 70 DEG C of temperature below, then can inhibit liquid composition variation, and etching condition is kept certain.By the temperature for improving etching solution Degree, etching speed rise, but in terms of also considering to be suppressed to the composition of lesser etching solution, optimal place is suitably determined Manage temperature.

In addition, engraving method through the invention, can carry out being laminated in together on glass substrate includes layers of copper and titanium The etching of the plural layers of layer, and after etching, available wiring shape good as shown in Figure 1.

In engraving method of the invention, the etch target object of etching solution is: substrate the glass such as shown in Fig. 1 On stack gradually by titanium or barrier layer (titanium layer) He Youtong formed with titanium titanium based material as main component or be main with copper On plural layers comprising layers of copper and titanium layer made of the metal line that the material (layers of copper) of ingredient is formed, further coating protection Layer, is exposed transfer to desired pattern mask, is developed and form desired protection layer pattern, etching is consequently formed Object.Herein, in the present invention, the plural layers comprising layers of copper and titanium layer are with there are layers of copper on titanium layer as shown in Figure 1 Scheme is representative, also includes: further there is the scheme of the three-decker of titanium layer in layers of copper.

In engraving method of the invention, as shown in Figure 1 there are be with copper on titanium titanium layer as main component The etch target object of the layers of copper of main component is preferred from the viewpoint of the performance for effectively playing etching solution of the invention.Separately Outside, such aobvious comprising being preferred for plate with copper layers of copper as main component and with the multilayer film of titanium titanium layer as main component Show that device etc. shows the wiring of equipment etc..There are the etch target objects of layers of copper from the viewpoint of using field on titanium layer as a result, It is also preferred embodiment.

Thin copper film is not particularly limited as long as being laminated by copper or with copper material as main component, should as stacking The titanium based material of barrier layer, can enumerate titanium and its nitride i.e. titanium nitride, be not limited to these titanium compounds.

Etch target object, that is, plural layers thickness of the invention is usually 20nm~1500nm, and preferably 50nm~ 1200nm, more preferably 100nm~1000nm, further preferably 150nm~800nm.

In engraving method of the invention, for the concentration of (A) hydrogen peroxide contained in etching solution and (B) nitric acid, as above It states and is consumed like that respectively as the oxidant of thin copper film, and (B) nitric acid is also consumed in the dissolution for the copper being oxidized, because This, generates etching caused by the reduction due to the concentration of (A) hydrogen peroxide and (B) nitric acid in the etching solution that uses sometimes The reduction of energy.Under such circumstances, (A) hydrogen peroxide and (B) nitric acid are added by appropriate addition simultaneously or respectively, so as to Extend the bath service life and uses.

Embodiment

Then, the present invention is described in more detail according to embodiment, but the present invention is not by any restriction of these examples.

The production example of plural layers comprising layers of copper and titanium layer

On the glass substrate with thickness 25nm sputtered titanium, then, with the sputter thickness copper of 400nm, stacking wiring raw material Layers of copper.Then, coat protective layer is exposed transfer to pattern mask, then develops, and forms wiring pattern, thus Production includes the plural layers of layers of copper and titanium layer on the glass substrate.

The appropriate etching period (just etching time (JET)) of engraving method and copper and titanium layer

By the above method, layers of copper and titanium will be laminated in 35 DEG C using etching solution described in table 1~6 and table 10,11 The glass substrate of layer impregnates 150 seconds, is washed, is made it dry later using nitrogen.

Using the time until reaching glass substrate based on the etching visually observed as appropriate etching period, according to following institute The benchmark stated is judged.

Determine:

E:90 seconds~120 seconds

G:80 seconds or more~less than 90 seconds, more than 120 seconds~140 seconds

B: less than 80 second, more than 140 seconds

E and G are set as qualified.

The cross-section observation of the plural layers comprising layers of copper and titanium layer after etching

The plural layers sample comprising layers of copper and titanium layer obtained by above-mentioned engraving method is cut off, it is aobvious using scanning electron Micro mirror (model: S5000H type Hitachi Co., Ltd manufacture), (acceleration voltage 2kV, accelerates electric current with 50000 times of multiplying power 10 μ A) observation section.

Based on gained SEM image, cone angle shown in FIG. 1 (5), top CD loss (a), bottom CD loss (b) are measured With hangover (c).

Shape after etching using cone angle (°), top CD loss (μm), bottom CD loss (μm), hangover (μm) according to Under benchmark determined.

Determine:

Top CD loss (=a × 2) is 2.5 μm or less and is set as qualified

Bottom CD loss (=b × 2) is 1.5 μm or less and is set as qualified

Hangover (=c × 2) is 0.4 μm or less and is set as qualified

Cone angle is 20 °~60 ° and is set as qualified.

The production example of corrosion evaluation glass, silica or silicon nitride board

The coat protective layer on glass, silica or silicon nitride board is exposed transfer to pattern mask, then into Row development, forms wiring pattern, the substrate as evaluation.

Evaluation to the corrosion of glass substrate

By corrosion evaluation obtained above with glass substrate be impregnated in table 6,10,11 described in 20 minutes in etching solution, so After washed, made it dry using nitrogen.

It is measured and is corroded using contact roughmeter (manufacture of Contourecord 2700SD3 Tokyo Seimitsu Co., Ltd) The difference in height in portion and non-corrosive portion calculates corrosion rate, is evaluated according to determinating reference below.Show the result in table 7,12 With 13.

Determine:

E:50nm/ minutes or less

G: more than 50nm/ minutes~60nm/ minutes or less

B: more than 60nm/ minutes

E and G are set as qualified.

Evaluation to the corrosion of silica or silicon nitride board

Corrosion evaluation obtained above silica or silicon nitride board are impregnated in etching solution described in table 6,10,11 In 5 minutes, then washed, made it dry using nitrogen.

Using scanning electron microscope (model: S5000H type Hitachi Co., Ltd manufactures), with multiplying power 50000 The section in observation the corrosion portion and non-corrosive portion (acceleration voltage 2kV, acceleration 10 μ A of electric current) again.Based on gained SEM image, calculate Corrosion rate out is evaluated according to determinating reference below.Show the result in table 8,9 and 14~17.

Determine:

E:Below

G: it is more thanBelow

B: it is more than

E and G are set as qualified.

The evaluation of Stability of Hydrogen Peroxide

Before keeping when the etching solution that will be dissolved with copper 4000ppm and titanium 360ppm is taken care of 2 hours in 50 DEG C of water-baths Afterwards, concentration of hydrogen peroxide is measured, the decomposition rate of hydrogen peroxide is found out.The analysis of concentration of hydrogen peroxide is by utilizing potassium permanganate Oxidimetry carry out.Hydrogen peroxide decomposition rate is found out by following formula, is commented according to determinating reference below Valence.Show the result in table 6,10,11.

Hydrogen peroxide decomposition rate (%/hour)=(concentration of hydrogen peroxide after concentration of hydrogen peroxide-keeping before keeping)/is protected The pipe time

Determine:

Below E:0.050%/hour

G: more than 0.050%/hour~0.075%/below hour

B: more than 0.075%/hour

E and G are set as qualified.

Examples 1 to 10

It joined 5.88 mass % of hydrogen peroxide, 4.12 mass % of nitric acid, 0.25 mass %, 5- ammonia of ammonium acid fluoride In the etching solution of 0.21 mass % of base -1H-TETRAZOLE, 0.03 mass % of phenylurea and water, in such a way that pH value becomes 1.5~2.5, 2- ethylaminoethanol (embodiment 1) as amine compounds, 2-dimethylaminoethanol (embodiment 2), 3 methoxypropyl amine is added (embodiment 3), n-butylamine (embodiment 4), N- methyl-n-butylamine (embodiment 5), isopropanolamine (embodiment 6), 3- amino -1- Propyl alcohol (embodiment 7), N- butylethanolamine (embodiment 8), N, N- dimethylamino -2- propyl alcohol (embodiment 9) and 2- methoxyl group Ethamine (embodiment 10).

By the glass substrate obtained above with the plural layers comprising layers of copper and titanium layer in 35 in above-mentioned etching solution DEG C dipping is etched for 150 seconds, the plural layers sample comprising layers of copper and titanium layer after being etched.For gained sample, lead to Above-mentioned electron microscope observation is crossed, cone angle (°), top CD loss (a, μm), bottom CD loss (b, μm) and trail (c, μ are found out M), Tables 1 and 2 is recorded the result in.

The etching solution for knowing Examples 1 to 10 is that can implement to etch the excellent etching solution for etching of shape.

Comparative example 1~10

In embodiment 4, by the concentration of hydrogen peroxide be set as 3.0 mass % (comparative example 1) and 9.0 mass % (comparative example 2), Concentration of nitric acid is set as 0.70 mass % (comparative example 3) and 9.00 mass % (comparative example 4), 5- amino -1H-TETRAZOLE are set as 0.08 matter Amount % (comparative example 5) and the concentration of 0.60 mass % (comparative example 6), amine compounds (n-butylamine) are set as 0.20 mass % and (compare Example 7) and 11.0 mass % (comparative example 8) and ammonium acid fluoride be set as 0.08 mass % (comparative example 9) and 0.80 mass % (ratio Compared with example 10) when, generation can not measure a problem that etching shape or cloth heading line off.Result is summarized in table 3 and table 4.

Comparative example 11~15

Etching solution is made similarly to Example 1, amine compounds (comparative example 15) are not only added, become 1.5 with pH value~ Hexylamine (comparative example 11), diethylenetriamines (comparative example 12), 2- (1- piperazinyl) ethamine (comparative example 13) is added in 2.5 mode Or triethanolamine (comparative example 14), thus while being etched, but desired etching is unable to get due to the generation of hangover Shape (table 5).

[table 1]

The manufacture of 1 Mitsubishi Gas Chemical Co., Ltd of ※

The manufacture of 2 Wako Pure Chemical Industries, Ltd. of ※

3 ammonium acid fluoride of ※, STELLA CHEMIFA CORPORATION manufacture

4 5- amino of ※ -1H-TETRAZOLE, Wako Pure Chemical Industries, Ltd.'s manufacture

5 amine compounds of ※:

Embodiment 1:2- ethylaminoethanol (Wako Pure Chemical Industries, Ltd.'s manufacture)

Embodiment 2:2- dimethylaminoethanol (Wako Pure Chemical Industries, Ltd.'s manufacture)

Embodiment 3:3- methoxy propanamine (Wako Pure Chemical Industries, Ltd.'s manufacture)

Embodiment 4: n-butylamine (Wako Pure Chemical Industries, Ltd.'s manufacture)

Embodiment 5:N- methyl-n-butylamine (Wako Pure Chemical Industries, Ltd.'s manufacture)

6 phenylurea of ※, Wako Pure Chemical Industries, Ltd.'s manufacture

[table 2]

The manufacture of 1 Mitsubishi Gas Chemical Co., Ltd of ※

The manufacture of 2 Wako Pure Chemical Industries, Ltd. of ※

3 ammonium acid fluoride of ※, STELLA CHEMIFA CORPORATION manufacture

5 amine compounds of ※:

Embodiment 6: isopropanolamine (Wako Pure Chemical Industries, Ltd.'s manufacture)

Embodiment 7:3- amino -1- propyl alcohol (Wako Pure Chemical Industries, Ltd.'s manufacture)

Embodiment 8:N- butylethanolamine (Tokyo Chemical Industry Co., Ltd's manufacture)

Embodiment 9:N, N- dimethylamino -2- propyl alcohol (Wako Pure Chemical Industries, Ltd.'s manufacture)

Embodiment 10:2- methoxyethyl amine (Wako Pure Chemical Industries, Ltd.'s manufacture)

6 phenylurea of ※, Wako Pure Chemical Industries, Ltd.'s manufacture

[table 3]

The manufacture of 1 Mitsubishi Gas Chemical Co., Ltd of ※

The manufacture of 2 Wako Pure Chemical Industries, Ltd. of ※

3 ammonium acid fluoride of ※, STELLA CHEMIFA CORPORATION manufacture

5 n-butylamine of ※, Wako Pure Chemical Industries, Ltd.'s manufacture

6 phenylurea of ※, Wako Pure Chemical Industries, Ltd.'s manufacture

[table 4]

The manufacture of 1 Mitsubishi Gas Chemical Co., Ltd of ※

The manufacture of 2 Wako Pure Chemical Industries, Ltd. of ※

3 ammonium acid fluoride of ※, STELLA CHEMIFA CORPORATION manufacture

5 n-butylamine of ※, Wako Pure Chemical Industries, Ltd.'s manufacture

6 phenylurea of ※, Wako Pure Chemical Industries, Ltd.'s manufacture

[table 5]

The manufacture of 1 Mitsubishi Gas Chemical Co., Ltd of ※

The manufacture of 2 Wako Pure Chemical Industries, Ltd. of ※

3 fluoride ion supply source of ※:

Comparative example 11~13: ammonium acid fluoride, STELLA CHEMIFA CORPORATION manufacture

Comparative example 14: ammonium fluoride, Wako Pure Chemical Industries, Ltd.'s manufacture

5 alkali composition compound of ※:

Comparative example 11: hexylamine, Wako Pure Chemical Industries, Ltd.'s manufacture

Comparative example 12: diethylenetriamines, Wako Pure Chemical Industries, Ltd.'s manufacture

Comparative example 13:2- (1- piperazinyl) ethamine, Wako Pure Chemical Industries, Ltd.'s manufacture

Comparative example 14: triethanolamine, Wako Pure Chemical Industries, Ltd.'s manufacture

6 phenylurea of ※, Wako Pure Chemical Industries, Ltd.'s manufacture

It can be etched within the object time using the embodiment of etching solution of the invention, and the wiring shape after etching Good (table 1,2).

On the other hand, concentration of hydrogen peroxide is less than in the comparative example 1 of desired concentration range, due to etching speed deficiency It can not be etched at the appointed time.In addition, concentration of hydrogen peroxide is more than etching in the comparative example 2 of desired concentration range Speed becomes too fast, and CD loss becomes excessive.Concentration of nitric acid is less than in the comparative example 3 of desired concentration range, due to etching speed Degree is insufficient and can not be etched at the appointed time.Concentration of nitric acid is more than etching speed in the comparative example 4 of desired concentration range Degree becomes too fast, after etching the stipulated time, is routed on substrate and does not remain.Azoles concentration is less than the comparative example 5 of desired concentration range In, etching speed becomes too fast, and CD loss becomes excessive (more than, table 3).

The concentration of azole is more than that can not provide in the comparative example 6 of desired concentration range since etching speed is insufficient It is etched in time.The concentration of amine compounds is less than in the comparative example 7 of desired concentration range, and etching speed becomes too fast, After etching the stipulated time, it is routed on substrate and does not remain.The concentration of amine compounds is more than the comparative example 8 of desired concentration range In, it can not be etched at the appointed time since etching speed is insufficient.The concentration of fluorine compounds is less than desired concentration model In the comparative example 9 enclosed, etching speed is insufficient, generates the etch residue (hangover) of titanium layer, is unable to measure wiring shape.Fluorine compounds Concentration be more than desired concentration range comparative example 10 in, due to the etching speed of titanium layer it is too fast and be routed in generate gap, It is unable to get desired cross sectional shape (more than, table 4).

Using in the comparative example 11~14 of the amine compounds other than the amine compounds of the present application, generates and be originated from titanium layer The trailing phenomenon for etching the titanium layer of delay, is unable to get desired cross sectional shape.Without using in the comparative example 15 of amine compounds, lose Carving speed becomes too fast, etch and be routed on substrate and do not remain after the stipulated time (more than, table 5).

Embodiment 11~15

It joined 5.46 mass % of hydrogen peroxide, 4.66 mass % of nitric acid, 0.34 mass %, 5- ammonia of ammonium acid fluoride In the etching solution of 0.21 mass % of base -1H-TETRAZOLE, 0.03 mass % of phenylurea and water, in such a way that pH value becomes 1.5~2.5, It is added as the 3 methoxypropyl amine (embodiment 11) of amine compounds, methylbutylamine (embodiment 12), 2- amino -1- butane -1- Alcohol (embodiment 13), n-butylamine (embodiment 14), cyclohexylamine (embodiment 15).Later, copper powders are added in the liquid In addition to this 4000ppm and titanium powder 360ppm carries out test similarly to Example 1, implement same as Example 1 comment Valence carries out the evaluation test of Stability of Hydrogen Peroxide.Acquired results are summarized in table 6.

Embodiment 16~30

Glass, silica and silicon nitride etch evaluation is impregnated respectively in etching solution identical with embodiment 11~15 to use Substrate is etched, and for gained sample, carries out corrosive evaluation to each baseplate material.Acquired results are summarized in table 7 ~9.

Comparative example 16,17,19~22

It joined 5.46 mass % of hydrogen peroxide, 4.66 mass % of nitric acid, 0.34 mass %, 5- ammonia of ammonium acid fluoride In the etching solution of 0.21 mass % of base -1H-TETRAZOLE, 0.03 mass % of phenylurea and water, in such a way that pH value becomes 1.5~2.5, The potassium hydroxide (comparative example 16), ammonia (comparative example 17), diethylenetriamines (comparative example 19), 2- (2- as alkali composition is added Amino ethoxy) ethyl alcohol (comparative example 20), dimethylamine (comparative example 21), piperazine (comparative example 22), copper is added in gained liquid Powder 4000ppm and titanium powder 360ppm similarly test with embodiment 11~15.Acquired results are summarized in 10 He of table Table 11.

Comparative example 18

By the nitric acid of comparative example 16 instead of 5.06 mass % of sulfuric acid, positive fourth is added in such a way that pH value becomes 1.5~2.5 Copper powders 4000ppm and titanium powder 360ppm is added in amine in gained liquid, similarly test with comparative example 16.By institute It obtains result and is recorded in table 10.

Comparative example 23,24

By the nitric acid of comparative example 16 instead of 4.66 mass % (comparative example of 5.50 mass % (comparative example 23) of phosphoric acid or acetic acid 24), be added 0.89 mass % of n-butylamine, in gained liquid be added copper powders 4000ppm and titanium powder 360ppm, carry out with than It is similarly tested compared with example 16.Acquired results are recorded in table 11.

Comparative example 25

The ammonium acid fluoride concentration of embodiment 14 is set as 0.55 mass %, in addition to this, is carried out similarly to Example 14 Test.Acquired results are recorded in table 11.

Comparative example 26~35

The corrosion evaluation for impregnating glass respectively in etching solution identical with comparative example 16~25 is etched with substrate, right In gained sample, corrosion rate is calculated respectively and is evaluated.Acquired results are summarized in table 12 and 13.

Comparative example 36~45

The corrosion evaluation of impregnation of silica is lost with substrate respectively in etching solution identical with comparative example 16~25 It carves, for gained sample, calculates corrosion rate respectively and evaluated.Acquired results are summarized in table 14 and 15.

Comparative example 46~55

The corrosion evaluation for impregnating silicon nitride respectively in etching solution identical with comparative example 16~25 is etched with substrate, For gained sample, corrosion rate is calculated respectively and is evaluated.Acquired results are summarized in table 16 and 17.

[table 6]

The manufacture of 1 Mitsubishi Gas Chemical Co., Ltd of ※

The manufacture of 2 Wako Pure Chemical Industries, Ltd. of ※

3 ammonium acid fluoride of ※, STELLA CHEMIFA CORPORATION manufacture

5 amine compounds of ※:

Embodiment 11:3- methoxy propanamine (Wako Pure Chemical Industries, Ltd.'s manufacture)

Embodiment 12: methylbutylamine (manufacture of ALDRICH Co., Ltd.)

Embodiment 13:2- amino -1- butane -1- alcohol (Wako Pure Chemical Industries, Ltd.'s manufacture)

Embodiment 14: n-butylamine (Wako Pure Chemical Industries, Ltd.'s manufacture)

Embodiment 15: cyclohexylamine (Wako Pure Chemical Industries, Ltd.'s manufacture)

6 phenylurea of ※, Wako Pure Chemical Industries, Ltd.'s manufacture

The manufacture of 7 Wako Pure Chemical Industries, Ltd. of ※

The manufacture of 8 Wako Pure Chemical Industries, Ltd. of ※

[table 7]

[table 8]

[table 9]

[table 10]

The manufacture of 1 Mitsubishi Gas Chemical Co., Ltd of ※

2 sour component of ※:

Comparative example 16,17,19,20: nitric acid, Wako Pure Chemical Industries, Ltd.'s manufacture

Comparative example 18: sulfuric acid, Wako Pure Chemical Industries, Ltd.'s manufacture

3 ammonium acid fluoride of ※, STELLA CHEMIFA CORPORATION manufacture

5 alkali cpd of ※:

Comparative example 16: potassium hydroxide, Wako Pure Chemical Industries, Ltd.'s manufacture

Comparative example 17: ammonia, Mitsubishi Gas Chemical Co., Ltd's system

Comparative example 18: n-butylamine, Wako Pure Chemical Industries, Ltd.'s manufacture

Comparative example 19: diethylenetriamines, Wako Pure Chemical Industries, Ltd.'s manufacture

Comparative example 20:2- (2- amino ethoxy) ethyl alcohol, Wako Pure Chemical Industries, Ltd.'s manufacture

6 phenylurea of ※, Wako Pure Chemical Industries, Ltd.'s manufacture

The manufacture of 7 Wako Pure Chemical Industries, Ltd. of ※

The manufacture of 8 Wako Pure Chemical Industries, Ltd. of ※

[table 11]

The manufacture of 1 Mitsubishi Gas Chemical Co., Ltd of ※

2 sour component of ※:

Comparative example 21,22,25: nitric acid, Wako Pure Chemical Industries, Ltd.'s manufacture

Comparative example 23: phosphoric acid, Wako Pure Chemical Industries, Ltd.'s manufacture

Comparative example 24: acetic acid, Wako Pure Chemical Industries, Ltd.'s manufacture

3 ammonium acid fluoride of ※, STELLA CHEMIFA CORPORATION manufacture

5 alkali cpd of ※:

Comparative example 21: dimethylamine, Wako Pure Chemical Industries, Ltd.'s manufacture

Comparative example 22: piperazine, Wako Pure Chemical Industries, Ltd.'s manufacture

Comparative example 23,24,25: n-butylamine, Wako Pure Chemical Industries, Ltd.'s manufacture

6 phenylurea of ※, Wako Pure Chemical Industries, Ltd.'s manufacture

The manufacture of 7 Wako Pure Chemical Industries, Ltd. of ※

The manufacture of 8 Wako Pure Chemical Industries, Ltd. of ※

[table 12]

[table 13]

[table 14]

[table 15]

[table 16]

[table 17]

It can be etched within the desired time using the embodiment 11~30 (table 6~9) of etching solution of the invention, and Wiring shape after etching is good.In addition, judging that the corrosion rate of glass, silica or silicon nitride and hydrogen peroxide decompose speed Degree is adequately suppressed, and metal concentration, which is got higher, also can be used.

On the other hand, using common alkali composition, that is, potassium hydroxide, the comparative example 16,17,26,27,36,37,46,47 of ammonia In (table 10, table 12~17), the decomposition rate of glass, the corrosion rate of silica and hydrogen peroxide is big, is not available.Make Use sulfuric acid as acid comparative example 18 (table 10) in, etching speed becomes too fast, etch the stipulated time after, the wiring on substrate disappears It loses.

Use amine compounds other than the present application as in the comparative example 19,20,21,22 of alkali composition, hydrogen peroxide Stability be substantially reduced and be not available.In turn, in comparative example 19, the etch residue (hangover) of titanium layer is generated, can not be measured Wiring shape (table 10,11).

Use phosphoric acid as in the comparative example 23,33,43,53 (table 11~17) of sour component, titanium powder in etching solution not Dissolution, can not carry out the evaluation as etching solution.

Use acetic acid as in the comparative example 24,34,44,54 (table 11~14) of acid ingredient described in patent document 2, nothing PH is adjusted to defined range by method, titanium powder can not be made to be dissolved in etching solution.

The concentration of fluorine compounds is more than glass, titanium dioxide in the comparative example 35,45,55 (table 12~17) of desired concentration The corrosion rate of silicon or silicon nitride obviously becomes faster and is not available.

Industrial availability

Etching solution of the invention can be suitable for comprising as main component with copper layers of copper as main component and with titanium The plural layers of titanium layer, the etching that plural layers made of layers of copper are especially laminated on titanium layer.Use the etching side of the etching solution Method can be etched the wiring with the plural layers comprising layers of copper and titanium layer together, and the cloth after etching can be made linear Shape be it is good, therefore, high production rate can be reached.In addition, the consumption of hydrogen peroxide is few, it is economically excellent.

Claims

1. a kind of etching solution, for the etching solution for etching the plural layers being laminated on substrate, the substrate use is selected from One or more of glass, silica and silicon nitride, the plural layers comprising being with copper layers of copper as main component and with titanium The titanium layer of main component,

The etching solution is the aqueous solution comprising following ingredient and pH value is 1.5~2.5:

(A) concentration of hydrogen peroxide is 4.5~7.5 mass %；

(B) concentration of nitric acid is 0.8~6 mass %；

(C) concentration of fluorine compounds is 0.2~0.5 mass %；

(D) concentration of azole is 0.14~0.3 mass %；

(E) concentration of amine compounds be 0.4~10 mass %, the amine compounds be selected from have 1 or more optionally by methoxy The alkanamine (E1) of the alkyl of the carbon number 2~5 of straight-chain replaced base or branched has 1 or 2 straight-chains or branched Carbon number 2~5 hydroxy alkyl and any alkanol with 1 or the alkyl of the carbon number 2~5 of 2 straight-chains or branched Amine (E2), carbon number 2~5 with straight-chain or branched alkylidene diamines (E3) and cyclohexylamine (E4) in a kind with On；With

(F) concentration of stabilizer of hydrogen peroxide is 0.005~0.1 mass %,

Wherein, in the etching solution add copper 4000ppm and titanium 360ppm and in 50 DEG C save 2 hours when the etching solution in Hydrogen peroxide stability be 0.075%/hour below.

2. etching solution according to claim 1, wherein (C) fluorine compounds are to be fluorinated selected from hydrofluoric acid, ammonium fluoride and acid One or more of ammonium.

3. etching solution according to claim 1, wherein (D) azole is 5- amino -1H-TETRAZOLE.

4. etching solution according to claim 1, wherein (E) amine compounds be selected from isopropanolamine, 3- amino -1- propyl alcohol, N- butylethanolamine, N, N- dimethylamino -2- propyl alcohol, 2- methoxyethyl amine, cyclohexylamine, n-butylamine, dibutyl amine, tert-butylamine, N- methyl-n-butylamine, 1,4- diaminobutane, 2- amino-n-butyl alcohol, 5- amino -1- amylalcohol, 3 methoxypropyl amine, 2- diformazan One or more of base ethylaminoethanol and 2- ethylaminoethanol.

5. etching solution according to claim 1, wherein (F) stabilizer of hydrogen peroxide is selected from phenylurea and phenolsulfonic acid One or more of.

6. etching solution according to claim 1, wherein CD loss in top is for 2.5 μm hereinafter, CD loss in bottom is 1.5 μm It is below 0.4 μm or less with hangover.

7. etching solution according to claim 1, wherein the corrosion rate of glass is 60nm/ minutes or less.

8. etching solution according to claim 1, wherein the corrosion rate of silica and silicon nitride is/ minute with Under.

9. etching solution according to claim 1 is comprising using copper layers of copper as main component and using titanium as main component Titanium layer plural layers appropriate etching period be 80 seconds~140 seconds.

10. etching solution according to claim 1, wherein be laminated in using in glass, silica and silicon nitride Plural layers on a kind or more of substrate be with stacking on titanium titanium layer as main component with copper layers of copper as main component and At.

11. etching solution according to claim 1 or 2, wherein (E) amine compounds are selected from 3 methoxypropyl amine, N- methyl- One or more of n-butylamine, n-butylamine, 2- amino-n-butyl alcohol, cyclohexylamine, N- butylethanolamine, 5- amino -1- amylalcohol.

12. etching solution according to claim 1 or 2, wherein the content of (E) amine compounds in the etching solution be 2~ 8 mass %.

13. etching solution according to claim 1 or 2, wherein the content of (D) azole in the etching solution be 0.15~ 0.25 mass %.

14. a kind of comprising with copper layers of copper as main component and with the etching side of the plural layers of titanium titanium layer as main component Method, which is characterized in that connect etching solution described in any one of the plural layers being laminated on substrate and claim 1~13 Touching, the substrate are used selected from one or more of glass, silica and silicon nitride, and the plural layers include based on copper Want the layers of copper of ingredient and with titanium titanium layer as main component.