WO2019064506A1 - Etching solution and etching concentrate for multilayer film, and etching method - Google Patents

Etching solution and etching concentrate for multilayer film, and etching method Download PDF

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WO2019064506A1
WO2019064506A1 PCT/JP2017/035529 JP2017035529W WO2019064506A1 WO 2019064506 A1 WO2019064506 A1 WO 2019064506A1 JP 2017035529 W JP2017035529 W JP 2017035529W WO 2019064506 A1 WO2019064506 A1 WO 2019064506A1
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acid
mass
etching solution
etching
total amount
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PCT/JP2017/035529
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French (fr)
Japanese (ja)
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祐二 白濱
真 着能
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パナソニックＩｐマネジメント株式会社
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Priority to JP2019544111A priority Critical patent/JP6793312B2/en
Priority to PCT/JP2017/035529 priority patent/WO2019064506A1/en
Priority to CN201780094862.7A priority patent/CN111094627B/en
Publication of WO2019064506A1 publication Critical patent/WO2019064506A1/en

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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F1/00—Etching metallic material by chemical means
    • C23F1/10—Etching compositions
    • C23F1/14—Aqueous compositions
    • C23F1/16—Acidic compositions
    • C23F1/18—Acidic compositions for etching copper or alloys thereof
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F1/00—Etching metallic material by chemical means
    • C23F1/10—Etching compositions
    • C23F1/14—Aqueous compositions
    • C23F1/16—Acidic compositions
    • C23F1/26—Acidic compositions for etching refractory metals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
    • H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
    • H01L21/308—Chemical or electrical treatment, e.g. electrolytic etching using masks

Definitions

  • the present invention relates to an etching solution for a multilayer film, an etching solution and an etching method used for etching a multilayer film of copper and titanium used for wiring of flat panel displays such as liquid crystal and organic EL.
  • Aluminum has been used as a wiring material for TFTs (Thin Film Transistors) of flat panel displays (FPDs) such as liquid crystal and organic EL (Electro-Luminescence).
  • FPDs Thin Film Transistors
  • LCDs flat panel displays
  • Electro-Luminescence Electro-Luminescence
  • large-screen, high-definition FPDs have become widespread, and wiring materials to be used have been required to have lower resistance than aluminum. Therefore, copper having a resistance lower than that of aluminum has recently been used as a wiring material.
  • adhesion to the substrate and diffusion to the semiconductor substrate. That is, in the case of using for gate wiring, adhesion may not be sufficient between substrates such as glass even when using a sputtering method that is considered to have a relatively high impact energy to the substrate. In addition, in the case of using in source / drain wiring, there is a problem that the adhered copper is diffused to the underlying silicon, and the electrical design value of the semiconductor is changed.
  • a multilayer structure was employed in which a molybdenum film is first formed on a semiconductor substrate, and a copper film is formed thereon.
  • titanium has been adopted as a base layer of a copper film in order to further ensure the isolation and adhesion to the base.
  • the wiring of FPD is formed by wet etching a multilayer film formed by sputtering. This is because a large area can be formed at once, which makes it possible to shorten the process.
  • the following points are considered important for the etching solution for wet etching of the wiring.
  • (2) The wiring cross section after processing is a forward taper of a predetermined angle.
  • the etching rate does not change by containing copper ions (the bath life is long). (4) There should be little generation of precipitates.
  • Patent Document 1 as an etching solution for a copper / titanium laminated film, (A) hydrogen peroxide, (B) Nitric acid, (C) ammonium fluoride and / or ammonium acid fluoride as a fluoride ion source, (D) 5-amino-1H-tetrazole, (E) containing tetraalkylammonium hydroxide and / or (hydroxyalkyl) trialkylammonium hydroxide as quaternary ammonium hydroxide and (F) phenyl urea and / or phenol sulfonic acid, An etchant for a multilayer film having a pH of 1.5 to 2.5 is disclosed.
  • Patent Document 1 It has been shown that the etching solution of Patent Document 1 can be etched in a suitable range with respect to top CD loss, bottom CD loss, barrier film tailing, taper angle, etc. which are indicators of side etching of the lower titanium film and upper copper film. There is.
  • the range (bath life) in which the above-mentioned characteristics can be maintained is set to 4000 ppm.
  • the amount of metal ions exceeds this value, decomposition of hydrogen peroxide and nitric acid proceeds, and the performance can not be maintained.
  • the present invention is conceived to solve the above-mentioned problems, and even if the metal ion concentration in the etching solution becomes high, the change in etching performance can be kept within an acceptable range, and it takes time for composition control. It is an object of the present invention to provide a copper / titanium etching solution which can be reduced.
  • the etching solution for a multilayer film according to the present invention is An etching solution for etching a multilayer film of copper and titanium, (A) hydrogen peroxide, (B) a fluorine ion supply source, (C) azoles, (D) hydrogen peroxide stabilizer, (E) with an organic acid, (F) amines, (G) contains water,
  • the organic acid is selected from methanesulfonic acid and lactic acid based on the total amount of etching solution.
  • the methanesulfonic acid contains 0.2% by mass to 1.5% by mass with respect to the total amount of the etching solution
  • at least one type of organic acid of lactic acid, succinic acid, glutaric acid and malonic acid is used in combination,
  • lactic acid is contained in the organic acid used in combination
  • the lactic acid is 2.0% by mass to 10.0% by mass with respect to the total amount of the etching solution
  • succinic acid is contained in the organic acid used in combination
  • the succinic acid is 4.5% by mass to 5.5% by mass with respect to the total amount of the etching solution
  • glutaric acid is contained in the organic acid used in combination
  • the glutaric acid is 9.5% by mass to 10.5% by mass with respect to the total amount of the etching solution
  • malonic acid is contained in the organic acid used in combination
  • the malonic acid is 4.5% by mass to 5.5% by mass with respect to the total amount of the etching solution
  • the organic acid is only lactic acid
  • the etching method according to the present invention is Bringing the above etching solution into contact with a substrate to be treated in which a resist pattern is disposed on a multilayer film of copper and titanium;
  • the method is characterized by including the step of maintaining the contact state for a predetermined time.
  • the etching solution according to the present invention can maintain each parameter of the side etching in a suitable range even if the metal ion concentration in the etching solution is 8,000 ppm. Therefore, even when etching a substrate with a thick copper film, it is possible to carry out the conventional composition control (determination of the amount and timing of addition of components, total amount, etc.).
  • etching solution for copper and titanium multilayer films according to the present invention will be described below.
  • the following description shows one embodiment of the etching solution according to the present invention, and the following embodiments and examples may be modified without departing from the spirit of the present invention.
  • the numerical range is indicated by “A to B”, it means “more than A and less than B”. That is, it means a large range including the numerical value A and a small range including the numerical value B.
  • the etching solution for a multilayer film according to the present invention contains hydrogen peroxide, a fluorine ion supply source, an azole, a hydrogen peroxide stabilizer, an organic acid, an amine and water. Each component will be described in detail below.
  • ⁇ Hydrogen peroxide> copper is oxidized to form copper oxide (CuO), which is dissolved by an acid (organic acid). Hydrogen peroxide is used as an oxidizing agent to oxidize copper. Hydrogen peroxide is preferably 4.0% by mass to 8.8% by mass, more preferably 5.0% by mass to 7.0% by mass, and 5.5% by mass to 6.5% by mass of the etching solution. % Is most preferable.
  • Fluoride ion is useful for dissolving titanium.
  • the source of fluorine ions is not particularly limited as long as fluorine is ionized in the etching solution. Hydrofluoric acid, ammonium fluoride, ammonium hydrogen fluoride and the like can be suitably used. In particular, ammonium fluoride (NH 4 F: CAS No. 12125-01-8) can be suitably used.
  • the fluorine ion source corrodes the substrate itself if the content is too high to corrode the glass. 0.2% by mass to 1.0% by mass is preferable based on the total amount of the etching solution.
  • the etching solution for a multilayer film according to the present invention contains azoles in order to suppress the etching rate of Cu.
  • azoles triazoles, tetrazoles, imidazoles, thiazoles etc. can be used suitably. More specifically, the following can be listed.
  • triazoles 1H-benzotriazole, 5-methyl-1H-benzotriazole, 3-amino-1H-triazole and the like can be suitably used.
  • tetrazole 1H-tetrazole, 5-methyl-1H-tetrazole, 5-phenyl-1H-tetrazole, 5-amino-1H-tetrazole and the like can be suitably used.
  • imidazoles 1H-imidazole, 1H-benzimidazole and the like can be suitably used.
  • thiazoles 1,3-thiazole, 4-methylthiazole and the like can be suitably used.
  • 5-amino-1H-tetrazole (CAS No. 4418-61-5: hereinafter also referred to as "5A1HT”) is particularly preferable.
  • the content of these azoles is preferably 0.005% by mass to 1.0% by mass, more preferably 0.01% by mass to 0.5% by mass, and most preferably 0.01% by mass with respect to the total amount of the etching solution. It is preferable to contain up to 0.10 mass%.
  • the etching solution for a multilayer film according to the present invention utilizes hydrogen peroxide as an oxidant. Since hydrogen peroxide is self-decomposable, a decomposition inhibitor that suppresses its decomposition is added. Hydrogen peroxide decomposition inhibitors are also referred to as hydrogen peroxide stabilizers.
  • urea-based hydrogen peroxide stabilizers such as phenylurea, allylurea, 1,3-dimethylurea and thiourea, phenylacetic acid amide, phenylethylene glycol, 1-propanol, Lower alcohols such as 2-propanol are often used.
  • BG exerts a remarkable effect of suppressing the decomposition of hydrogen peroxide even when the Cu concentration is as high as 8,000 ppm or more.
  • BG is effective when it is added to the etching solution at a certain level or more, and even if it is added in a large amount, the effect is saturated. If the amount of other necessary components can be secured, the effect as an etching solution can be exhibited even if it is added in a large amount. However, adding more BG increases the cost. Considering the effect and the price, there is no point in adding more than 5.0% by mass to the total amount of the etching solution.
  • BG as a hydrogen peroxide stabilizer may be contained in an amount of 0.1% by mass to 5.0% by mass, based on the total amount of the etching solution, from 0.5% by mass to 2.5% by mass. It is more preferable that the content is 0.7% by mass to 1.5% by mass.
  • phenyl urea and hydrogen peroxide react with each other to cause azoles and excess, when used conventionally as a hydrogen peroxide decomposition inhibitor. A precipitate different from the hydrogen oxide reactant was produced. On the other hand, BG does not generate such precipitates. Therefore, BG is a suitable hydrogen peroxide stabilizer also in terms of the formation of precipitates.
  • Organic acid serves to etch the copper film and to adjust the taper angle of the cross section of the etched interconnection. In addition, it is considered that it also has a function of suppressing the decomposition of hydrogen peroxide to some extent.
  • An acidic organic acid is used as the organic acid.
  • organic acid examples include aliphatic carboxylic acids having 1 to 18 carbon atoms, aromatic carboxylic acids having 6 to 10 carbon atoms, amino acids having 1 to 10 carbon atoms, and sulfonic acids having 1 to 10 carbon atoms. .
  • Examples of aliphatic carboxylic acids having 1 to 18 carbon atoms include formic acid, acetic acid, propionic acid, lactic acid, diglycolic acid, pyruvic acid, malic acid, butyric acid, hydroxybutyric acid, tartaric acid, succinic acid, malic acid, maleic acid and fumaric acid , Valeric acid, glutaric acid, itaconic acid, adipic acid, caproic acid, citric acid, propane tricarboxylic acid, trans-aconitic acid, enanthate, caprylic acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linole Preferred are acid and linolenic acid.
  • Preferred examples of the aromatic carboxylic acid having 6 to 10 carbon atoms include benzoic acid, salicylic acid, mandelic acid, phthalic acid, isophthalic acid and terephthalic acid.
  • amino acid having 1 to 10 carbon atoms carbamic acid, alanine, glycine, asparagine, aspartic acid, sarcosine, serine, glutamine, glutamic acid, 4-aminobutyric acid, iminodibutyric acid, arginine, leucine, isoleucine, nitrilotriacetic acid, etc. Is preferably mentioned.
  • sulfonic acid having 1 to 10 carbon atoms methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid and the like are preferable.
  • lactic acid, succinic acid, glutaric acid, malonic acid and methanesulfonic acid can be suitably used as the acidic organic acid.
  • Methanesulfonic acid (CAS number: 75-75-2) is not used alone, but is always used in combination with other acidic organic acids.
  • the amount of methanesulfonic acid is preferably 0.2% by mass to 1.5% by mass with respect to the total amount of the etching solution.
  • the acid organic acid to be used in combination is lactic acid (mixed state (DL-lactic acid) CAS number: 50-21-5), the range of 2.0 mass% to 10.0 mass% of lactic acid with respect to the total amount of the etching solution is preferable.
  • L-lactic acid or D-lactic acid may be used alone as lactic acid.
  • succinic acid (CAS No. 11015-6)
  • succinic acid is preferably in the range of 4.5% by mass to 5.5% by mass with respect to the total amount of the etching solution.
  • the acid organic acid used in combination is glutaric acid (CAS number: 110-94-1), and the glutaric acid is preferably in the range of 9.5% by mass to 10.5% by mass with respect to the total amount of the etching solution.
  • the acid organic acid used in combination is malonic acid (CAS number: 141-82-2)
  • the malonic acid is preferably in the range of 4.5% by mass to 5.5% by mass with respect to the total amount of the etching solution.
  • Lactic acid can be used alone.
  • the range of 4.0% by mass to 5.0% by mass is preferable with respect to the total amount of the etching solution.
  • the amine compound is responsible for adjusting the pH of the etching solution.
  • the amine compound one having 2 to 10 carbon atoms can be suitably used. More specifically, ethylenediamine, trimethylenediamine, tetramethylenediamine, 1,2-propanediamine, 1,3-propanediamine, N, N-dimethyl-1,3-propanediamine, N, N-diethyl-1 , 3-propanediamine, 1,3-diaminobutane, 2,3-diaminobutane, pentamethylenediamine, 2,4-diaminopentane, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, N-methyl Ethylenediamine, N, N-dimethylethylenediamine, trimethylethylenediamine, N-ethylethylenediamine, N, N-diethylethylenediamine, triethyl
  • triisopropanolamine (CAS No. 122-20-3) is particularly preferable.
  • the amine compound is preferably contained in an amount of 0.5% by mass to 3.0% by mass, more preferably 0.6% by mass to 2.5% by mass, based on the total amount of the etching solution. It is most preferable if it is 2.0 mass%.
  • the etching solution for dilution is additionally added to the usual etching solution for multilayer film so that the Cu ion concentration becomes about 2,000 ppm to 4,000 ppm. Because the decomposition rate of hydrogen peroxide is increased, the hydrogen peroxide concentration is reduced. However, since the etching solution according to the present invention suppresses the decomposition rate of hydrogen peroxide, it is not necessary to add the etching solution for dilution of Cu ions even when the Cu ion concentration becomes higher. More specifically, it is not necessary to add an etching solution for dilution to a Cu concentration of the etching solution of at least 8,000 ppm.
  • ⁇ Others> water and various additives generally used in the range that does not inhibit the etching performance may be added to the etching solution for a multilayer film of the present invention. Since water is intended for precision processing, it is desirable that there be no foreign matter present. Pure water or ultrapure water is preferred. Further, it goes without saying that the range of the content ratio of each component described above is appropriately adjusted to be 100% by mass in the total amount of the etching solution.
  • the etching solution for a multilayer film according to the present invention is preferably used in the range of pH 1 to 4, more preferably pH 1.5 to 2.5. Also, the etching solution can be used between 20 ° C. and 60 ° C. The temperature is more preferably 30 ° C. to 55 ° C., and most preferably 35 ° C. to 50 ° C.
  • Hydrogen peroxide is used in the multilayer film etching solution according to the present invention. Hydrogen peroxide self decomposes. Therefore, the etching solution contains a hydrogen peroxide decomposition inhibitor. However, for storage, hydrogen peroxide (or hydrogen peroxide solution) and other liquids may be stored separately. Alternatively, only the hydrogen peroxide (or hydrogen peroxide water), water, and the raw material from which copper ions are removed (referred to as "etching liquid raw material”) may be stored collectively. In addition, the thing of a liquid and the thing of forms other than a liquid may exist in an etching liquid raw material. That is, the etching solution for a multilayer film according to the present invention may be completed by combining an etching solution raw material, water, and hydrogen peroxide (or hydrogen peroxide water).
  • the etching solution raw material and water may be mixed to prepare a solution of the etching liquid raw material.
  • This solution may be water in a proportion smaller than the proportion of water in the etching solution shown in the examples described later.
  • the solution of the etching solution raw material produced with the etching solution raw material and water is called "etching concentrate.”
  • the etching solution completed by mixing hydrogen peroxide in a predetermined ratio may be called “complete etching solution”.
  • the etching concentrate is convenient for storage and transfer since it has a smaller volume due to the absence of a portion of hydrogen peroxide and water as compared to a complete etching solution. Therefore, the etching solution for a multilayer film (complete etching solution) of the present invention may be completed by combining the etching solution, water and hydrogen peroxide.
  • the etching concentrate is composed of the components obtained by removing hydrogen peroxide from the complete etching solution according to the present invention, and adding hydrogen peroxide and water to a predetermined concentration completes the etching solution of the present invention.
  • the etching concentrate can be expressed by defining the composition ratio of each component when the hydrogen peroxide is a complete etching solution prepared to have a predetermined concentration.
  • the water of the etching concentrate may have an amount sufficient to dissolve the etching solution raw material. That is, considering that hydrogen peroxide is supplied as a hydrogen peroxide solution which is an aqueous solution, the etching solution for a multilayer film of the present invention should be completed by combining the etching concentrate, water, and hydrogen peroxide water. Can.
  • each component ratio of the etching concentrate is represented by a ratio to the total amount when the etching solution is completed. Therefore, the sum of the respective components of the etching concentrate does not reach 100% by mass.
  • the object using the etching solution for a multilayer film according to the present invention is that titanium or a titanium alloy (also referred to simply as “titanium” including titanium alloy) is a lower layer, and copper or a copper alloy (also referred to simply as "copper” including a copper alloy) Is a multilayer film of copper / titanium with an upper layer.
  • the thickness of the lower layer titanium is thinner than the thickness of the upper layer copper. Assuming that the thickness of the lower layer is t0 and the thickness of the upper layer is t1, the range of t1 / t0 is in the range of 16 to 32.
  • the etchant for a multilayer film according to the present invention can be stored for a long time by storing hydrogen peroxide, an etching solution raw material and water separately during storage. Then, in actual use, these are mixed to complete the etching solution.
  • the method of preparation is not limited as long as the concentration of hydrogen peroxide finally reaches a predetermined concentration.
  • an etching concentrate is prepared by mixing a predetermined amount of water with the etching solution raw material.
  • Hydrogen peroxide is usually supplied as a hydrogen peroxide solution having a concentration higher than the hydrogen peroxide concentration of the etching solution for a multilayer film according to the present invention. Therefore, a predetermined amount of hydrogen peroxide solution and etching concentrate (which may further contain water) are prepared.
  • This process may be called a process of preparing an etching solution for multilayer film. Note that this step does not have to be performed immediately before etching, and etching may be performed using an etching solution that has been prepared in advance including hydrogen peroxide.
  • the etching solution When the etching is performed, the etching solution is used under the conditions of pH 1 to 4 and 20 ° C. to 60 ° C. as described above. Therefore, it is desirable that the object to be etched (substrate to be processed) be also preheated to this temperature.
  • the method of bringing the substrate to be treated into contact with the etching solution is not particularly limited. As in the shower type, the etching solution may be dispersed to the substrate to be processed from above, or a method of dipping the substrate to be processed in a pool of etching solution may be used. This may be called a step of bringing the etching solution for multilayer film into contact with the substrate to be treated.
  • the etching must maintain the contact between the substrate to be processed and the etching solution for a predetermined time. This is a step of maintaining the contact between the substrate to be processed and the etching solution for a predetermined time.
  • the substrate to be treated is a substrate in a state in which a titanium layer and a copper layer are laminated on a base material such as glass, and a resist pattern for pattern formation is formed on this laminated film.
  • titanium was deposited to a thickness of 25 nm by sputtering on a glass substrate, copper was subsequently deposited to a thickness of 600 nm, and a Cu / Ti multilayer film sample was produced. .
  • a resist patterned in a wiring shape was formed on this copper film, and used as a substrate for taper angle evaluation. That is, the substrate comprises a glass substrate, a titanium film, a copper film thereon, and a patterned resist layer on the copper film.
  • Etching was performed by immersing the substrate in an etching solution for the time of just etching. After the sample after etching was washed and dried, the wiring portion was cut at right angles to the wiring direction, and the cut surface was observed.
  • FIG. 1 A schematic view of the cross-sectional shape is shown in FIG. Referring to FIG. 1, the cut surface is formed of a glass substrate 10, a titanium layer 12, a copper layer 14, and a resist layer 16.
  • a virtual surface 18 perpendicular to the glass substrate 10 formed between the end 16 a of the resist layer 16 and the glass substrate 10 is an ideal edge surface.
  • the actual edge surface has different etching rates on the upper and lower surfaces of the film, and is an inclined surface as shown in the figure.
  • the copper layer 14 directly below the end 16 a of the resist layer 16 is not present because the etching proceeds. Therefore, the end 16a of the resist layer 16 is wedge-shaped.
  • the copper layer 14 is deeply eroded from the virtual surface 18 in a direction closer to the resist layer 16 than in a direction closer to the glass substrate 10.
  • the titanium layer 12 which is the lower layer of the copper layer 14 has a slight degree of erosion from the virtual surface 18 due to the difference in etching rate with copper.
  • top CD critical dimension: line width
  • bottom CD loss The angle ⁇ of the slope from the end 14 ba of the lower surface 14 b of the copper layer 14 to the end 14 aa of the upper surface 14 a.
  • the top CD loss, the bottom CD loss, and the taper angle are represented by symbols “a”, “b”, and “ ⁇ ”, respectively. Since the top CD loss and the bottom CD loss usually occur on both sides of the line width, a value twice as large as the measured value is used as the evaluation value. That is, if the top CD loss is 0.5 ⁇ m when observing the cross section of a certain sample, the evaluation value of the top CD loss is 1.0 ⁇ m. However, here, the measured values of the top CD loss a and the bottom CD loss b of only one side of the wiring are shown in the table.
  • the top CD loss a is preferably 0.5 ⁇ m to 2.0 ⁇ m, and the bottom CD loss b is preferably 0.3 ⁇ m to 1.0 ⁇ m.
  • the taper angle ⁇ may be 30 ° to 80 °.
  • the “glass corrosion rate” was determined by measuring the level difference between the eroded portion and the non-eroded portion of the sample subjected to the etching experiment with a step measuring device.
  • the unit is nm / min.
  • the glass corrosion rate may be 30 to 60 nm / min.
  • “Evaluation Cu concentration” is a case where etching is performed while dissolving a predetermined amount of copper in the etching solution as a sample, and the taper angle ⁇ , the top CD loss a, or the bottom CD loss b is out of the preferable range Alternatively, the concentration immediately before the concentration at which etching could not be continued due to other causes was used. If the "evaluation Cu concentration" is high, it may be said that the bus life is long.
  • Example 1 As an acidic organic acid, 0.3% by mass of methanesulfonic acid, 9.0% by mass of lactic acid, As an amine compound, 0.75% by mass of triisopropanolamine, As a hydrogen peroxide stabilizer 0.90% by mass of 2-butoxyethanol, As azoles, 0.04 mass% of 5-amino-1H-tetrazole As a fluoride ion source, 0.4 mass% of ammonium fluoride The etching liquid raw material which consists of these is mixed with 72.04 mass% of water, and the etching concentrate was prepared. In addition, each component ratio in an etching concentrate is mixed with the hydrogen-peroxide solution mentioned later, and is represented by the ratio with respect to the total amount when the etching liquid is completed. The same applies to the following examples and comparative examples.
  • the etching concentrate is mixed with 16.57% by weight of 35% hydrogen peroxide water (5.8% by weight of hydrogen peroxide and 10.77% by weight of water based on the total amount of etching solution), and the hydrogen peroxide concentration is A 5.8% by mass etchant was prepared.
  • the total amount of water is 82.81% by mass.
  • the solution temperature was 35 ° C.
  • the concentration of each component in the entire etching solution and the result of each evaluation item are shown in Table 1. In Table 1, the total amount of water is described as "the balance”. The same applies to Table 2 below.
  • Example 2 As an acidic organic acid, 1.0% by mass of methanesulfonic acid, 2.7% by mass of lactic acid, As an amine compound, 2.0% by mass of triisopropanolamine, As a hydrogen peroxide stabilizer 0.90% by mass of 2-butoxyethanol, As azoles, 0.04 mass% of 5-amino-1H-tetrazole As a fluoride ion source, 0.8 mass% of ammonium fluoride The etching liquid raw material which consists of these is mixed with 75.99 mass% of water, and the etching concentrate was prepared.
  • the etching concentrate is mixed with 16.57% by weight of 35% hydrogen peroxide water (5.8% by weight of hydrogen peroxide and 10.77% by weight of water based on the total amount of etching solution), and the hydrogen peroxide concentration is A 5.8% by mass etchant was prepared.
  • the total amount of water is 86.76% by mass.
  • the solution temperature was 35 ° C.
  • the concentration of each component in the entire etching solution and the result of each evaluation item are shown in Table 1.
  • Example 3 As an acidic organic acid, 0.3% by mass of methanesulfonic acid, 5.0% by mass of succinic acid, As an amine compound, 0.75% by mass of triisopropanolamine, As a hydrogen peroxide stabilizer 0.90% by mass of 2-butoxyethanol, As azoles, 0.04 mass% of 5-amino-1H-tetrazole As a fluoride ion source, 0.4 mass% of ammonium fluoride The etching liquid raw material which consists of these is mixed with 76.04 mass% of water, and the etching concentrate was prepared.
  • the etching concentrate is mixed with 16.57% by weight of 35% hydrogen peroxide water (5.8% by weight of hydrogen peroxide and 10.77% by weight of water based on the total amount of etching solution), and the hydrogen peroxide concentration is A 5.8% by mass etchant was prepared.
  • the total amount of water is 86.81% by mass.
  • the solution temperature was 35 ° C.
  • the concentration of each component in the entire etching solution and the result of each evaluation item are shown in Table 1.
  • Example 4 As an acidic organic acid, 0.5% by mass of methanesulfonic acid, 10.0% by mass of glutaric acid, As an amine compound, 0.75% by mass of triisopropanolamine, As a hydrogen peroxide stabilizer 0.90% by mass of 2-butoxyethanol, As azoles, 0.04 mass% of 5-amino-1H-tetrazole As a fluoride ion source, 0.4 mass% of ammonium fluoride The etching liquid raw material which consists of these is mixed with 70.84 mass% of water, and the etching concentrate was prepared.
  • the etching concentrate is mixed with 16.57% by weight of 35% hydrogen peroxide water (5.8% by weight of hydrogen peroxide and 10.77% by weight of water based on the total amount of etching solution), and the hydrogen peroxide concentration is A 5.8% by mass etchant was prepared.
  • the total amount of water is 81.61% by mass.
  • the solution temperature was 35 ° C.
  • the concentration of each component in the entire etching solution and the result of each evaluation item are shown in Table 1.
  • Example 5 As an acidic organic acid, 0.3% by mass of methanesulfonic acid, 5.0% by mass of malonic acid, As an amine compound, 1.5% by mass of triisopropanolamine, As a hydrogen peroxide stabilizer 0.90% by mass of 2-butoxyethanol, As azoles, 0.04 mass% of 5-amino-1H-tetrazole As a fluoride ion source, 0.4 mass% of ammonium fluoride The etching liquid raw material which consists of these is mixed with 75.29 mass% of water, and the etching concentrate was prepared.
  • the etching concentrate is mixed with 16.57% by weight of 35% hydrogen peroxide water (5.8% by weight of hydrogen peroxide and 10.77% by weight of water based on the total amount of etching solution), and the hydrogen peroxide concentration is A 5.8% by mass etchant was prepared.
  • the total amount of water is 86.06% by mass.
  • the solution temperature was 35 ° C.
  • the concentration of each component in the entire etching solution and the result of each evaluation item are shown in Table 1.
  • Example 6 As an acidic organic acid, 4.5% by mass of lactic acid, As an amine compound, 0.75% by mass of triisopropanolamine, As a hydrogen peroxide stabilizer 0.90% by mass of 2-butoxyethanol, As azoles, 0.04 mass% of 5-amino-1H-tetrazole As a fluoride ion source, 0.4 mass% of ammonium fluoride
  • the etching liquid raw material which consists of these is mixed with 76.84 mass% of water, and the etching concentrate was prepared.
  • the etching concentrate is mixed with 16.57% by weight of 35% hydrogen peroxide water (5.8% by weight of hydrogen peroxide and 10.77% by weight of water based on the total amount of etching solution), and the hydrogen peroxide concentration is A 5.8% by mass etchant was prepared.
  • the total amount of water is 87.61% by mass.
  • the solution temperature was 35 ° C.
  • the concentration of each component in the entire etching solution and the result of each evaluation item are shown in Table 1.
  • the etching concentrate is mixed with 16.57% by weight of 35% hydrogen peroxide water (5.8% by weight of hydrogen peroxide and 10.77% by weight of water based on the total amount of etching solution), and the hydrogen peroxide concentration is A 5.8% by mass etchant was prepared.
  • the total amount of water is 67.14% by mass.
  • the solution temperature was 35 ° C.
  • the concentration of each component in the entire etching solution and the result of each evaluation item are shown in Table 2.
  • the etching concentrate is mixed with 16.57% by weight of 35% hydrogen peroxide water (5.8% by weight of hydrogen peroxide and 10.77% by weight of water based on the total amount of etching solution), and the hydrogen peroxide concentration is A 5.8% by mass etchant was prepared.
  • the total amount of water is 77.34% by mass.
  • the solution temperature was 35 ° C.
  • the concentration of each component in the entire etching solution and the result of each evaluation item are shown in Table 2.
  • the etching concentrate is mixed with 16.57% by weight of 35% hydrogen peroxide water (5.8% by weight of hydrogen peroxide and 10.77% by weight of water based on the total amount of etching solution), and the hydrogen peroxide concentration is A 5.8% by mass etchant was prepared.
  • the total amount of water is 77.59% by mass.
  • the solution temperature was 35 ° C.
  • the concentration of each component in the entire etching solution and the result of each evaluation item are shown in Table 2.
  • the etching concentrate is mixed with 16.57% by weight of 35% hydrogen peroxide water (5.8% by weight of hydrogen peroxide and 10.77% by weight of water based on the total amount of etching solution), and the hydrogen peroxide concentration is A 5.8% by mass etchant was prepared.
  • the total amount of water is 91.61% by mass.
  • the solution temperature was 35 ° C.
  • the concentration of each component in the entire etching solution and the result of each evaluation item are shown in Table 2.
  • the etching concentrate is mixed with 16.57% by weight of 35% hydrogen peroxide water (5.8% by weight of hydrogen peroxide and 10.77% by weight of water based on the total amount of etching solution), and the hydrogen peroxide concentration is A 5.8% by mass etchant was prepared.
  • the total amount of water is 82.81% by mass.
  • the solution temperature was 35 ° C.
  • the concentration of each component in the entire etching solution and the result of each evaluation item are shown in Table 2.
  • Example 6 is only lactic acid as the organic acid.
  • the organic acid was able to suitably etch the copper / titanium multilayer film with only lactic acid.
  • Table 2 lists comparative examples.
  • the amount of ammonium fluoride is 0.26% by mass, which is less than the examples shown in Table 1.
  • Comparative Examples 1 and 2 the state of just etching could not be achieved within the specified time, and an etching residue occurred. Therefore, the index of side etching such as taper angle could not be measured.
  • time out was described.
  • Comparative Example 3 is a composition containing methanesulfonic acid and lactic acid as the organic acid.
  • the index for the side etching is the value, but the tapered portion was not tapered, and the etching surface was very irregular in shape. In the remarks of Table 2, it described as "(theta) defect.”
  • the comparative example 4 is a thing of only methanesulfonic acid as an organic acid.
  • methanesulfonic acid and glycolic acid are used in combination as the organic acid. In either case, the state of just etching did not occur within the specified time, and there was unmelted material. In the remarks of Table 2, "time out" was described.
  • methanesulfonic acid is in the range of 0.2 mass% to 1.5 mass% with respect to the total amount, and when lactic acid is used in combination, lactic acid is 2.0 mass% to 10.0 mass%. desirable.
  • succinic acid When succinic acid is used in combination, 4.5% by mass to 5.5% by mass of succinic acid is preferable, and when glutaric acid is used in combination, glutaric acid is preferably 9.5% by mass to 10.5% by mass, When malonic acid is used in combination, malonic acid is preferably 4.5% by mass to 5.5% by mass.
  • lactic acid can also be used alone as an organic acid.
  • the content of lactic acid at that time is preferably 4.0% by mass to 5.0% by mass.
  • the etching solution is composed of hydrogen peroxide, a fluorine ion source, an azole, a hydrogen peroxide stabilizer, an organic acid, an amine and water, and the organic acid is methanesulfonic acid.
  • those containing at least one selected from lactic acid, succinic acid, glutanoic acid and malonic acid can suitably etch a copper / titanium multilayer film, and also have a long bath life. Therefore, even if the film thickness of copper is increased, it is not necessary to adjust the composition of the etching solution frequently.
  • the etching solution according to the present invention can be suitably used when etching a multilayer film of titanium and copper.
  • the characteristics of the side etching can be maintained, so that the predetermined etching rate range can be maintained for a long time even if the copper film thickness becomes large.

Abstract

Provided is an etching solution which is for etching a multilayer film composed of a copper layer having a large film thickness and a titanium base layer, and can be used even when the concentration of metal ions is 8,000 ppm or higher. The etching solution includes (a) hydrogen peroxide, (b) a fluorine ion supply source, (c) azoles, (d) a hydrogen peroxide stabilizer, (e) an organic acid, (f) amines, and (g) water, wherein a methane sulfonic acid and one organic acid among lactic acid, succinic acid, glutaric acid, and malonic acid are used as the organic acid, or lactic acid is used alone as the organic acid.

Description

多層膜用エッチング液とエッチング濃縮液およびエッチング方法Etching solution for multilayer film, etching solution and etching method
　本発明は、液晶、有機ＥＬ等のフラットパネルディスプレイの配線用に用いられる銅およびチタンの多層膜をエッチングする際に用いる、多層膜用エッチング液とエッチング濃縮液およびエッチング方法に関する。 The present invention relates to an etching solution for a multilayer film, an etching solution and an etching method used for etching a multilayer film of copper and titanium used for wiring of flat panel displays such as liquid crystal and organic EL.
　液晶や有機ＥＬ（Ｅｌｅｃｔｒｏ－Ｌｕｍｉｎｅｓｃｅｎｃｅ）等のフラットパネルディスプレイ（ＦＰＤ）のＴＦＴ（Ｔｈｉｎ　Ｆｉｌｍ　Ｔｒａｎｓｉｓｔｏｒ）は、配線材料としてアルミニウムが使用されてきた。近年、大画面で高精細度のＦＰＤが普及し、使用される配線材料には、アルミニウムよりも低抵抗のものが求められた。そこで、近年アルミニウムより低抵抗である銅を配線材料として用いられるようになった。 Aluminum has been used as a wiring material for TFTs (Thin Film Transistors) of flat panel displays (FPDs) such as liquid crystal and organic EL (Electro-Luminescence). In recent years, large-screen, high-definition FPDs have become widespread, and wiring materials to be used have been required to have lower resistance than aluminum. Therefore, copper having a resistance lower than that of aluminum has recently been used as a wiring material.
　銅を配線材料として用いると、基板との間の接着力と、半導体基材への拡散という２つの問題が生じる。つまり、ゲート配線で用いる場合は、比較的基材への衝突エネルギーが大きいとされるスパッタリング法を用いても、ガラスなどの基板の間で接着力が十分でない場合がある。また、ソース・ドレイン配線で用いる場合は、付着した銅が下地となるシリコンへ拡散し、半導体の電気的設計値を変えてしまうという問題が生じる。 When copper is used as a wiring material, two problems occur: adhesion to the substrate and diffusion to the semiconductor substrate. That is, in the case of using for gate wiring, adhesion may not be sufficient between substrates such as glass even when using a sputtering method that is considered to have a relatively high impact energy to the substrate. In addition, in the case of using in source / drain wiring, there is a problem that the adhered copper is diffused to the underlying silicon, and the electrical design value of the semiconductor is changed.
　この問題を解決するため、半導体基材上にモリブデン膜を最初に形成しておき、その上に銅膜を形成する多層構造が採用された。しかし、下地とのアイソレーションおよび接着性をより確実にするため、銅膜の下地層としてチタンが採用されてきている。 In order to solve this problem, a multilayer structure was employed in which a molybdenum film is first formed on a semiconductor substrate, and a copper film is formed thereon. However, titanium has been adopted as a base layer of a copper film in order to further ensure the isolation and adhesion to the base.
　また、大型のＦＰＤが普及に伴い、より抵抗の低い銅配線パターンが求められた。画面が広くなると、画素に給電するための配線長が長くなり、また高精細にするために線幅を狭くする必要がある。そこで、銅膜の厚みを厚くして抵抗を低下させることが検討されている。 Further, with the spread of large-sized FPDs, copper wiring patterns with lower resistance have been required. As the screen becomes wider, the wiring length for supplying power to the pixels becomes longer, and it is necessary to narrow the line width for high definition. Therefore, it has been studied to increase the thickness of the copper film to reduce the resistance.
　ＦＰＤの配線は、スパッタリング法で形成された多層膜をウエットエッチングによって形成される。大面積を一気に形成できるので、工程の短縮化が可能だからである。ここで、配線のウエットエッチング用のエッチング液には、以下の点が重要とされている。
（１）加工精度が高く基板全面にわたり一様に加工できること。
（２）加工後の配線断面が所定の角度の順テーパーであること。
（３）銅イオンが含まれることでエッチングレートが変化しないこと（バスライフが長いこと）。
（４）析出物の発生が少ないこと。 The wiring of FPD is formed by wet etching a multilayer film formed by sputtering. This is because a large area can be formed at once, which makes it possible to shorten the process. Here, the following points are considered important for the etching solution for wet etching of the wiring.
(1) High processing accuracy and uniform processing over the entire surface of the substrate.
(2) The wiring cross section after processing is a forward taper of a predetermined angle.
(3) The etching rate does not change by containing copper ions (the bath life is long).
(4) There should be little generation of precipitates.
　特許文献１には、銅／チタンの積層膜のエッチング液として、
（Ａ）過酸化水素、
（Ｂ）硝酸、
（Ｃ）フッ素イオン供給源としてフッ化アンモニウム及び／又は酸性フッ化アンモニウム、
（Ｄ）５－アミノ－１Ｈ－テトラゾール、
（Ｅ）第四級アンモニウムヒドロキシドとしてテトラアルキルアンモニウムヒドロキシド及び／又は（ヒドロキシアルキル）トリアルキルアンモニウムヒドロキシド及び
（Ｆ）フェニル尿素及び／又はフェノールスルホン酸を含み、
ｐＨが１．５～２．５である多層膜用エッチング液が開示されている。 In Patent Document 1, as an etching solution for a copper / titanium laminated film,
(A) hydrogen peroxide,
(B) Nitric acid,
(C) ammonium fluoride and / or ammonium acid fluoride as a fluoride ion source,
(D) 5-amino-1H-tetrazole,
(E) containing tetraalkylammonium hydroxide and / or (hydroxyalkyl) trialkylammonium hydroxide as quaternary ammonium hydroxide and (F) phenyl urea and / or phenol sulfonic acid,
An etchant for a multilayer film having a pH of 1.5 to 2.5 is disclosed.
　特許文献１のエッチング液は、下層のチタン膜および上層の銅膜のサイドエッチングの指標であるトップＣＤロス、ボトムＣＤロス、バリア膜テイリング、テーパー角などに関して好適な範囲でエッチングできることが示されている。 It has been shown that the etching solution of Patent Document 1 can be etched in a suitable range with respect to top CD loss, bottom CD loss, barrier film tailing, taper angle, etc. which are indicators of side etching of the lower titanium film and upper copper film. There is.
　一方、特許文献１のエッチング液は、上記の特性を維持できる範囲（バスライフ）を４０００ｐｐｍとしている。金属イオン量がこの値以上になると、過酸化水素や硝酸の分解が進み、性能を維持できないからとされている。 On the other hand, in the etching solution of Patent Document 1, the range (bath life) in which the above-mentioned characteristics can be maintained is set to 4000 ppm. When the amount of metal ions exceeds this value, decomposition of hydrogen peroxide and nitric acid proceeds, and the performance can not be maintained.
国際公開２０１１－０９３４４５号（特許５６８５２０４号）International Publication No. 2011-093445 (Patent No. 5685204)
　銅の膜厚が増えると、サイドエッチングの挙動も変化する。したがって、膜厚に応じたエッチング液組成の調整が必要となる。しかし、銅の膜厚が増えると、エッチング液中の金属イオン濃度の上昇も早くなる。結果、エッチング液の成分管理のための追添の手間が多く必要となるという課題が生じる。 As the film thickness of copper increases, the behavior of side etching also changes. Therefore, it is necessary to adjust the etching solution composition according to the film thickness. However, when the film thickness of copper increases, the increase of the metal ion concentration in the etching solution also becomes faster. As a result, there arises a problem that much time and effort for additional control for controlling the components of the etching solution is required.
　本発明は上記の課題を解決するために想到されたものであり、エッチング液中の金属イオン濃度が高くなっても、エッチングの性能の変化を許容範囲に収めることができ、組成管理の手間を軽減することができる銅／チタン用エッチング液を提供することにある。 The present invention is conceived to solve the above-mentioned problems, and even if the metal ion concentration in the etching solution becomes high, the change in etching performance can be kept within an acceptable range, and it takes time for composition control. It is an object of the present invention to provide a copper / titanium etching solution which can be reduced.
　より具体的に、本発明に係る多層膜用エッチング液は、
　銅とチタンの多層膜をエッチングするエッチング液であって、
（ａ）過酸化水素と、
（ｂ）フッ素イオン供給源と、
（ｃ）アゾール類と、
（ｄ）過酸化水素安定剤と、
（ｅ）有機酸と、
（ｆ）アミン類と、
（ｇ）水を含み、
　前記有機酸はエッチング液全量に対してメタンスルホン酸と乳酸から選ばれ、
　前記有機酸にメタンスルホン酸を含む場合は、前記メタンスルホン酸は、エッチング液全量に対して０．２質量％～１．５質量％含み、
　　さらに、少なくとも乳酸、コハク酸、グルタル酸、マロン酸のうち一種の有機酸が併用され、
　　　前記併用される有機酸に乳酸を含む場合は、前記乳酸は、エッチング液全量に対して２．０質量％～１０．０質量％であり、
　　　前記併用される有機酸にコハク酸を含む場合、前記コハク酸は、エッチング液全量に対して４．５質量％～５．５質量％であり、
　　　前記併用される有機酸にグルタル酸を含む場合、前記グルタル酸は、エッチング液全量に対して９．５質量％～１０．５質量％であり、
　　　前記併用される有機酸にマロン酸を含む場合、前記マロン酸は、エッチング液全量に対して４．５質量％～５．５質量％であり、
　前記有機酸が乳酸だけの場合は、前記乳酸はエッチング液全量に対して４．０質量％～５．０質量％であることを特徴とする。 More specifically, the etching solution for a multilayer film according to the present invention is
An etching solution for etching a multilayer film of copper and titanium,
(A) hydrogen peroxide,
(B) a fluorine ion supply source,
(C) azoles,
(D) hydrogen peroxide stabilizer,
(E) with an organic acid,
(F) amines,
(G) contains water,
The organic acid is selected from methanesulfonic acid and lactic acid based on the total amount of etching solution.
When the organic acid contains methanesulfonic acid, the methanesulfonic acid contains 0.2% by mass to 1.5% by mass with respect to the total amount of the etching solution,
Furthermore, at least one type of organic acid of lactic acid, succinic acid, glutaric acid and malonic acid is used in combination,
When lactic acid is contained in the organic acid used in combination, the lactic acid is 2.0% by mass to 10.0% by mass with respect to the total amount of the etching solution,
When succinic acid is contained in the organic acid used in combination, the succinic acid is 4.5% by mass to 5.5% by mass with respect to the total amount of the etching solution,
When glutaric acid is contained in the organic acid used in combination, the glutaric acid is 9.5% by mass to 10.5% by mass with respect to the total amount of the etching solution,
When malonic acid is contained in the organic acid used in combination, the malonic acid is 4.5% by mass to 5.5% by mass with respect to the total amount of the etching solution,
When the organic acid is only lactic acid, the content of the lactic acid is 4.0% by mass to 5.0% by mass with respect to the total amount of the etching solution.
　また、本発明に係るエッチング方法は、
　上記のエッチング液を銅とチタンの多層膜にレジストパターンが配された被処理基板に接触させる工程と、
　前記接触させた状態を所定時間維持する工程を有することを特徴とする。 Moreover, the etching method according to the present invention is
Bringing the above etching solution into contact with a substrate to be treated in which a resist pattern is disposed on a multilayer film of copper and titanium;
The method is characterized by including the step of maintaining the contact state for a predetermined time.
　本発明に係るエッチング液は、エッチング液中の金属イオン濃度が８，０００ｐｐｍでもサイドエッチングの各パラメータを好適な範囲に維持することができる。したがって、銅の膜厚を厚くした基板をエッチングする際にも、これまで通りの組成管理（成分や全量の追添等の量や時期の決定）を行うことができる。 The etching solution according to the present invention can maintain each parameter of the side etching in a suitable range even if the metal ion concentration in the etching solution is 8,000 ppm. Therefore, even when etching a substrate with a thick copper film, it is possible to carry out the conventional composition control (determination of the amount and timing of addition of components, total amount, etc.).
エッチングされた配線の断面を表す概念図である。It is a conceptual diagram showing the cross section of the etched wiring.
　以下本発明に係る銅およびチタンの多層膜用エッチング液について説明する。なお、以下の説明は本発明に係るエッチング液の一実施形態を示すものであり、本発明の趣旨を逸脱しない範囲で、以下の実施形態および実施例は改変されてもよい。なお、以下の説明において、数値範囲を「Ａ～Ｂ」で示した場合、「Ａ以上、Ｂ以下」の意味である。すなわち、数値Ａを含んで大きく、且つ数値Ｂを含んで小さい範囲を意味する。 The etching solution for copper and titanium multilayer films according to the present invention will be described below. The following description shows one embodiment of the etching solution according to the present invention, and the following embodiments and examples may be modified without departing from the spirit of the present invention. In the following description, when the numerical range is indicated by “A to B”, it means “more than A and less than B”. That is, it means a large range including the numerical value A and a small range including the numerical value B.
　本発明に係る多層膜用エッチング液は、過酸化水素と、フッ素イオン供給源と、アゾール類と、過酸化水素安定剤と、有機酸と、アミン類と、水を含む。以下、それぞれの成分について詳説する。 The etching solution for a multilayer film according to the present invention contains hydrogen peroxide, a fluorine ion supply source, an azole, a hydrogen peroxide stabilizer, an organic acid, an amine and water. Each component will be described in detail below.
　＜過酸化水素＞
　銅のエッチングは、銅が酸化され、酸化銅（ＣｕＯ）となり、酸（有機酸）により溶解される。過酸化水素は、銅を酸化する酸化剤として用いられる。過酸化水素は、エッチング液全量の４．０質量％～８．８質量％が好ましく、５．０質量％～７．０質量％であればより好ましく、５．５質量％～６．５質量％であれば最も好ましい。 <Hydrogen peroxide>
In the etching of copper, copper is oxidized to form copper oxide (CuO), which is dissolved by an acid (organic acid). Hydrogen peroxide is used as an oxidizing agent to oxidize copper. Hydrogen peroxide is preferably 4.0% by mass to 8.8% by mass, more preferably 5.0% by mass to 7.0% by mass, and 5.5% by mass to 6.5% by mass of the etching solution. % Is most preferable.
　＜フッ素イオン供給源＞
　チタンの溶解にはフッ素イオンが有用である。フッ素イオンの供給源としては、エッチング液中でフッ素がイオン化するものであれば特に限定はない。フッ化水素酸、フッ化アンモニウム、フッ化水素アンモニウム等が好適に利用できる。特にフッ化アンモニウム（ＮＨ４Ｆ：ＣＡＳ番号１２１２５－０１－８）は好適に利用することができる。フッ素イオン供給源は、ガラスを侵食するため含有量が多すぎると基板自体を腐食させる。エッチング液全量に対して０．２質量％～１．０質量％が好ましい。 <Fluoride ion supply source>
Fluoride ion is useful for dissolving titanium. The source of fluorine ions is not particularly limited as long as fluorine is ionized in the etching solution. Hydrofluoric acid, ammonium fluoride, ammonium hydrogen fluoride and the like can be suitably used. In particular, ammonium fluoride (NH 4 F: CAS No. 12125-01-8) can be suitably used. The fluorine ion source corrodes the substrate itself if the content is too high to corrode the glass. 0.2% by mass to 1.0% by mass is preferable based on the total amount of the etching solution.
　＜アゾール類＞
　本発明に係る多層膜用エッチング液では、Ｃｕのエッチングレートを抑制するためにアゾール類を含有する。アゾール類としては、トリアゾール類、テトラゾール類、イミダゾール類、チアゾール類等が好適に利用することができる。より具体的には、以下のものが列挙できる。トリアゾール類としては、１Ｈ－ベンゾトリアゾール、５－メチル－１Ｈ－ベンゾトリアゾール、３－アミノ－１Ｈ－トリアゾール等が好適に利用できる。 <Azoles>
The etching solution for a multilayer film according to the present invention contains azoles in order to suppress the etching rate of Cu. As azoles, triazoles, tetrazoles, imidazoles, thiazoles etc. can be used suitably. More specifically, the following can be listed. As the triazoles, 1H-benzotriazole, 5-methyl-1H-benzotriazole, 3-amino-1H-triazole and the like can be suitably used.
　テトラゾール類としては、１Ｈ－テトラゾール、５－メチル－１Ｈ－テトラゾール、５－フェニル－１Ｈ－テトラゾール、５－アミノ－１Ｈ－テトラゾール等が好適に利用できる。また、イミダゾール類としては、１Ｈ－イミダゾール、１Ｈ－ベンゾイミダゾール等が好適に利用できる。また、チアゾール類としては、１，３－チアゾール、４－メチルチアゾール等が好適に利用できる。 As tetrazole, 1H-tetrazole, 5-methyl-1H-tetrazole, 5-phenyl-1H-tetrazole, 5-amino-1H-tetrazole and the like can be suitably used. Also, as imidazoles, 1H-imidazole, 1H-benzimidazole and the like can be suitably used. In addition, as thiazoles, 1,3-thiazole, 4-methylthiazole and the like can be suitably used.
　なお、これらのうち、テトラゾール類はエッチングレート抑制に効果が高く、とりわけ５－アミノ－１Ｈ－テトラゾール（ＣＡＳ番号４４１８－６１－５：以後「５Ａ１ＨＴ」とも呼ぶ。）が好ましい。 Among these, tetrazoles are highly effective in suppressing the etching rate, and 5-amino-1H-tetrazole (CAS No. 4418-61-5: hereinafter also referred to as "5A1HT") is particularly preferable.
　これらのアゾール類は、エッチング液全量に対して、０．００５質量％～１．０質量％がよく、より好ましくは０．０１質量％～０．５質量％、最も好ましくは０．０１質量％～０．１０質量％含有させるのがよい。 The content of these azoles is preferably 0.005% by mass to 1.0% by mass, more preferably 0.01% by mass to 0.5% by mass, and most preferably 0.01% by mass with respect to the total amount of the etching solution. It is preferable to contain up to 0.10 mass%.
　＜過酸化水素安定剤＞
　本発明に係る多層膜用エッチング液では、酸化剤として過酸化水素を利用している。過酸化水素は、自己分解するため、その分解を抑制する分解抑制剤を添加する。過酸化水素分解抑制剤は、過酸化水素安定剤とも呼ぶ。 <Peroxide stabilizer>
The etching solution for a multilayer film according to the present invention utilizes hydrogen peroxide as an oxidant. Since hydrogen peroxide is self-decomposable, a decomposition inhibitor that suppresses its decomposition is added. Hydrogen peroxide decomposition inhibitors are also referred to as hydrogen peroxide stabilizers.
　特に、本発明に係るエッチング液の場合、Ｃｕ濃度が８，０００ｐｐｍまでエッチングレートの変化がわずかであることが必要である。本発明では、２－ブトキシエタノール（ＣＡＳ番号１１１－７６－２：以下「ＢＧ」とも呼ぶ。）が好適に用いられる。 In particular, in the case of the etching solution according to the present invention, it is necessary that the change of the etching rate is small up to 8,000 ppm of Cu. In the present invention, 2-butoxyethanol (CAS number 111-76-2: hereinafter also referred to as “BG”) is suitably used.
　従来、過酸化水素安定剤としては、フェニル尿素、アリル尿素、１，３－ジメチル尿素、チオ尿素などの尿素系過酸化水素安定剤のほか、フェニル酢酸アミド、フェニルエチレングリコールや、１－プロパノール、２－プロパノール等の低級アルコールなどがよく用いられていた。しかし、ＢＧはＣｕ濃度が８，０００ｐｐｍ以上の高い濃度になっても、過酸化水素の分解を抑制する顕著な効果を発揮することがわかった。 Conventionally, as hydrogen peroxide stabilizers, in addition to urea-based hydrogen peroxide stabilizers such as phenylurea, allylurea, 1,3-dimethylurea and thiourea, phenylacetic acid amide, phenylethylene glycol, 1-propanol, Lower alcohols such as 2-propanol are often used. However, it has been found that BG exerts a remarkable effect of suppressing the decomposition of hydrogen peroxide even when the Cu concentration is as high as 8,000 ppm or more.
　なお、ＢＧは、エッチング液に一定以上入れることで効果があり、多量に入れても効果は飽和する。他の必要成分量を確保できれば、多量に入れてもエッチング液としての効果は発揮する。しかし、ＢＧを多く加えることで、コストは高くなる。効果と価格を考慮するとエッチング液全量に対して５．０質量％を超えて添加する意味はない。 BG is effective when it is added to the etching solution at a certain level or more, and even if it is added in a large amount, the effect is saturated. If the amount of other necessary components can be secured, the effect as an etching solution can be exhibited even if it is added in a large amount. However, adding more BG increases the cost. Considering the effect and the price, there is no point in adding more than 5.0% by mass to the total amount of the etching solution.
　また、エッチング液中の過酸化水素の割合が上記に示した範囲内であれば、ＢＧは、エッチング液全量に対して０．１質量％以上含有されていれば効果を奏する。したがって、過酸化水素安定剤としてのＢＧは、エッチング液全量に対して０．１質量％～５．０質量％含有されていればよく、０．５質量％～２．５質量％含有されていればより好ましく、０．７質量％～１．５質量％含有されていれば最も好ましい。 In addition, if the ratio of hydrogen peroxide in the etching solution is within the range described above, the effect is exerted if BG is contained in an amount of 0.1% by mass or more with respect to the total amount of the etching solution. Therefore, BG as a hydrogen peroxide stabilizer may be contained in an amount of 0.1% by mass to 5.0% by mass, based on the total amount of the etching solution, from 0.5% by mass to 2.5% by mass. It is more preferable that the content is 0.7% by mass to 1.5% by mass.
　なお、従来過酸化水素分解抑制剤として使われていたフェニル尿素は、エッチング液全量に対して０．２質量％を超えて含有させると、フェニル基と過酸化水素が反応し、アゾール類と過酸化水素の反応物とは異なる析出物を生じた。一方、ＢＧはそのような析出物を発生させない。したがって析出物の生成という点からも、ＢＧは好適な過酸化水素安定剤である。 In addition, when it is contained in excess of 0.2% by mass with respect to the total amount of etching solution, phenyl urea and hydrogen peroxide react with each other to cause azoles and excess, when used conventionally as a hydrogen peroxide decomposition inhibitor. A precipitate different from the hydrogen oxide reactant was produced. On the other hand, BG does not generate such precipitates. Therefore, BG is a suitable hydrogen peroxide stabilizer also in terms of the formation of precipitates.
　＜有機酸＞
　有機酸は、銅膜をエッチングするとともに、エッチングされた配線の断面のテーパー角度を調整する役目を負う。また、過酸化水素の分解を抑制する機能もある程度有すると考えられる。有機酸には酸性有機酸を用いる。 <Organic acid>
The organic acid serves to etch the copper film and to adjust the taper angle of the cross section of the etched interconnection. In addition, it is considered that it also has a function of suppressing the decomposition of hydrogen peroxide to some extent. An acidic organic acid is used as the organic acid.
　有機酸としては、炭素数１～１８の脂肪族カルボン酸、炭素数６～１０の芳香族カルボン酸のほか、炭素数１～１０のアミノ酸、炭素数１～１０のスルホン酸などが好ましく挙げられる。 Preferred examples of the organic acid include aliphatic carboxylic acids having 1 to 18 carbon atoms, aromatic carboxylic acids having 6 to 10 carbon atoms, amino acids having 1 to 10 carbon atoms, and sulfonic acids having 1 to 10 carbon atoms. .
　炭素数１～１８の脂肪族カルボン酸としては、ギ酸、酢酸、プロピオン酸、乳酸、ジグリコール酸、ピルビン酸、マロン酸、酪酸、ヒドロキシ酪酸、酒石酸、コハク酸、リンゴ酸、マレイン酸、フマル酸、吉草酸、グルタル酸、イタコン酸、アジピン酸、カプロン酸、クエン酸、プロパントリカルボン酸、ｔｒａｎｓ－アコニット酸、エナント酸、カプリル酸、ラウリン酸、ミリスチン酸、パルミチン酸、ステアリン酸、オレイン酸、リノール酸、リノレン酸などが好ましく挙げられる。 Examples of aliphatic carboxylic acids having 1 to 18 carbon atoms include formic acid, acetic acid, propionic acid, lactic acid, diglycolic acid, pyruvic acid, malic acid, butyric acid, hydroxybutyric acid, tartaric acid, succinic acid, malic acid, maleic acid and fumaric acid , Valeric acid, glutaric acid, itaconic acid, adipic acid, caproic acid, citric acid, propane tricarboxylic acid, trans-aconitic acid, enanthate, caprylic acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linole Preferred are acid and linolenic acid.
　炭素数６～１０の芳香族カルボン酸としては、安息香酸、サリチル酸、マンデル酸、フタル酸、イソフタル酸、テレフタル酸などが好ましく挙げられる。 Preferred examples of the aromatic carboxylic acid having 6 to 10 carbon atoms include benzoic acid, salicylic acid, mandelic acid, phthalic acid, isophthalic acid and terephthalic acid.
　また、炭素数１～１０のアミノ酸としては、カルバミン酸、アラニン、グリシン、アスパラギン、アスパラギン酸、サルコシン、セリン、グルタミン、グルタミン酸、４－アミノ酪酸、イミノジ酪酸、アルギニン、ロイシン、イソロイシン、ニトリロ三酢酸などが好ましく挙げられる。
　また、炭素数１～１０のスルホン酸としては、メタンスルホン酸、ベンゼンスルホン酸、ｐ－トルエンスルホン酸等が好ましい。 Further, as the amino acid having 1 to 10 carbon atoms, carbamic acid, alanine, glycine, asparagine, aspartic acid, sarcosine, serine, glutamine, glutamic acid, 4-aminobutyric acid, iminodibutyric acid, arginine, leucine, isoleucine, nitrilotriacetic acid, etc. Is preferably mentioned.
Further, as the sulfonic acid having 1 to 10 carbon atoms, methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid and the like are preferable.
　上記有機酸のなかでも、酸性有機酸として乳酸、コハク酸、グルタル酸、マロン酸、メタンスルホン酸が好適に利用できる。 Among the above organic acids, lactic acid, succinic acid, glutaric acid, malonic acid and methanesulfonic acid can be suitably used as the acidic organic acid.
　メタンスルホン酸（ＣＡＳ番号：７５－７５－２）は、単独で用いられることはなく、必ず他の酸性有機酸と併用される。この場合、メタンスルホン酸はエッチング液全量に対して０．２質量％～１．５質量％であるのが好ましい。 Methanesulfonic acid (CAS number: 75-75-2) is not used alone, but is always used in combination with other acidic organic acids. In this case, the amount of methanesulfonic acid is preferably 0.2% by mass to 1.5% by mass with respect to the total amount of the etching solution.
　併用される酸性有機酸が乳酸（混合状態（ＤＬ－乳酸）ＣＡＳ番号：５０－２１－５）の場合、乳酸はエッチング液全量に対して２．０質量％～１０．０質量％の範囲が好ましい。なお、乳酸はＬ－乳酸若しくはＤ－乳酸を単独で用いてもよい。 When the acid organic acid to be used in combination is lactic acid (mixed state (DL-lactic acid) CAS number: 50-21-5), the range of 2.0 mass% to 10.0 mass% of lactic acid with respect to the total amount of the etching solution is preferable. L-lactic acid or D-lactic acid may be used alone as lactic acid.
　また、併用される酸性有機酸がコハク酸（ＣＡＳ番号：１１０－１５－６）の場合、コハク酸はエッチング液全量に対して４．５質量％～５．５質量％の範囲が好ましい。 When the acidic organic acid to be used in combination is succinic acid (CAS No. 11015-6), succinic acid is preferably in the range of 4.5% by mass to 5.5% by mass with respect to the total amount of the etching solution.
　また、併用される酸性有機酸がグルタル酸（ＣＡＳ番号：１１０－９４－１）の、グルタル酸はエッチング液全量に対して９．５質量％～１０．５質量％の範囲が好ましい。 In addition, the acid organic acid used in combination is glutaric acid (CAS number: 110-94-1), and the glutaric acid is preferably in the range of 9.5% by mass to 10.5% by mass with respect to the total amount of the etching solution.
　また、併用される酸性有機酸がマロン酸（ＣＡＳ番号：１４１－８２－２）の場合、マロン酸はエッチング液全量に対して４．５質量％～５．５質量％の範囲が好ましい。 When the acid organic acid used in combination is malonic acid (CAS number: 141-82-2), the malonic acid is preferably in the range of 4.5% by mass to 5.5% by mass with respect to the total amount of the etching solution.
　なお、乳酸は単独で用いることができる。乳酸を単独で用いた場合は、エッチング液全量に対して４．０質量％～５．０質量％の範囲が好ましい。 Lactic acid can be used alone. When lactic acid is used alone, the range of 4.0% by mass to 5.0% by mass is preferable with respect to the total amount of the etching solution.
　＜アミン化合物＞
　アミン化合物はエッチング液のｐＨ調整を担う。アミン化合物としては、炭素数２～１０のものが好適に利用できる。より具体的には、エチレンジアミン、トリメチレンジアミン、テトラメチレンジアミン、１，２－プロパンジアミン、１，３－プロパンジアミン、Ｎ，Ｎ－ジメチル－１，３－プロパンジアミン、Ｎ，Ｎ－ジエチル－１，３－プロパンジアミン、１，３－ジアミノブタン、２，３－ジアミノブタン、ペンタメチレンジアミン、２，４－ジアミノペンタン、ヘキサメチレンジアミン、ヘプタメチレンジアミン、オクタメチレンジアミン、ノナメチレンジアミン、Ｎ－メチルエチレンジアミン、Ｎ，Ｎ－ジメチルエチレンジアミン、トリメチルエチレンジアミン、Ｎ－エチルエチレンジアミン、Ｎ，Ｎ－ジエチルエチレンジアミン、トリエチルエチレンジアミン、１，２，３－トリアミノプロパン、ヒドラジン、トリス（２－アミノエチル）アミン、テトラ（アミノメチル）メタン、ジエチレントリアミン、トリエチレンテトラミン、テトラエチルペンタミン、ヘプタエチレンオクタミン、ノナエチレンデカミン、ジアザビシクロウンデセンなどのポリアミン；エタノールアミン、Ｎ－メチルエタノールアミン、Ｎ－メチルジエタノールアミン、Ｎ－エチルエタノールアミン、Ｎ－アミノエチルエタノールアミン、Ｎ－プロピルエタノールアミン、Ｎ－ブチルエタノールアミン、ジエタノールアミン、トリエタノールアミン、トリイソプロパノールアミン、１－アミノ－２－プロパノール、Ｎ－メチルイソプロパノールアミン、Ｎ－エチルイソプロパノールアミン、Ｎ－プロピルイソプロパノールアミン、２－アミノプロパン－１－オール、Ｎ－メチル－２－アミノ－プロパン－１－オール、Ｎ－エチル－２－アミノ－プロパン－１－オール、１－アミノプロパン－３－オール、Ｎ－メチル－１－アミノプロパン－３－オール、Ｎ－エチル－１－アミノプロパン－３－オール、１－アミノブタン－２－オール、Ｎ－メチル－１－アミノブタン－２－オール、Ｎ－エチル－１－アミノブタン－２オール、２－アミノブタン－１－オール、Ｎ－メチル－２－アミノブタン－１－オール、Ｎ－エチル－２－アミノブタン－１－オール、３－アミノブタン－１－オール、Ｎ－メチル－３－アミノブタン－１－オール、Ｎ－エチル－３－アミノブタン－１－オール、１－アミノブタン－４－オール、Ｎ－メチル１－アミノブタン－４－オール、Ｎ－エチル－１－アミノブタン－４－オール、１－アミノ－２－メチルプロパン－２－オール、２－アミノ－２－メチルプロパン－１－オール、１－アミノペンタン－４－オール、２－アミノ－４－メチルペンタン－１－オール、２－アミノヘキサン－１－オール、３－アミノヘプタン－４－オール、１－アミノオクタン－２－オール、５－アミノオクタン－４－オール、１－アミノプパン－２，３－ジオール、２－アミノプロパン－１，３－ジオール、トリス（オキシメチル）アミノメタン、１，２－ジアミノプロパン－３－オール、１，３－ジアミノプロパン－２－オール、２－（２－アミノエトキシ）エタノール、２－（２－アミノエチルアミノ）エタノール、ジグリコールアミンなどのアルカノールアミンが好ましく挙げられる。これらの有機酸は、単独で又は複数を組み合わせて用いることができる。 <Amine compound>
The amine compound is responsible for adjusting the pH of the etching solution. As the amine compound, one having 2 to 10 carbon atoms can be suitably used. More specifically, ethylenediamine, trimethylenediamine, tetramethylenediamine, 1,2-propanediamine, 1,3-propanediamine, N, N-dimethyl-1,3-propanediamine, N, N-diethyl-1 , 3-propanediamine, 1,3-diaminobutane, 2,3-diaminobutane, pentamethylenediamine, 2,4-diaminopentane, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, N-methyl Ethylenediamine, N, N-dimethylethylenediamine, trimethylethylenediamine, N-ethylethylenediamine, N, N-diethylethylenediamine, triethylethylenediamine, 1,2,3-triaminopropane, hydrazine, tris (2-aminoethyl) amide Polyamines such as tetra (aminomethyl) methane, diethylenetriamine, triethylenetetramine, tetraethylpentamine, heptaethyleneoctamine, nonaethylene decamine, diazabicycloundecene and the like; ethanolamine, N-methylethanolamine, N-methyldiethanolamine N-ethyl ethanolamine, N-aminoethyl ethanolamine, N-propyl ethanolamine, N-butyl ethanolamine, diethanolamine, triethanolamine, triisopropanolamine, 1-amino-2-propanol, N-methylisopropanolamine N-ethylisopropanolamine, N-propylisopropanolamine, 2-aminopropan-1-ol, N-methyl-2-amino-propan-1-o , N-ethyl-2-amino-propan-1-ol, 1-aminopropan-3-ol, N-methyl-1-aminopropan-3-ol, N-ethyl-1-aminopropan-3-ol 1-aminobutan-2-ol, N-methyl-1-aminobutan-2-ol, N-ethyl-1-aminobutan-2-ol, 2-aminobutan-1-ol, N-methyl-2-aminobutane-1-ol -Ol, N-ethyl-2-aminobutan-1-ol, 3-aminobutan-1-ol, N-methyl-3-aminobutan-1-ol, N-ethyl-3-aminobutan-1-ol, 1-aminobutane- 4-ol, N-methyl 1-aminobutan-4-ol, N-ethyl-1-aminobutan-4-ol, 1-amino-2-methylpropan-2-ol, 2-amino-2-methylpropan-1-ol, 1-aminopentan-4-ol, 2-amino-4-methylpentan-1-ol, 2-aminohexan-1-ol, 3-aminoheptane-4 -Ol, 1-aminooctan-2-ol, 5-aminooctan-4-ol, 1-aminopropane-2,3-diol, 2-aminopropane-1,3-diol, tris (oxymethyl) aminomethane, Alkanolamines such as 1,2-diaminopropan-3-ol, 1,3-diaminopropan-2-ol, 2- (2-aminoethoxy) ethanol, 2- (2-aminoethylamino) ethanol, and diglycolamine Is preferably mentioned. These organic acids can be used alone or in combination of two or more.
　これらの中でも、トリイソプロパノールアミン（ＣＡＳ番号１２２－２０－３）が特に好ましい。また、アミン化合物はエッチング液全量に対して、０．５質量％～３．０質量％含有させるのが好ましく、０．６質量％～２．５質量％であればより好ましく、０．７～２．０質量％なら最も好ましい。 Among these, triisopropanolamine (CAS No. 122-20-3) is particularly preferable. The amine compound is preferably contained in an amount of 0.5% by mass to 3.0% by mass, more preferably 0.6% by mass to 2.5% by mass, based on the total amount of the etching solution. It is most preferable if it is 2.0 mass%.
　＜銅イオン＞
　通常の多層膜用エッチング液は、Ｃｕイオン濃度が２，０００ｐｐｍから４，０００ｐｐｍ程度になるように、希釈用のエッチング液が追添される。過酸化水素の分解速度が速くなるため、過酸化水素濃度が低下してしまうからである。しかし、本発明に係るエッチング液は、過酸化水素の分解速度を抑制するので、より高いＣｕイオン濃度になっても、Ｃｕイオンの希釈のためのエッチング液の追添は不要である。より具体的には、エッチング液のＣｕ濃度が少なくとも８，０００ｐｐｍまでは、希釈のためのエッチング液を追添する必要はない。 <Copper ion>
The etching solution for dilution is additionally added to the usual etching solution for multilayer film so that the Cu ion concentration becomes about 2,000 ppm to 4,000 ppm. Because the decomposition rate of hydrogen peroxide is increased, the hydrogen peroxide concentration is reduced. However, since the etching solution according to the present invention suppresses the decomposition rate of hydrogen peroxide, it is not necessary to add the etching solution for dilution of Cu ions even when the Cu ion concentration becomes higher. More specifically, it is not necessary to add an etching solution for dilution to a Cu concentration of the etching solution of at least 8,000 ppm.
　＜その他＞
　本発明の多層膜用エッチング液には、これらの成分の他、水と、エッチング性能を阻害しない範囲で通常用いられる各種添加剤が添加されてもよい。水は、精密加工を目的とするため、異物が存在しない物が望ましい。純水若しくは超純水であれば好ましい。また、上記に説明した各成分の含有比率の範囲は、エッチング液総量で１００質量％になるように適宜それぞれ調整されるのは言うまでもない。 <Others>
In addition to these components, water and various additives generally used in the range that does not inhibit the etching performance may be added to the etching solution for a multilayer film of the present invention. Since water is intended for precision processing, it is desirable that there be no foreign matter present. Pure water or ultrapure water is preferred. Further, it goes without saying that the range of the content ratio of each component described above is appropriately adjusted to be 100% by mass in the total amount of the etching solution.
　＜ｐＨ、温度＞
　本発明に係る多層膜用エッチング液は、ｐＨ１～４、より好ましくはｐＨ１．５～２．５の範囲で使用されるのが好ましい。また、エッチング液は、２０℃から６０℃の間で使用することができる。より好ましくは３０℃から５５℃であり、最も好ましくは３５℃から５０℃がよい。 <PH, temperature>
The etching solution for a multilayer film according to the present invention is preferably used in the range of pH 1 to 4, more preferably pH 1.5 to 2.5. Also, the etching solution can be used between 20 ° C. and 60 ° C. The temperature is more preferably 30 ° C. to 55 ° C., and most preferably 35 ° C. to 50 ° C.
　＜保存＞
　本発明に係る多層膜用エッチング液には、過酸化水素が用いられる。過酸化水素は自己分解する。そのためエッチング液には、過酸化水素分解抑制剤が含まれている。しかし、保存の際には、過酸化水素（若しくは過酸化水素水）とその他の液体を分けて保存しても良い。また、過酸化水素（若しくは過酸化水素水）、水および銅イオンを除いた原料（「エッチング液原料」と呼ぶ。）だけをまとめて保存してもよい。なお、エッチング液原料には、液体のものと液体以外の形態のものが存在してもよい。すなわち、本発明に係る多層膜用エッチング液は、エッチング液原料と、水と、過酸化水素（若しくは過酸化水素水）を合わせて完成させてもよい。 <Save>
Hydrogen peroxide is used in the multilayer film etching solution according to the present invention. Hydrogen peroxide self decomposes. Therefore, the etching solution contains a hydrogen peroxide decomposition inhibitor. However, for storage, hydrogen peroxide (or hydrogen peroxide solution) and other liquids may be stored separately. Alternatively, only the hydrogen peroxide (or hydrogen peroxide water), water, and the raw material from which copper ions are removed (referred to as "etching liquid raw material") may be stored collectively. In addition, the thing of a liquid and the thing of forms other than a liquid may exist in an etching liquid raw material. That is, the etching solution for a multilayer film according to the present invention may be completed by combining an etching solution raw material, water, and hydrogen peroxide (or hydrogen peroxide water).
　また、エッチング液原料と水を混ぜ合わせ、エッチング液原料の溶液を作製しておいてよい。この溶液は、後述する実施例で示すエッチング液の水の割合より少ない割合の水であってもよい。エッチング液原料と水で作製したエッチング液原料の溶液を「エッチング濃縮液」と呼ぶ。これに対して過酸化水素を所定の割合で混合し完成されたエッチング液を「完全エッチング液」と呼んでもよい。エッチング濃縮液は、完全エッチング液と比べると過酸化水素および水の一部が無い分だけ体積が少ないので、保存や移送の際には便利である。したがって、本発明の多層膜用エッチング液（完全エッチング液）は、エッチング濃縮液と水と過酸化水素を合わせて完成させてもよい。 Further, the etching solution raw material and water may be mixed to prepare a solution of the etching liquid raw material. This solution may be water in a proportion smaller than the proportion of water in the etching solution shown in the examples described later. The solution of the etching solution raw material produced with the etching solution raw material and water is called "etching concentrate." On the other hand, the etching solution completed by mixing hydrogen peroxide in a predetermined ratio may be called "complete etching solution". The etching concentrate is convenient for storage and transfer since it has a smaller volume due to the absence of a portion of hydrogen peroxide and water as compared to a complete etching solution. Therefore, the etching solution for a multilayer film (complete etching solution) of the present invention may be completed by combining the etching solution, water and hydrogen peroxide.
　したがって、エッチング濃縮液は、本発明に係る完全エッチング液から過酸化水素を除いた成分で構成され、過酸化水素と水を所定の濃度になるように添加すれば、本発明のエッチング液が完成する。すなわち、エッチング濃縮液は、過酸化水素を所定の濃度になるように調製した完全エッチング液にした時の各成分の組成比を規定することで表すことができる。 Therefore, the etching concentrate is composed of the components obtained by removing hydrogen peroxide from the complete etching solution according to the present invention, and adding hydrogen peroxide and water to a predetermined concentration completes the etching solution of the present invention. Do. That is, the etching concentrate can be expressed by defining the composition ratio of each component when the hydrogen peroxide is a complete etching solution prepared to have a predetermined concentration.
　ここで、エッチング濃縮液の水は、エッチング液原料が溶解するだけの量があればよい。つまり、過酸化水素が水溶液である過酸化水素水として供給されると考えると、本発明の多層膜用エッチング液は、エッチング濃縮液と水と過酸化水素水の３つを合わせて完成させることができる。 Here, the water of the etching concentrate may have an amount sufficient to dissolve the etching solution raw material. That is, considering that hydrogen peroxide is supplied as a hydrogen peroxide solution which is an aqueous solution, the etching solution for a multilayer film of the present invention should be completed by combining the etching concentrate, water, and hydrogen peroxide water. Can.
　また、水はエッチング濃縮液若しくは過酸化水素水に含めてしまえば、エッチング濃縮液と過酸化水素水の２つを合わせて完成させることもできる。また、本明細書において、エッチング濃縮液の各成分比率は、エッチング液が完成したときの全量に対する比率で表す。したがって、エッチング濃縮液の各成分の合計は、１００質量％にはならない。 In addition, if water is included in the etching concentrate or the hydrogen peroxide solution, it can be completed by combining the etching concentrate and the hydrogen peroxide solution. Moreover, in the present specification, each component ratio of the etching concentrate is represented by a ratio to the total amount when the etching solution is completed. Therefore, the sum of the respective components of the etching concentrate does not reach 100% by mass.
　＜エッチング方法＞
　本発明に係る多層膜用エッチング液を用いる対象は、チタン若しくはチタン合金（チタン合金を含め単に「チタン」とも呼ぶ。）が下層で、銅若しくは銅合金（銅合金を含め単に「銅」とも呼ぶ。）が上層となった銅／チタンの多層膜である。下層のチタンの厚みは、上層の銅の厚みより薄い。下層の厚みをｔ０とし上層の厚みをｔ１とすると、ｔ１／ｔ０の範囲が１６から３２までの範囲の構成である。ｔ１／ｔ０の範囲がこの範囲を外れて、チタン層が厚すぎると、チタン層の残渣が生じやすく、逆に薄すぎるとＣｕ層の下地層としての役割を果たさなくなる。 <Etching method>
The object using the etching solution for a multilayer film according to the present invention is that titanium or a titanium alloy (also referred to simply as "titanium" including titanium alloy) is a lower layer, and copper or a copper alloy (also referred to simply as "copper" including a copper alloy) Is a multilayer film of copper / titanium with an upper layer. The thickness of the lower layer titanium is thinner than the thickness of the upper layer copper. Assuming that the thickness of the lower layer is t0 and the thickness of the upper layer is t1, the range of t1 / t0 is in the range of 16 to 32. If the range of t1 / t0 is out of this range and the titanium layer is too thick, the residue of the titanium layer tends to be produced, and conversely, if it is too thin, it does not play a role as the underlayer of the Cu layer.
　本発明に係る多層膜用エッチング液は、保存の際に、過酸化水素とエッチング液原料および水を分けて保存しておくことで長期保存が可能になる。そして、実際に使用する際には、これらを調合してエッチング液を完成させる。調合の方法は、最終的に過酸化水素の濃度が所定の濃度になれば、限定されるものではない。 The etchant for a multilayer film according to the present invention can be stored for a long time by storing hydrogen peroxide, an etching solution raw material and water separately during storage. Then, in actual use, these are mixed to complete the etching solution. The method of preparation is not limited as long as the concentration of hydrogen peroxide finally reaches a predetermined concentration.
　一例を示すと、一定量の水にエッチング液原料を混ぜたエッチング濃縮液を調製しておく。過酸化水素は通常本発明に係る多層膜用エッチング液の過酸化水素濃度より高い濃度の過酸化水素水として供給される。そこで、過酸化水素水とエッチング濃縮液（さらに水があってもよい）を所定量ずつ調合する。この工程を多層膜用エッチング液を調合する工程と呼んでもよい。なお、この工程は、エッチングの直前に行う必要はなく、予め過酸化水素を含めて調製されたエッチング液を用いてエッチングしてもよい。 As an example, an etching concentrate is prepared by mixing a predetermined amount of water with the etching solution raw material. Hydrogen peroxide is usually supplied as a hydrogen peroxide solution having a concentration higher than the hydrogen peroxide concentration of the etching solution for a multilayer film according to the present invention. Therefore, a predetermined amount of hydrogen peroxide solution and etching concentrate (which may further contain water) are prepared. This process may be called a process of preparing an etching solution for multilayer film. Note that this step does not have to be performed immediately before etching, and etching may be performed using an etching solution that has been prepared in advance including hydrogen peroxide.
　エッチングを行う際は、上記の通り、ｐＨ１～４で、２０℃から６０℃の条件でエッチング液を使用する。したがって、エッチングの被対象物（被処理基板）も、この温度に余熱されるのが望ましい。被処理基板をエッチング液に接触させる方法は、特に限定されない。シャワー式のように上方からエッチング液を被処理基板に対して散布してもよいし、エッチング液のプールに被処理基板をディップさせる方法でもよい。これを多層膜用エッチング液を被処理基板に接触させる工程と呼んでも良い。 When the etching is performed, the etching solution is used under the conditions of pH 1 to 4 and 20 ° C. to 60 ° C. as described above. Therefore, it is desirable that the object to be etched (substrate to be processed) be also preheated to this temperature. The method of bringing the substrate to be treated into contact with the etching solution is not particularly limited. As in the shower type, the etching solution may be dispersed to the substrate to be processed from above, or a method of dipping the substrate to be processed in a pool of etching solution may be used. This may be called a step of bringing the etching solution for multilayer film into contact with the substrate to be treated.
　またエッチングは、被処理基板とエッチング液の接触を所定の時間維持しなければならない。これは被処理基板とエッチング液の接触を所定の時間維持する工程である。 In addition, the etching must maintain the contact between the substrate to be processed and the etching solution for a predetermined time. This is a step of maintaining the contact between the substrate to be processed and the etching solution for a predetermined time.
　なお、被処理基板とは、ガラス等の基材の上にチタン層と銅層が積層され、この積層膜にパターン形成のためのレジストパターンが形成されている状態の基板である。 The substrate to be treated is a substrate in a state in which a titanium layer and a copper layer are laminated on a base material such as glass, and a resist pattern for pattern formation is formed on this laminated film.
　＜各種評価方法の説明＞
　本発明に係る多層膜用エッチング液に対しては、ジャストエッチングの際の、被処理基板を切断し、ＳＥＭによる観察でサイドエッチングの指標を調べた。 <Description of various evaluation methods>
In the case of the etching solution for a multilayer film according to the present invention, the substrate to be treated at the time of just etching was cut, and the index of side etching was examined by observation with a SEM.
　より具体的には、まず、ガラス基板上にスパッタ法でチタンを２５ｎｍの厚みで成膜し、その上に続けて銅を６００ｎｍの厚みで成膜し、Ｃｕ／Ｔｉの多層膜サンプルを作製した。この銅膜の上に配線形状にパターニングしたレジストを形成し、テーパー角評価用の基材とした。つまり、基材は、ガラス基板とチタン膜とその上の銅膜と、銅膜上のパターニングされたレジスト層からなる。この基材をジャストエッチングする時間の間エッチング液に浸漬させ、エッチングを行った。エッチング後のサンプルを洗浄し、乾燥させた後、配線部分を配線方向に直角に切断し、切断面を観察した。 More specifically, first, titanium was deposited to a thickness of 25 nm by sputtering on a glass substrate, copper was subsequently deposited to a thickness of 600 nm, and a Cu / Ti multilayer film sample was produced. . A resist patterned in a wiring shape was formed on this copper film, and used as a substrate for taper angle evaluation. That is, the substrate comprises a glass substrate, a titanium film, a copper film thereon, and a patterned resist layer on the copper film. Etching was performed by immersing the substrate in an etching solution for the time of just etching. After the sample after etching was washed and dried, the wiring portion was cut at right angles to the wiring direction, and the cut surface was observed.
　切断面の観測は、ＳＥＭ（日立製：ＳＵ８０２０型）を用い、加速電圧１ｋＶ、３０，０００～５０，０００倍の条件で行った。なお、ジャストエッチングは、エッチング開始から膜が光を透過するまでの時間である。膜が光を透過した時点は目視で確認した。ただし、エッチングを開始してから３分経過しても、まだ膜が残っている場合は、「測定不可」とした。 The observation of the cut surface was performed using an SEM (manufactured by Hitachi: SU 8020) under conditions of an acceleration voltage of 1 kV and 30,000 to 50,000 times. Just etching is the time from the start of etching to the passage of light through the film. The point in time when the film transmitted light was checked visually. However, in the case where the film still remained even after 3 minutes from the start of the etching, it was regarded as "impossible to measure".
　切断面形状の模式図を図１に示す。図１を参照して、切断面は、ガラス基板１０と、チタン層１２と、銅層１４と、レジスト層１６で構成される。レジスト層１６の端１６ａからガラス基板１０との間にできるガラス基板１０に垂直な仮想面１８が理想的なエッジ面である。現実のエッジ面は、膜の上面と下面でエッチング速度が異なり、図に示すような傾斜面となる。 A schematic view of the cross-sectional shape is shown in FIG. Referring to FIG. 1, the cut surface is formed of a glass substrate 10, a titanium layer 12, a copper layer 14, and a resist layer 16. A virtual surface 18 perpendicular to the glass substrate 10 formed between the end 16 a of the resist layer 16 and the glass substrate 10 is an ideal edge surface. The actual edge surface has different etching rates on the upper and lower surfaces of the film, and is an inclined surface as shown in the figure.
　レジスト層１６の端１６ａの直下方の銅層１４は、エッチングが進行し存在しない。したがって、レジスト層１６の端１６ａは庇形状になっている。 The copper layer 14 directly below the end 16 a of the resist layer 16 is not present because the etching proceeds. Therefore, the end 16a of the resist layer 16 is wedge-shaped.
　また、銅層１４は、ガラス基板１０に近い方よりレジスト層１６に近い方が仮想面１８から深く浸食されている。銅層１４の下層であるチタン層１２は、銅とのエッチングレートの違いで仮想面１８からの浸食具合は浅い。 In addition, the copper layer 14 is deeply eroded from the virtual surface 18 in a direction closer to the resist layer 16 than in a direction closer to the glass substrate 10. The titanium layer 12 which is the lower layer of the copper layer 14 has a slight degree of erosion from the virtual surface 18 due to the difference in etching rate with copper.
　ここで、銅層１４の上面１４ａの端１４ａａと仮想面１８（レジスト層１６の端１６ａ）との間の距離ａを「トップＣＤ（Ｃｒｉｔｉｃａｌ　Ｄｉｍｅｎｓｉｏｎ：線幅）ロス」と呼ぶ。また、銅層１４の下面１４ｂの端１４ｂａと仮想面１８との距離ｂを「ボトムＣＤロス」と呼ぶ。また、銅層１４の下面１４ｂの端１４ｂａから上面１４ａの端１４ａａまでの斜面の角度θを「テーパー角」と呼ぶ。 Here, the distance a between the end 14 aa of the upper surface 14 a of the copper layer 14 and the virtual surface 18 (the end 16 a of the resist layer 16) is referred to as “top CD (critical dimension: line width) loss”. The distance b between the end 14ba of the lower surface 14b of the copper layer 14 and the virtual surface 18 is called "bottom CD loss". The angle θ of the slope from the end 14 ba of the lower surface 14 b of the copper layer 14 to the end 14 aa of the upper surface 14 a is referred to as a “taper angle”.
　トップＣＤロス、ボトムＣＤロス、テーパー角は、それぞれ記号「ａ」、「ｂ」、「θ」とする。なお、通常トップＣＤロス、ボトムＣＤロスは、線幅の両側で生じるため、測定値の２倍の値を評価値とする。すなわち、あるサンプルの断面を観測したときに、トップＣＤロスが０．５μｍであったとすると、トップＣＤロスの評価値は、１．０μｍとする。しかし、ここでは、配線の片側だけのトップＣＤロスａとボトムＣＤロスｂの測定値を表に表記した。 The top CD loss, the bottom CD loss, and the taper angle are represented by symbols “a”, “b”, and “θ”, respectively. Since the top CD loss and the bottom CD loss usually occur on both sides of the line width, a value twice as large as the measured value is used as the evaluation value. That is, if the top CD loss is 0.5 μm when observing the cross section of a certain sample, the evaluation value of the top CD loss is 1.0 μm. However, here, the measured values of the top CD loss a and the bottom CD loss b of only one side of the wiring are shown in the table.
　なお、トップＣＤロスａは、０．５μｍ～２．０μｍ、ボトムＣＤロスｂは０．３μｍ～１．０μｍであるのが望ましい。またテーパー角θは、３０°から８０°であればよい。 The top CD loss a is preferably 0.5 μm to 2.0 μm, and the bottom CD loss b is preferably 0.3 μm to 1.0 μm. The taper angle θ may be 30 ° to 80 °.
　「ガラス腐食速度」は、エッチング実験を行ったサンプルの浸食部分と非浸食部分の段差を段差測定器で測定し求めた。単位はｎｍ／ｍｉｎである。ガラス腐食速度は３０～６０ｎｍ／ｍｉｎであればよい。 The “glass corrosion rate” was determined by measuring the level difference between the eroded portion and the non-eroded portion of the sample subjected to the etching experiment with a step measuring device. The unit is nm / min. The glass corrosion rate may be 30 to 60 nm / min.
　「評価Ｃｕ濃度」は、サンプルとするエッチング液に、銅を所定量ずつ溶解させながらエッチングを行い、テーパー角θ、トップＣＤロスａ、ボトムＣＤロスｂの何れかが好ましい範囲からはずれた場合、若しくは他の原因で継続してエッチングができなくなった濃度の直前の濃度とした。「評価Ｃｕ濃度」が高いということはバスライフが長いと言ってもよい。 “Evaluation Cu concentration” is a case where etching is performed while dissolving a predetermined amount of copper in the etching solution as a sample, and the taper angle θ, the top CD loss a, or the bottom CD loss b is out of the preferable range Alternatively, the concentration immediately before the concentration at which etching could not be continued due to other causes was used. If the "evaluation Cu concentration" is high, it may be said that the bus life is long.
　以下に実施例および比較例の組成を示す。
　（実施例１）
　酸性有機酸として、
メタンスルホン酸を０．３質量％、
乳酸を９．０質量％、
　アミン化合物として、
トリイソプロパノールアミンを０．７５質量％、
　過酸化水素安定剤として、
２－ブトキシエタノールを０．９０質量％、
　アゾール類として、
５－アミノ－１Ｈ－テトラゾールを０．０４質量％
　フッ素イオン供給源として、
フッ化アンモニウムを０．４質量％
からなるエッチング液原料を水７２．０４質量％と調合し、エッチング濃縮液を調製した。なお、エッチング濃縮液での各成分比率は、後述する過酸化水素水と混合しエッチング液が完成したときの総量に対する比率で表す。以下の実施例および比較例についても同様である。 The compositions of the examples and comparative examples are shown below.
Example 1
As an acidic organic acid,
0.3% by mass of methanesulfonic acid,
9.0% by mass of lactic acid,
As an amine compound,
0.75% by mass of triisopropanolamine,
As a hydrogen peroxide stabilizer
0.90% by mass of 2-butoxyethanol,
As azoles,
0.04 mass% of 5-amino-1H-tetrazole
As a fluoride ion source,
0.4 mass% of ammonium fluoride
The etching liquid raw material which consists of these is mixed with 72.04 mass% of water, and the etching concentrate was prepared. In addition, each component ratio in an etching concentrate is mixed with the hydrogen-peroxide solution mentioned later, and is represented by the ratio with respect to the total amount when the etching liquid is completed. The same applies to the following examples and comparative examples.
　３５％過酸化水素水１６．５７重量％（エッチング液の全量に対して過酸化水素が５．８質量％と水分が１０．７７質量％）とエッチング濃縮液を混合し、過酸化水素濃度が５．８質量％のエッチング液を調製した。なお、水は全量で８２．８１質量％となる。また、液温は３５℃で用いた。エッチング液全体に占める各成分濃度と、各評価事項の結果を表１に示す。なお、表１では、水の全量は「残部」と記載した。以下表２を含め同様である。 The etching concentrate is mixed with 16.57% by weight of 35% hydrogen peroxide water (5.8% by weight of hydrogen peroxide and 10.77% by weight of water based on the total amount of etching solution), and the hydrogen peroxide concentration is A 5.8% by mass etchant was prepared. The total amount of water is 82.81% by mass. The solution temperature was 35 ° C. The concentration of each component in the entire etching solution and the result of each evaluation item are shown in Table 1. In Table 1, the total amount of water is described as "the balance". The same applies to Table 2 below.
　（実施例２）
　酸性有機酸として、
メタンスルホン酸を１．０質量％、
乳酸を２．７質量％、
　アミン化合物として、
トリイソプロパノールアミンを２．０質量％、
　過酸化水素安定剤として、
２－ブトキシエタノールを０．９０質量％、
　アゾール類として、
５－アミノ－１Ｈ－テトラゾールを０．０４質量％
　フッ素イオン供給源として、
フッ化アンモニウムを０．８質量％
からなるエッチング液原料を水７５．９９質量％と調合し、エッチング濃縮液を調製した。 (Example 2)
As an acidic organic acid,
1.0% by mass of methanesulfonic acid,
2.7% by mass of lactic acid,
As an amine compound,
2.0% by mass of triisopropanolamine,
As a hydrogen peroxide stabilizer
0.90% by mass of 2-butoxyethanol,
As azoles,
0.04 mass% of 5-amino-1H-tetrazole
As a fluoride ion source,
0.8 mass% of ammonium fluoride
The etching liquid raw material which consists of these is mixed with 75.99 mass% of water, and the etching concentrate was prepared.
　３５％過酸化水素水１６．５７重量％（エッチング液の全量に対して過酸化水素が５．８質量％と水分が１０．７７質量％）とエッチング濃縮液を混合し、過酸化水素濃度が５．８質量％のエッチング液を調製した。なお、水は全量で８６．７６質量％となる。また、液温は３５℃で用いた。エッチング液全体に占める各成分濃度と、各評価事項の結果を表１に示す。 The etching concentrate is mixed with 16.57% by weight of 35% hydrogen peroxide water (5.8% by weight of hydrogen peroxide and 10.77% by weight of water based on the total amount of etching solution), and the hydrogen peroxide concentration is A 5.8% by mass etchant was prepared. The total amount of water is 86.76% by mass. The solution temperature was 35 ° C. The concentration of each component in the entire etching solution and the result of each evaluation item are shown in Table 1.
　（実施例３）
　酸性有機酸として、
メタンスルホン酸を０．３質量％、
コハク酸を５．０質量％、
　アミン化合物として、
トリイソプロパノールアミンを０．７５質量％、
　過酸化水素安定剤として、
２－ブトキシエタノールを０．９０質量％、
　アゾール類として、
５－アミノ－１Ｈ－テトラゾールを０．０４質量％
　フッ素イオン供給源として、
フッ化アンモニウムを０．４質量％
からなるエッチング液原料を水７６．０４質量％と調合し、エッチング濃縮液を調製した。 (Example 3)
As an acidic organic acid,
0.3% by mass of methanesulfonic acid,
5.0% by mass of succinic acid,
As an amine compound,
0.75% by mass of triisopropanolamine,
As a hydrogen peroxide stabilizer
0.90% by mass of 2-butoxyethanol,
As azoles,
0.04 mass% of 5-amino-1H-tetrazole
As a fluoride ion source,
0.4 mass% of ammonium fluoride
The etching liquid raw material which consists of these is mixed with 76.04 mass% of water, and the etching concentrate was prepared.
　３５％過酸化水素水１６．５７重量％（エッチング液の全量に対して過酸化水素が５．８質量％と水分が１０．７７質量％）とエッチング濃縮液を混合し、過酸化水素濃度が５．８質量％のエッチング液を調製した。なお、水は全量で８６．８１質量％となる。また、液温は３５℃で用いた。エッチング液全体に占める各成分濃度と、各評価事項の結果を表１に示す。 The etching concentrate is mixed with 16.57% by weight of 35% hydrogen peroxide water (5.8% by weight of hydrogen peroxide and 10.77% by weight of water based on the total amount of etching solution), and the hydrogen peroxide concentration is A 5.8% by mass etchant was prepared. The total amount of water is 86.81% by mass. The solution temperature was 35 ° C. The concentration of each component in the entire etching solution and the result of each evaluation item are shown in Table 1.
　（実施例４）
　酸性有機酸として、
メタンスルホン酸を０．５質量％、
グルタル酸を１０．０質量％、
　アミン化合物として、
トリイソプロパノールアミンを０．７５質量％、
　過酸化水素安定剤として、
２－ブトキシエタノールを０．９０質量％、
　アゾール類として、
５－アミノ－１Ｈ－テトラゾールを０．０４質量％
　フッ素イオン供給源として、
フッ化アンモニウムを０．４質量％
からなるエッチング液原料を水７０．８４質量％と調合し、エッチング濃縮液を調製した。 (Example 4)
As an acidic organic acid,
0.5% by mass of methanesulfonic acid,
10.0% by mass of glutaric acid,
As an amine compound,
0.75% by mass of triisopropanolamine,
As a hydrogen peroxide stabilizer
0.90% by mass of 2-butoxyethanol,
As azoles,
0.04 mass% of 5-amino-1H-tetrazole
As a fluoride ion source,
0.4 mass% of ammonium fluoride
The etching liquid raw material which consists of these is mixed with 70.84 mass% of water, and the etching concentrate was prepared.
　３５％過酸化水素水１６．５７重量％（エッチング液の全量に対して過酸化水素が５．８質量％と水分が１０．７７質量％）とエッチング濃縮液を混合し、過酸化水素濃度が５．８質量％のエッチング液を調製した。なお、水は全量で８１．６１質量％となる。また、液温は３５℃で用いた。エッチング液全体に占める各成分濃度と、各評価事項の結果を表１に示す。 The etching concentrate is mixed with 16.57% by weight of 35% hydrogen peroxide water (5.8% by weight of hydrogen peroxide and 10.77% by weight of water based on the total amount of etching solution), and the hydrogen peroxide concentration is A 5.8% by mass etchant was prepared. The total amount of water is 81.61% by mass. The solution temperature was 35 ° C. The concentration of each component in the entire etching solution and the result of each evaluation item are shown in Table 1.
　（実施例５）
　酸性有機酸として、
メタンスルホン酸を０．３質量％、
マロン酸を５．０質量％、
　アミン化合物として、
トリイソプロパノールアミンを１．５質量％、
　過酸化水素安定剤として、
２－ブトキシエタノールを０．９０質量％、
　アゾール類として、
５－アミノ－１Ｈ－テトラゾールを０．０４質量％
　フッ素イオン供給源として、
フッ化アンモニウムを０．４質量％
からなるエッチング液原料を水７５．２９質量％と調合し、エッチング濃縮液を調製した。 (Example 5)
As an acidic organic acid,
0.3% by mass of methanesulfonic acid,
5.0% by mass of malonic acid,
As an amine compound,
1.5% by mass of triisopropanolamine,
As a hydrogen peroxide stabilizer
0.90% by mass of 2-butoxyethanol,
As azoles,
0.04 mass% of 5-amino-1H-tetrazole
As a fluoride ion source,
0.4 mass% of ammonium fluoride
The etching liquid raw material which consists of these is mixed with 75.29 mass% of water, and the etching concentrate was prepared.
　３５％過酸化水素水１６．５７重量％（エッチング液の全量に対して過酸化水素が５．８質量％と水分が１０．７７質量％）とエッチング濃縮液を混合し、過酸化水素濃度が５．８質量％のエッチング液を調製した。なお、水は全量で８６．０６質量％となる。また、液温は３５℃で用いた。エッチング液全体に占める各成分濃度と、各評価事項の結果を表１に示す。 The etching concentrate is mixed with 16.57% by weight of 35% hydrogen peroxide water (5.8% by weight of hydrogen peroxide and 10.77% by weight of water based on the total amount of etching solution), and the hydrogen peroxide concentration is A 5.8% by mass etchant was prepared. The total amount of water is 86.06% by mass. The solution temperature was 35 ° C. The concentration of each component in the entire etching solution and the result of each evaluation item are shown in Table 1.
　（実施例６）
　酸性有機酸として、
乳酸を４．５質量％、
　アミン化合物として、
トリイソプロパノールアミンを０．７５質量％、
　過酸化水素安定剤として、
２－ブトキシエタノールを０．９０質量％、
　アゾール類として、
５－アミノ－１Ｈ－テトラゾールを０．０４質量％
　フッ素イオン供給源として、
フッ化アンモニウムを０．４質量％
からなるエッチング液原料を水７６．８４質量％と調合し、エッチング濃縮液を調製した。 (Example 6)
As an acidic organic acid,
4.5% by mass of lactic acid,
As an amine compound,
0.75% by mass of triisopropanolamine,
As a hydrogen peroxide stabilizer
0.90% by mass of 2-butoxyethanol,
As azoles,
0.04 mass% of 5-amino-1H-tetrazole
As a fluoride ion source,
0.4 mass% of ammonium fluoride
The etching liquid raw material which consists of these is mixed with 76.84 mass% of water, and the etching concentrate was prepared.
　３５％過酸化水素水１６．５７重量％（エッチング液の全量に対して過酸化水素が５．８質量％と水分が１０．７７質量％）とエッチング濃縮液を混合し、過酸化水素濃度が５．８質量％のエッチング液を調製した。なお、水は全量で８７．６１質量％となる。また、液温は３５℃で用いた。エッチング液全体に占める各成分濃度と、各評価事項の結果を表１に示す。 The etching concentrate is mixed with 16.57% by weight of 35% hydrogen peroxide water (5.8% by weight of hydrogen peroxide and 10.77% by weight of water based on the total amount of etching solution), and the hydrogen peroxide concentration is A 5.8% by mass etchant was prepared. The total amount of water is 87.61% by mass. The solution temperature was 35 ° C. The concentration of each component in the entire etching solution and the result of each evaluation item are shown in Table 1.
　（比較例１）
　酸性有機酸として、
マロン酸を２０．０質量％、
　アミン化合物として、
水酸化テトラメチルアンモニウム（ＴＭＡＨ：ＣＡＳ番号７５－５９－２）を５．７質量％、
　過酸化水素安定剤として、
２－ブトキシエタノールを０．９０質量％、
　アゾール類として、
５－アミノ－１Ｈ－テトラゾールを０．２質量％
　フッ素イオン供給源として、
フッ化アンモニウムを０．２６質量％
からなるエッチング液原料を水５６．３７質量％と調合し、エッチング濃縮液を調製した。 (Comparative example 1)
As an acidic organic acid,
20.0% by weight of malonic acid,
As an amine compound,
5.7% by mass of tetramethylammonium hydroxide (TMAH: CAS number 75-59-2),
As a hydrogen peroxide stabilizer
0.90% by mass of 2-butoxyethanol,
As azoles,
0.2% by mass of 5-amino-1H-tetrazole
As a fluoride ion source,
0.26 mass% of ammonium fluoride
The etching liquid raw material which consists of these is mix | blended with 56.37 mass% of water, and the etching concentrate was prepared.
　３５％過酸化水素水１６．５７重量％（エッチング液の全量に対して過酸化水素が５．８質量％と水分が１０．７７質量％）とエッチング濃縮液を混合し、過酸化水素濃度が５．８質量％のエッチング液を調製した。なお、水は全量で６７．１４質量％となる。また、液温は３５℃で用いた。エッチング液全体に占める各成分濃度と、各評価事項の結果を表２に示す。 The etching concentrate is mixed with 16.57% by weight of 35% hydrogen peroxide water (5.8% by weight of hydrogen peroxide and 10.77% by weight of water based on the total amount of etching solution), and the hydrogen peroxide concentration is A 5.8% by mass etchant was prepared. The total amount of water is 67.14% by mass. The solution temperature was 35 ° C. The concentration of each component in the entire etching solution and the result of each evaluation item are shown in Table 2.
　（比較例２）
　酸性有機酸として、
メタンスルホン酸を２．３質量％
マロン酸を１０．０質量％、
　アミン化合物として、
水酸化テトラメチルアンモニウムを３．３質量％、
　過酸化水素安定剤として、
２－ブトキシエタノールを０．９０質量％、
　アゾール類として、
５－アミノ－１Ｈ－テトラゾールを０．１質量％
　フッ素イオン供給源として、
フッ化アンモニウムを０．２６質量％
からなるエッチング液原料を水６６．５７質量％と調合し、エッチング濃縮液を調製した。 (Comparative example 2)
As an acidic organic acid,
2.3% by mass of methanesulfonic acid
10.0% by mass of malonic acid,
As an amine compound,
3.3% by mass of tetramethylammonium hydroxide,
As a hydrogen peroxide stabilizer
0.90% by mass of 2-butoxyethanol,
As azoles,
0.1% by mass of 5-amino-1H-tetrazole
As a fluoride ion source,
0.26 mass% of ammonium fluoride
The etching liquid raw material which consists of these is mixed with 66.57 mass% of water, and the etching concentrate was prepared.
　３５％過酸化水素水１６．５７重量％（エッチング液の全量に対して過酸化水素が５．８質量％と水分が１０．７７質量％）とエッチング濃縮液を混合し、過酸化水素濃度が５．８質量％のエッチング液を調製した。なお、水は全量で７７．３４質量％となる。また、液温は３５℃で用いた。エッチング液全体に占める各成分濃度と、各評価事項の結果を表２に示す。 The etching concentrate is mixed with 16.57% by weight of 35% hydrogen peroxide water (5.8% by weight of hydrogen peroxide and 10.77% by weight of water based on the total amount of etching solution), and the hydrogen peroxide concentration is A 5.8% by mass etchant was prepared. The total amount of water is 77.34% by mass. The solution temperature was 35 ° C. The concentration of each component in the entire etching solution and the result of each evaluation item are shown in Table 2.
　（比較例３）
　酸性有機酸として、
メタンスルホン酸を０．３質量％
乳酸を１３．５質量％、
　アミン化合物として、
トリイソプロパノールアミンを１．５質量％、
　過酸化水素安定剤として、
２－ブトキシエタノールを０．９０質量％、
　アゾール類として、
５－アミノ－１Ｈ－テトラゾールを０．０１質量％
　フッ素イオン供給源として、
フッ化アンモニウムを０．４質量％
からなるエッチング液原料を水６６．８２質量％と調合し、エッチング濃縮液を調製した。 (Comparative example 3)
As an acidic organic acid,
0.3 mass% of methanesulfonic acid
13.5% by mass of lactic acid,
As an amine compound,
1.5% by mass of triisopropanolamine,
As a hydrogen peroxide stabilizer
0.90% by mass of 2-butoxyethanol,
As azoles,
0.01 mass% of 5-amino-1H-tetrazole
As a fluoride ion source,
0.4 mass% of ammonium fluoride
The etching liquid raw material which consists of these is mixed with water 66.82 mass%, and the etching concentrate is prepared.
　３５％過酸化水素水１６．５７重量％（エッチング液の全量に対して過酸化水素が５．８質量％と水分が１０．７７質量％）とエッチング濃縮液を混合し、過酸化水素濃度が５．８質量％のエッチング液を調製した。なお、水は全量で７７．５９質量％となる。また、液温は３５℃で用いた。エッチング液全体に占める各成分濃度と、各評価事項の結果を表２に示す。 The etching concentrate is mixed with 16.57% by weight of 35% hydrogen peroxide water (5.8% by weight of hydrogen peroxide and 10.77% by weight of water based on the total amount of etching solution), and the hydrogen peroxide concentration is A 5.8% by mass etchant was prepared. The total amount of water is 77.59% by mass. The solution temperature was 35 ° C. The concentration of each component in the entire etching solution and the result of each evaluation item are shown in Table 2.
　（比較例４）
　酸性有機酸として、
メタンスルホン酸を０．５質量％
　アミン化合物として、
トリイソプロパノールアミンを０．７５質量％、
　過酸化水素安定剤として、
２－ブトキシエタノールを０．９０質量％、
　アゾール類として、
５－アミノ－１Ｈ－テトラゾールを０．０４質量％
　フッ素イオン供給源として、
フッ化アンモニウムを０．４質量％
からなるエッチング液原料を水８０．８４質量％と調合し、エッチング濃縮液を調製した。 (Comparative example 4)
As an acidic organic acid,
0.5 mass% of methanesulfonic acid
As an amine compound,
0.75% by mass of triisopropanolamine,
As a hydrogen peroxide stabilizer
0.90% by mass of 2-butoxyethanol,
As azoles,
0.04 mass% of 5-amino-1H-tetrazole
As a fluoride ion source,
0.4 mass% of ammonium fluoride
The etching liquid raw material which consists of these is mixed with 80.84 mass% of water, and the etching concentrate was prepared.
　３５％過酸化水素水１６．５７重量％（エッチング液の全量に対して過酸化水素が５．８質量％と水分が１０．７７質量％）とエッチング濃縮液を混合し、過酸化水素濃度が５．８質量％のエッチング液を調製した。なお、水は全量で９１．６１質量％となる。また、液温は３５℃で用いた。エッチング液全体に占める各成分濃度と、各評価事項の結果を表２に示す。 The etching concentrate is mixed with 16.57% by weight of 35% hydrogen peroxide water (5.8% by weight of hydrogen peroxide and 10.77% by weight of water based on the total amount of etching solution), and the hydrogen peroxide concentration is A 5.8% by mass etchant was prepared. The total amount of water is 91.61% by mass. The solution temperature was 35 ° C. The concentration of each component in the entire etching solution and the result of each evaluation item are shown in Table 2.
　（比較例５）
　酸性有機酸として、
メタンスルホン酸を０．３質量％
グリコール酸を９．０質量％
　アミン化合物として、
トリイソプロパノールアミンを０．７５質量％、
　過酸化水素安定剤として、
２－ブトキシエタノールを０．９０質量％、
　アゾール類として、
５－アミノ－１Ｈ－テトラゾールを０．０４質量％
　フッ素イオン供給源として、
フッ化アンモニウムを０．４質量％
からなるエッチング液原料を水７２．０４質量％と調合し、エッチング濃縮液を調製した。 (Comparative example 5)
As an acidic organic acid,
0.3 mass% of methanesulfonic acid
9.0% by mass of glycolic acid
As an amine compound,
0.75% by mass of triisopropanolamine,
As a hydrogen peroxide stabilizer
0.90% by mass of 2-butoxyethanol,
As azoles,
0.04 mass% of 5-amino-1H-tetrazole
As a fluoride ion source,
0.4 mass% of ammonium fluoride
The etching liquid raw material which consists of these is mixed with 72.04 mass% of water, and the etching concentrate was prepared.
　３５％過酸化水素水１６．５７重量％（エッチング液の全量に対して過酸化水素が５．８質量％と水分が１０．７７質量％）とエッチング濃縮液を混合し、過酸化水素濃度が５．８質量％のエッチング液を調製した。なお、水は全量で８２．８１質量％となる。また、液温は３５℃で用いた。エッチング液全体に占める各成分濃度と、各評価事項の結果を表２に示す。
  The etching concentrate is mixed with 16.57% by weight of 35% hydrogen peroxide water (5.8% by weight of hydrogen peroxide and 10.77% by weight of water based on the total amount of etching solution), and the hydrogen peroxide concentration is A 5.8% by mass etchant was prepared. The total amount of water is 82.81% by mass. The solution temperature was 35 ° C. The concentration of each component in the entire etching solution and the result of each evaluation item are shown in Table 2.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　表１を参照する。実施例１乃至５は、有機酸としてメタンスルホン酸とその他の有機酸を併用したものである。これらの実施例においては、テーパー角、トップＣＤロスおよびボトムＣＤロスとも、好ましい範囲内でエッチングすることができた。また、これらの組成では、評価Ｃｕ濃度も８，０００ｐｐｍ以上であった。 See Table 1. In Examples 1 to 5, methanesulfonic acid and another organic acid are used in combination as the organic acid. In these examples, the taper angle, top CD loss and bottom CD loss could all be etched within the preferred ranges. Moreover, in these compositions, the evaluation Cu concentration was also 8,000 ppm or more.
　実施例６は有機酸として乳酸だけのものである。本発明に係るエッチング液では有機酸は、乳酸だけでも銅／チタンの多層膜を好適にエッチングすることができた。 Example 6 is only lactic acid as the organic acid. In the etching solution according to the present invention, the organic acid was able to suitably etch the copper / titanium multilayer film with only lactic acid.
　次に表２を参照する。表２は比較例を掲載したものである。比較例１および比較例２はいずれもフッ化アンモニウムが０．２６質量％であり、表１に示した各実施例よりも少ない場合である。比較例１および２ともに、規定時間内にジャストエッチの状態になることができず、エッチング残りが生じた。したがって、テーパー角等のサイドエッチングの指標は測定できなかった。表２の備考には「時間切れ」と記載した。 Next, refer to Table 2. Table 2 lists comparative examples. In each of Comparative Example 1 and Comparative Example 2, the amount of ammonium fluoride is 0.26% by mass, which is less than the examples shown in Table 1. In Comparative Examples 1 and 2, the state of just etching could not be achieved within the specified time, and an etching residue occurred. Therefore, the index of side etching such as taper angle could not be measured. In the remarks of Table 2, "time out" was described.
　比較例３は、有機酸としてメタンスルホン酸と乳酸を含んだ組成である。サイドエッチングの指標は値を掲載しているが、テーパー部分がテーパーになっておらず、形状が非常に乱れたエッチ面となっていた。表２の備考には「θ不良」と記載した。 Comparative Example 3 is a composition containing methanesulfonic acid and lactic acid as the organic acid. The index for the side etching is the value, but the tapered portion was not tapered, and the etching surface was very irregular in shape. In the remarks of Table 2, it described as "(theta) defect."
　比較例４は、有機酸としてメタンスルホン酸だけのものである。また比較例５は、有機酸としてメタンスルホン酸とグリコール酸を併用したものである。いずれの場合も、規定時間内にジャストエッチングの状態にならず、溶け残りがあった。表２の備考には「時間切れ」と記載した。 The comparative example 4 is a thing of only methanesulfonic acid as an organic acid. In Comparative Example 5, methanesulfonic acid and glycolic acid are used in combination as the organic acid. In either case, the state of just etching did not occur within the specified time, and there was unmelted material. In the remarks of Table 2, "time out" was described.
　以上のことより、メタンスルホン酸は全量に対して０．２質量％～１．５質量％の範囲であって、乳酸を併用する場合は乳酸は２．０質量％～１０．０質量％が望ましい。 From the above, methanesulfonic acid is in the range of 0.2 mass% to 1.5 mass% with respect to the total amount, and when lactic acid is used in combination, lactic acid is 2.0 mass% to 10.0 mass%. desirable.
　また、コハク酸を併用する場合、コハク酸は４．５質量％～５．５質量％がよく、グルタル酸を併用する場合、グルタル酸は９．５質量％～１０．５質量％がよく、マロン酸を併用する場合、マロン酸は４．５質量％～５．５質量％が望ましい。 When succinic acid is used in combination, 4.5% by mass to 5.5% by mass of succinic acid is preferable, and when glutaric acid is used in combination, glutaric acid is preferably 9.5% by mass to 10.5% by mass, When malonic acid is used in combination, malonic acid is preferably 4.5% by mass to 5.5% by mass.
　また、有機酸として乳酸は単独で使用することもできる。その際の乳酸は４．０質量％～５．０質量％が好適である。 Moreover, lactic acid can also be used alone as an organic acid. The content of lactic acid at that time is preferably 4.0% by mass to 5.0% by mass.
　以上のように、過酸化水素と、フッ素イオン供給源と、アゾールと、過酸化水素安定剤と、有機酸と、アミンと水で構成されるエッチング液であって、有機酸は、メタンスルホン酸と乳酸、コハク酸、グルタン酸、マロン酸から選ばれる少なくとも１種を含むものは、銅／チタンの多層膜を好適にエッチングすることができ、また、バスライフも長い。したがって、銅の膜厚が厚くなっても、頻繁にエッチング液の組成調整を行う必要がない。 As described above, the etching solution is composed of hydrogen peroxide, a fluorine ion source, an azole, a hydrogen peroxide stabilizer, an organic acid, an amine and water, and the organic acid is methanesulfonic acid. And those containing at least one selected from lactic acid, succinic acid, glutanoic acid and malonic acid can suitably etch a copper / titanium multilayer film, and also have a long bath life. Therefore, even if the film thickness of copper is increased, it is not necessary to adjust the composition of the etching solution frequently.
　本発明に係るエッチング液は、チタンと銅の多層膜をエッチングする際に好適に利用することができる。特に、銅イオン濃度が非常に高くなっても、サイドエッチングの特性を維持することができるので、銅の膜厚が厚くなっても長期間にわたって所定のエッチングレートの範囲を維持することができる。 The etching solution according to the present invention can be suitably used when etching a multilayer film of titanium and copper. In particular, even if the copper ion concentration becomes very high, the characteristics of the side etching can be maintained, so that the predetermined etching rate range can be maintained for a long time even if the copper film thickness becomes large.
ガラス基板１０
チタン層１２
銅層１４
（銅層１４の）上面１４ａ
（銅層１４の上面１４ａの）端１４ａａ
（銅層１４の）下面１４ｂ
（銅層１４の下面１４ｂの）端１４ｂａ
レジスト層１６
端１６ａ
仮想面１８
角度θ

  Glass substrate 10
Titanium layer 12
Copper layer 14
Top surface 14a (of copper layer 14)
End 14aa (of the top surface 14a of the copper layer 14)
Lower surface 14b (of copper layer 14)
End 14ba (of the lower surface 14b of the copper layer 14)
Resist layer 16
End 16a
Virtual plane 18
Angle θ

Claims (8)

  1. 　銅とチタンの多層膜をエッチングするエッチング液であって、
    （ａ）過酸化水素と、
    （ｂ）フッ素イオン供給源と、
    （ｃ）アゾール類と、
    （ｄ）過酸化水素安定剤と、
    （ｅ）有機酸と、
    （ｆ）アミン類と、
    （ｇ）水を含み、
    　前記有機酸はエッチング液全量に対してメタンスルホン酸と乳酸から選ばれ、
    　前記有機酸にメタンスルホン酸を含む場合は、前記メタンスルホン酸は、エッチング液全量に対して０．２質量％～１．５質量％含み、
    　　さらに、少なくとも乳酸、コハク酸、グルタル酸、マロン酸のうち一種の有機酸が併用され、
    　　　前記併用される有機酸に乳酸を含む場合は、前記乳酸は、エッチング液全量に対して２．０質量％～１０．０質量％であり、
    　　　前記併用される有機酸にコハク酸を含む場合、前記コハク酸は、エッチング液全量に対して４．５質量％～５．５質量％であり、
    　　　前記併用される有機酸にグルタル酸を含む場合、前記グルタル酸は、エッチング液全量に対して９．５質量％～１０．５質量％であり、
    　　　前記併用される有機酸にマロン酸を含む場合、前記マロン酸は、エッチング液全量に対して４．５質量％～５．５質量％であり、
    　前記有機酸が乳酸だけの場合は、前記乳酸はエッチング液全量に対して４．０質量％～５．０質量％であるエッチング液。     An etching solution for etching a multilayer film of copper and titanium,
    (A) hydrogen peroxide,
    (B) a fluorine ion supply source,
    (C) azoles,
    (D) hydrogen peroxide stabilizer,
    (E) with an organic acid,
    (F) amines,
    (G) contains water,
    The organic acid is selected from methanesulfonic acid and lactic acid based on the total amount of etching solution.
    When the organic acid contains methanesulfonic acid, the methanesulfonic acid contains 0.2% by mass to 1.5% by mass with respect to the total amount of the etching solution,
    Furthermore, at least one type of organic acid of lactic acid, succinic acid, glutaric acid and malonic acid is used in combination,
    When lactic acid is contained in the organic acid used in combination, the lactic acid is 2.0% by mass to 10.0% by mass with respect to the total amount of the etching solution,
    When succinic acid is contained in the organic acid used in combination, the succinic acid is 4.5% by mass to 5.5% by mass with respect to the total amount of the etching solution,
    When glutaric acid is contained in the organic acid used in combination, the glutaric acid is 9.5% by mass to 10.5% by mass with respect to the total amount of the etching solution,
    When malonic acid is contained in the organic acid used in combination, the malonic acid is 4.5% by mass to 5.5% by mass with respect to the total amount of the etching solution,
    When the organic acid is only lactic acid, the lactic acid is 4.0% by mass to 5.0% by mass with respect to the total amount of the etching liquid.
  2. 　前記フッ素イオン供給源は、フッ化アンモニウムである請求項１に記載されたエッチング液。 The etching solution according to claim 1, wherein the fluorine ion source is ammonium fluoride.
  3. 　前記アゾール類は、５－アミノ－１Ｈ－テトラゾールである請求項１または２に記載されたエッチング液。 The etching solution according to claim 1, wherein the azole is 5-amino-1H-tetrazole.
  4. 　前記過酸化水素安定剤は、２－ブトキシエタノールである請求項１乃至３の何れか一の請求項に記載されたエッチング液。 The etching solution according to any one of claims 1 to 3, wherein the hydrogen peroxide stabilizer is 2-butoxyethanol.
  5. 　前記アミン類はトリイソプロパノールアミンである請求項１乃至４の何れか一の請求項に記載されたエッチング液。 The etching solution according to any one of claims 1 to 4, wherein the amines are triisopropanolamine.
  6. 　銅とチタンの積層膜をエッチングするエッチング液を濃縮したエッチング濃縮液であって、
    （ｂ）フッ素イオン供給源と、
    （ｃ）アゾール類と、
    （ｄ）過酸化水素安定剤と、
    （ｅ）有機酸と、
    （ｆ）アミン類と、
    （ｇ）水を含み、
    　前記有機酸はエッチング液全量に対してメタンスルホン酸と乳酸から選ばれ、
    　前記有機酸にメタンスルホン酸を含む場合は、前記メタンスルホン酸は、過酸化水素を全量の４．０質量％～８．８質量％になるように混合した請求項１乃至５の何れかに記載された完全エッチング液の全量に対して０．２質量％～１．５質量％含み、
    　　さらに、少なくとも乳酸、コハク酸、グルタル酸、マロン酸のうちもう一種の有機酸が併用され、
    　　　前記併用される有機酸に乳酸を含む場合は、前記乳酸は、前記完全エッチング液の全量に対して２．０質量％～１０．０質量％であり、
    　　　前記併用される有機酸にコハク酸を含む場合、前記コハク酸は、前記完全エッチング液の全量に対して４．５質量％～５．５質量％であり、
    　　　前記併用される有機酸にグルタル酸を含む場合、前記グルタル酸は、前記完全エッチング液の全量に対して９．５質量％～１０．５質量％であり、
    　　　前記併用される有機酸にマロン酸を含む場合、前記マロン酸は、前記完全エッチング液全量に対して４．５質量％～５．５質量％であり、
    　前記有機酸が乳酸だけの場合は、前記乳酸は前記完全エッチング液の全量に対して４．０質量％～５．０質量％であるエッチング濃縮液。     It is an etching concentrate obtained by concentrating an etching solution for etching a laminated film of copper and titanium,
    (B) a fluorine ion supply source,
    (C) azoles,
    (D) hydrogen peroxide stabilizer,
    (E) with an organic acid,
    (F) amines,
    (G) contains water,
    The organic acid is selected from methanesulfonic acid and lactic acid based on the total amount of etching solution.
    6. The methanesulfonic acid according to any one of claims 1 to 5, wherein hydrogen peroxide is mixed so as to be 4.0 mass% to 8.8 mass% of the total amount when the organic acid contains methanesulfonic acid. 0.2% by mass to 1.5% by mass with respect to the total amount of the complete etching solution described
    Furthermore, at least one other organic acid of lactic acid, succinic acid, glutaric acid and malonic acid is used in combination,
    When lactic acid is contained in the organic acid used in combination, the lactic acid is 2.0% by mass to 10.0% by mass with respect to the total amount of the complete etching solution,
    When succinic acid is contained in the organic acid used in combination, the succinic acid is 4.5% by mass to 5.5% by mass with respect to the total amount of the complete etching solution,
    When glutaric acid is contained in the combined organic acid, the glutaric acid is 9.5% to 10.5% by mass with respect to the total amount of the complete etching solution,
    When malonic acid is contained in the combined organic acid, the malonic acid is 4.5% by mass to 5.5% by mass with respect to the total amount of the complete etching solution,
    When the organic acid is only lactic acid, the etching concentrate whose lactic acid is 4.0% by mass to 5.0% by mass with respect to the total amount of the complete etching solution.
  7. 　請求項１乃至５の何れか一の請求項に記載されたエッチング液を銅とチタンの多層膜にレジストパターンが配された被処理基板に接触させる工程と、
    　前記接触させた状態を所定時間維持する工程を有するエッチング方法。     Bringing the etching solution according to any one of claims 1 to 5 into contact with a substrate to be treated in which a resist pattern is disposed on a multilayer film of copper and titanium;
    An etching method comprising the step of maintaining the contact state for a predetermined time.
  8. 　請求項６に記載されたエッチング濃縮液と過酸化水素および水を混合し、請求項１乃至５に記載されたエッチング液を調製する工程と、
    　前記エッチング液を銅とチタンの多層膜にレジストパターンが配された被処理基板に接触させる工程と
    　前記接触させた状態を所定時間維持する工程を有するエッチング方法。     Mixing the etching concentrate according to claim 6 with hydrogen peroxide and water to prepare the etching solution according to claims 1 to 5;
    An etching method comprising the steps of: bringing the etching solution into contact with a substrate to be treated in which a resist pattern is disposed on a multilayer film of copper and titanium; and maintaining the contact state for a predetermined time.
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