WO2016152091A1 - Etching liquid for multilayer film, etching concentrate, and etching method - Google Patents

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

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WO2016152091A1
WO2016152091A1 PCT/JP2016/001462 JP2016001462W WO2016152091A1 WO 2016152091 A1 WO2016152091 A1 WO 2016152091A1 JP 2016001462 W JP2016001462 W JP 2016001462W WO 2016152091 A1 WO2016152091 A1 WO 2016152091A1
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Prior art keywords
etching
hydrogen peroxide
mass
acid
etching solution
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PCT/JP2016/001462
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French (fr)
Japanese (ja)
Inventor
真 着能
佑典 鬼頭
真一郎 淵上
善秀 小佐野
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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 CN201680001594.5A priority Critical patent/CN106460197B/en
Publication of WO2016152091A1 publication Critical patent/WO2016152091A1/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
    • H01L21/30—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 a multilayer film etching solution, an etching concentrate, and an etching method used when etching a multilayer film of a copper layer and a molybdenum layer 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 (FPD) such as liquid crystal and organic EL (Electro-Luminescence).
  • FPD Thin Film Transistors
  • FPD flat panel displays
  • the wiring material used has been required to have a resistance lower than that of aluminum.
  • copper which has a lower resistance than aluminum, has been used as a wiring material.
  • a multilayer structure in which a molybdenum layer is first formed on a substrate or a semiconductor substrate and then a copper layer is formed thereon is employed.
  • the FPD wiring is formed by wet etching a multilayer film formed by a sputtering method. This is because a large area can be formed at a stretch, and the process can be shortened.
  • the following points are important for wet etching of wiring. (1) Processing accuracy is high and uniform. (2) The wiring cross section after processing is a forward taper of a predetermined angle. (3) Etching performance is unlikely to deteriorate due to copper ions contained in the etching solution (long bath life). (4) There is little generation of precipitates.
  • the first item high processing accuracy and uniformity, is an essential item when processing not only wet etching but also micro regions.
  • the shape of the wiring cross section which is the second item, is a shape necessary for performing reliable wiring formation when forming large-area FPD wirings at once. This is because, if the etched edge portion of the multilayer film of the copper layer and the molybdenum layer can be formed with a forward taper of 30 to 60 degrees from the substrate, an etching failure will occur, and the etching rate of copper and molybdenum will increase. This is because a margin for ensuring product quality can be secured even if the balance is different.
  • the third item is the life problem of the etching solution itself.
  • a large amount of etching solution is required.
  • These etching solutions are circulated from the viewpoint of cost. The cost is lower when the period (life) in which the etching performance can be maintained is as long as possible.
  • the fourth item is not only a problem for maintaining the etching apparatus but also a problem related to the quality problem of the product.
  • the piping of the etching apparatus may be clogged, or the holes of the shower nozzle for spraying the etching solution may be clogged. These phenomena cause the operation of the etching apparatus to stop, leading to an increase in cost.
  • the deposit adheres to the product via the etching solution, it causes a short circuit or disconnection, which directly affects the quality of the product.
  • Patent Document 2 An etching solution of a copper molybdenum film containing a predetermined amount of each of a fluorine compound and deionized water has been reported (Patent Document 2).
  • An etching solution for a multilayer thin film containing a copper layer and a molybdenum layer having a pH of 2.5 to 5 has been reported (Patent Document 4).
  • JP 2002-302780 A Patent No. 4282927 JP 2004-193620 A (Patent No. 4448322) JP 2007-005790 A (Patent No. 5111790) Japanese Patent No. 5051323
  • Patent Document 1 discloses a specific etching solution in the case of a mixed solution of hydrogen peroxide and an organic acid, only that the copper and molybdenum can be etched simultaneously by adjusting the ratio of hydrogen peroxide.
  • the composition of is not disclosed at all.
  • Patent Documents 2 and 3 use a fluorine compound in the composition. Accordingly, there is a problem that not only the glass substrate or the silicon substrate is etched, but also an environmental load is increased when the etching solution is discarded.
  • Patent Document 4 examines the etching of a multilayer film of a copper layer and a molybdenum layer in detail.
  • the composition of the etching solution of Patent Document 4 has a problem that a large amount of precipitates are generated in the etching solution.
  • hydrogen peroxide is self-decomposing. If left untreated, the proportion of hydrogen peroxide decreases and the etching rate changes greatly. Therefore, the decomposition of hydrogen peroxide must be suppressed to some extent.
  • the present invention has been conceived in view of the above-described problems, and is an etching solution composition for a multilayer film including a copper layer and a molybdenum layer that satisfies the point important for wet etching of wiring described in [Background Art]. Is to provide.
  • the present invention provides an etching solution, a concentrated solution thereof, and an etching method that do not generate precipitates in the etching solution and that do not increase the environmental load during disposal.
  • an etching solution for a multilayer film including a copper layer and a molybdenum layer according to the present invention, Hydrogen peroxide, Inorganic acids, An acidic organic acid, Neutral organic acids, An amine compound; It contains hydrogen peroxide decomposition inhibitor.
  • the etching liquid which concerns on this invention can be comprised in the state of a concentrate so that it may not become bulky at the time of a preservation
  • an etching concentrate for a multilayer film comprising a copper layer and a molybdenum layer according to the present invention, Inorganic acids, An acidic organic acid, Neutral organic acids, An amine compound; A hydrogen peroxide decomposition inhibitor; It contains water.
  • the etching method of the multilayer film including the copper layer and the molybdenum layer according to the present invention is as follows: Inorganic acids, An acidic organic acid, Neutral organic acids, An amine compound; A step of preparing an etching solution for multilayer film by preparing an etching concentrate containing hydrogen peroxide decomposition inhibitor and water, water and hydrogen peroxide; The method includes a step of bringing the multilayer film etching solution into contact with a substrate to be processed.
  • the cross-sectional shape of the etched wiring becomes a forward taper, and the shape is maintained even when overetching is performed. Moreover, since it is a structure which does not contain the azole compound which produces
  • the etching concentrate according to the present invention does not contain hydrogen peroxide and a predetermined amount of water from the above-mentioned etching solution, so that it can be stored or transported without being bulky and causing little change over time.
  • the etching concentrate and hydrogen peroxide can be handled separately, it is possible to easily adjust the concentration of the etching liquid whose component concentration has changed due to use.
  • the etching method according to the present invention prepares an etching solution having a stable composition at any time because the etching concentrated solution and the hydrogen peroxide solution are prepared and the etching solution is prepared and brought into contact with the substrate to be processed.
  • the cross section of the formed wiring has a forward taper, and even when overetching, the taper angle can be etched while maintaining a suitable angle range.
  • the etching solution according to the present invention does not contain substances such as phosphorus compounds, chlorine compounds, and fluorine compounds, there is an advantage that the burden on the environment is light when discarded.
  • the etching solution according to the present invention is characterized in that no precipitate is generated in the etching solution. As shown in the examples described later, it was strongly suggested that the cause of the precipitate was a reaction product of an azole compound and hydrogen peroxide. Therefore, the etching solution according to the present invention does not contain an azole compound.
  • phosphorus compounds, fluorine compounds, and chlorine compounds are not included. However, it may be included when it does not affect the etching performance and product quality, or when the environmental load at the time of disposal is below the standard established in each country. Further, such an amount may be interpreted as not including.
  • ⁇ Hydrogen peroxide> In the etching of copper, copper is oxidized to become copper oxide (CuO), which is dissolved by an inorganic acid. Etching of molybdenum is oxidized to molybdenum oxide (MoO 3 ) and dissolved in water. Hydrogen peroxide is used as an oxidizing agent that oxidizes copper and molybdenum. Hydrogen peroxide is preferably 3.50% by mass or more and 5.80% by mass or less of the total amount of the etching solution. Hydrogen peroxide is also called “overwater”.
  • Inorganic acids are used to dissolve oxidized copper. Phosphorus compounds and fluorine compounds are not used in order not to affect the substrate material such as glass or silicon and to reduce the environmental load when discarding the etchant. Also, hydrochloric acid is not used. Nitric acid and sulfuric acid can be suitably used.
  • the inorganic acid is included in the range of 0.01% by mass or more and 2.00% by mass or less, preferably 0.02% by mass or more and 1.50% by mass or less with respect to the total amount of the etching solution.
  • the organic acid component mainly serves to adjust the taper angle of the cross section of the etched wiring. It is also considered to have a function to suppress the decomposition of hydrogen peroxide to some extent.
  • the organic acid component a combination of an acidic organic acid and a neutral organic acid is used. Moreover, you may combine both an acidic organic acid and a neutral organic acid.
  • organic acids that can be used include aliphatic carboxylic acids having 1 to 18 carbon atoms, aromatic carboxylic acids having 6 to 10 carbon atoms, and amino acids having 1 to 10 carbon atoms.
  • aliphatic carboxylic acids having 1 to 18 carbon atoms include formic acid, acetic acid, propionic acid, lactic acid, glycolic acid, diglycolic acid, pyruvic acid, malonic acid, butyric acid, hydroxybutyric acid, tartaric acid, succinic acid, malic acid, maleic acid , Fumaric acid, valeric acid, glutaric acid, itaconic acid, adipic acid, caproic acid, adipic acid, citric acid, propanetricarboxylic acid, trans-aconitic acid, enanthic acid, caprylic acid, lauric acid, myristic acid, palmitic acid, stearin Preferred are acid, oleic acid, linoleic acid, linolenic acid and the like.
  • 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 acids having 1 to 10 carbon atoms include carbamic acid, alanine, glycine, asparagine, aspartic acid, sarcosine, serine, glutamine, glutamic acid, 4-aminobutyric acid, iminodibutyric acid, arginine, leucine, isoleucine, nitrilotriacetic acid, etc. Are preferred.
  • glycolic acid and malic acid can be suitably used as the acidic organic acid.
  • glycolic acid and malic acid can obtain suitable characteristics by simultaneously using two kinds.
  • glycolic acid is preferably 0.5% by mass or more and 5.00% by mass or less, more preferably 1.00% by mass or more and 2.00% by mass with respect to the total amount of the etching solution. It is good to contain below mass%. Further, malic acid is preferably contained in an amount of 0.10% by mass or more and 1.00% by mass or less, and more preferably 0.50% by mass or more and 0.80% by mass or less based on the total amount of the etching solution.
  • glycine, alanine or ⁇ -alanine can be suitably used as the neutral organic acid.
  • the neutral organic acid is preferably contained in an amount of 0.10% by mass to 3.00% by mass with respect to the total amount of the etching solution.
  • the amine compound is mainly responsible for adjusting the pH of the etching solution.
  • the amine compound those 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, trieth
  • the amine compound is preferably contained in an amount of 0.50% by mass or more and 2.00% by mass or less, more preferably 0.75% by mass or more and 1.50% by mass or less based on the total amount of the etching solution. .
  • etching solution according to the present invention hydrogen peroxide is used as an oxidizing agent. Since hydrogen peroxide self-decomposes, a decomposition inhibitor that suppresses the decomposition is added. This is for extending the life of the etching solution.
  • the main hydrogen peroxide decomposition inhibitors include phenyl urea, allyl urea, 1,3-dimethylurea, urea-based hydrogen peroxide stabilizers such as thiourea, phenylacetamide, phenylethylene glycol, 1-propanol, Preferred are lower alcohols such as 2-propanol and ethers such as 2-butoxyethanol (ethylene glycol monobutyl ether).
  • the hydrogen peroxide decomposition inhibitor is improved by the presence of malic acid, which is an acidic organic acid, in combination with the hydrogen peroxide decomposition inhibitor. These substances are considered to suppress the decomposition of hydrogen peroxide by acting on hydrogen peroxide and suppressing the generation of radicals.
  • the etching rate according to the present invention changes as the Cu ion concentration increases as etching progresses and Cu ions and Mo ions are included.
  • the operation of the etching equipment is controlled by adding an etching concentrate and hydrogen peroxide so that the change in etching rate is within a certain allowable range. Is preferred. Therefore, the etching solution may contain a predetermined range of Cu ions. Specifically, if the Cu ions are contained in an amount of 500 ppm to 7000 ppm, preferably 2000 ppm to 4000 ppm with respect to the total amount of the etching solution, a change in the etching rate is easily assumed.
  • the etching solution according to the present invention may contain molybdenum ions.
  • Mo ions are approximately one-tenth of the Cu ions. Therefore, Mo ions may be included in the range of 50 to 700 ppm, preferably 200 ppm to 400 ppm.
  • etching solution of the present invention various commonly used additives may be added to the etching solution of the present invention as long as water and etching performance are not impaired. Since water is used for precision processing, it is preferable that water does not exist. Pure water or ultrapure water is preferable.
  • the etching solution according to the present invention is preferably used in the range of pH 2 to 5, more preferably pH 3 to 4.5, and most preferably pH 3.3 to 3.9.
  • the etching liquid which concerns on this invention can be used between 18 degreeC or more and 40 degrees C or less. More preferably, it is 18 degreeC or more and 35 degrees C or less, Most preferably, 20 degreeC or more and 32 degrees C or less are good.
  • Hydrogen peroxide is used for the etching solution according to the present invention. Hydrogen peroxide is self-degrading. Therefore, the etchant contains a hydrogen peroxide decomposition inhibitor. However, when storing, the hydrogen peroxide solution and other liquids may be stored separately. Alternatively, a raw material excluding hydrogen peroxide and copper ions (referred to as an “etching liquid raw material”) and water may be mixed to prepare an etching liquid raw material solution. 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 etchant raw material prepared by mixing the etchant raw material and water is called “etching concentrate”.
  • the etching concentrate has a smaller volume as compared with the etching liquid because there is no hydrogen peroxide, so it is convenient for storage and transport.
  • an “etching highly concentrated solution” in which water of the “etching concentrated solution” is reduced may be used.
  • Etching highly concentrated liquid means what contains 20% or more and 70% or less of water.
  • the etching concentrate contains more than 70% water. Therefore, the etching solution of the present invention may be completed by combining the etching concentrate and hydrogen peroxide solution, or may be completed by combining the etching high concentration solution, water, and hydrogen peroxide solution.
  • the target for using the etching solution according to the present invention is a multilayer film of copper layer / molybdenum layer in which molybdenum is a lower layer and copper is an upper layer.
  • the lower molybdenum layer is thinner than the upper copper.
  • the range of t0 / t1 is in the range of 0.01 to 0.2. If the range of t0 / t1 is out of this range and the Mo layer is too thick, the Mo layer residue tends to be generated, and conversely, if it is too thin, the Cu layer can no longer serve as an underlayer.
  • the substrate and the base layer on which the molybdenum layer and the copper layer are formed are not particularly limited, and include glass, silicon, amorphous silicon, IGZO (Indium, Gallium, Zinc), oxygen ( It may be a metal oxide such as an amorphous semiconductor composed of Oxide).
  • the etching solution according to the present invention can be stored by storing the hydrogen peroxide solution, the highly concentrated etching solution, and water (hydrogen peroxide solution and the etching concentrated solution) separately during storage. Become. Therefore, in actual use, these are mixed to complete the etching solution.
  • the blending method is not limited as long as the concentration of hydrogen peroxide finally reaches a predetermined concentration.
  • an etching concentrate prepared by mixing an etching solution raw material with a certain amount of water is prepared.
  • Hydrogen peroxide is usually supplied as a hydrogen peroxide solution having a concentration higher than that of the etching solution according to the present invention. Therefore, a predetermined amount of hydrogen peroxide solution and etching concentrate is prepared. This step may be called a step of preparing a multilayer film etching solution.
  • an etching solution may be prepared by preparing a high etching concentration solution, water, and hydrogen peroxide solution having a higher concentration than the etching concentration solution.
  • Copper ions can be mixed at any stage of preparing an etching concentrate (or highly concentrated etching solution) with an etchant raw material and water, or when preparing an etching solution with an etching concentrate and hydrogen peroxide. it can.
  • the etching solution may be added after being prepared.
  • an etching concentrate and hydrogen peroxide water are additionally added to the etching solution already used, it is not necessary to add copper ions. This is because copper ions are already present in the etching solution.
  • the etching solution is used under the conditions of pH 2 to 5 and 18 ° C. to 40 ° C. Therefore, it is desirable that the object to be etched is also preheated to this temperature.
  • the method for bringing the substrate to be treated into contact with the etching solution is not particularly limited. An etching solution may be sprayed on the substrate to be processed from above as in a shower type, or a method of dipping the substrate to be processed into a pool of etching solution may be used. This step may be called a step of bringing the multilayer film etching solution into contact with the substrate to be processed.
  • the substrate to be processed is formed by laminating a molybdenum layer (Mo layer) and a copper layer (Cu layer) on a base material such as glass, and a pattern of a resist layer for pattern formation is formed on the laminated film. It is a substrate in a state of being.
  • Mo layer molybdenum layer
  • Cu layer copper layer
  • etching solution according to the present invention the etching rate of copper and molybdenum (nm / min), the taper angle (°) of the cross section of the etched wiring, the undercut of the molybdenum layer, the molybdenum layer remaining on the substrate ( Evaluation was performed on the items of “Mo residue”), over-etching resistance, presence of precipitates, and hydrogen peroxide decomposition rate (mass% / day).
  • the etching rate was measured as follows. First, a single layer film having a thickness of 300 nm for copper and 150 nm for molybdenum was formed on a silicon wafer on which a thermal oxide film of 100 nm was formed by sputtering. The copper film and the molybdenum film were brought into contact with an etching solution at 30 ° C. (may be 35 ° C. in some comparative examples) for 20 to 60 seconds.
  • the resistance value of the film before and after etching was measured using a constant current application type 4-terminal 4-probe resistivity meter (manufactured by Mitsubishi Chemical Analytech: MCP-T610 type). The change in film thickness was calculated from the change in resistance value, and the etching rate was calculated.
  • the taper angle (referred to as “taper angle” in the table below) was measured as follows. First, a molybdenum layer having a thickness of 20 nm was formed on a glass substrate by a sputtering method, and a copper layer having a thickness of 300 nm was subsequently formed thereon to prepare a Cu / Mo multilayer film sample. A resist patterned into a wiring shape was formed on the copper layer, and a substrate for taper angle evaluation was obtained. That is, the taper angle evaluation base material includes a substrate, a molybdenum layer, a copper layer thereon, and a patterned resist layer on the copper layer. Etching was performed by immersing this base for taper angle evaluation in an etching solution for the time of just etching. After the etching sample was washed and dried, the wiring portion was cut and the cut surface was observed.
  • an angle 5 formed by the substrate 1 and the etched inclined surface 6 is a taper angle (°).
  • the taper angle 5 is 30 ° or more and 60 ° or less, it is judged as a circle ( ⁇ ). If it was out of the range of this angle, it was judged as X (x).
  • “Mal” means success or success, and “X” means failure or failure.
  • the Mo layer is indicated by reference numeral 3
  • the Cu layer is indicated by reference numeral 2
  • the resist layer is indicated by reference numeral 4.
  • the thickness of the Cu layer 2 is indicated by t1
  • the thickness of the Mo layer 3 is indicated by t0.
  • Undercut of the molybdenum layer 3 (referred to as “Mo undercut” in the following table) is etched faster than the copper layer 2 between the molybdenum layer 3 and the substrate 1 as indicated by reference numeral 10 in FIG. State (reverse taper).
  • the evaluation can be performed simultaneously with the evaluation of the taper angle 5. If the undercut 10 of the molybdenum layer 3 was not found by observation at 30,000 to 50,000 times the SEM, it was judged as a circle ( ⁇ ), and if found, it was judged as a cross ( ⁇ ).
  • Mo residue The Mo residue (referred to as “Mo residue” in the following table) was determined to be “X” when the residue was confirmed by observation with an optical microscope and SEM, and “M” when the residue was not confirmed.
  • the optical microscope was observed with bright field observation and dark field observation at a magnification of about 100 times.
  • SEM it observed by 30,000 times to 50,000 times.
  • Over-etching resistance refers to taper angle 5 when etching is twice the time required for just etching, undercut 10 of molybdenum layer 3, Mo residue Was observed, and if all were "Mal” evaluation, it was judged as Mull ( ⁇ ). If any one of them is judged as “X”, it is X (X).
  • Presence / absence of precipitates was determined by visually determining whether or not precipitates were formed in the bottle after the etching solution was prepared and left in the bottle at room temperature for a predetermined time (several days).
  • the etching solution is filtered with a filter paper, the foreign matter remaining on the filter paper is washed with pure water and dried at room temperature, and the obtained crystals and powder are converted into FT-IR (Shimadzu IR affinity). ) And SEM-EDX (Horiba Seisakusho). If the precipitate was not visually observed, it was judged as round ( ⁇ ), and if it was visually confirmed, it was judged as X (x).
  • the decomposition rate of hydrogen peroxide is also an important item.
  • the hydrogen peroxide decomposition rate was also examined as an evaluation item.
  • the hydrogen peroxide decomposition rate (referred to as “perhydrolysis rate” in the table below) is the hydrogen peroxide concentration immediately after the preparation of the etchant and after the lapse of a predetermined time (about 24 hours), and the titration reagent is potassium permanganate. The measurement was performed using an automatic titrator (GP-200 manufactured by Mitsubishi Chemical Analytech). Then, the decomposition rate was calculated from the amount of change in the hydrogen peroxide concentration.
  • the decrease amount of the hydrogen peroxide concentration after 24 hours is less than 0.24% by mass, it is evaluated as a double circle ( ⁇ ), and if it is 0.24% by mass or more and 0.96% by mass or less, ⁇ ), and when it exceeded 0.96 mass%, it was evaluated as X (x).
  • the amount of decrease in the hydrogen peroxide concentration after 24 hours is described as, for example, “0.24 mass% / day”.
  • the double circle represents a particularly desirable result among the acceptance criteria.
  • a value extremely close to the boundary value was evaluated as a triangle ( ⁇ ).
  • Example 1 1.29 mass% nitric acid, 1.14% by weight of glycolic acid, 0.85% by mass of malic acid, ⁇ -alanine 1.42% by mass, 1.71% by mass of 1 amino 2-propanol, 0.11% by mass of phenylurea, 1.16% by mass of 1-propanol 1.29 mass% of 2-butoxyethanol
  • the etching liquid raw material which consists of was mixed with water 91.03 mass%, and the etching concentrated liquid was prepared.
  • Hydrogen peroxide and etching concentrate were mixed to prepare an etching solution having a hydrogen peroxide concentration of 4.50% by mass. Further, copper sulfate and molybdenum powder were added to prepare a copper ion concentration of 2000 ppm and a molybdenum ion concentration of 200 ppm. The liquid temperature was 30 ° C. Table 1 shows the concentration of each component in the etching concentrate and the result of each evaluation item. Table 3 shows the concentration of each component in the entire etching solution.
  • Example 2 0.09 mass% nitric acid, 1.44% by weight of glycolic acid, 0.86% by mass of malic acid, 0.91% by mass of ⁇ -alanine, 0.87% by mass of 1 amino 2-propanol, 0.11% by mass of phenylurea, 1.15% by mass of 1-propanol 1.28 mass% of 2-butoxyethanol An etching solution raw material consisting of 93.29% by mass of water was prepared to prepare an etching concentrate.
  • Hydrogen peroxide and etching concentrate were mixed to prepare an etching solution having a hydrogen peroxide concentration of 4.50% by mass. Further, copper sulfate and molybdenum powder were added to prepare a copper ion concentration of 2000 ppm and a molybdenum ion concentration of 200 ppm. The liquid temperature was 30 ° C. Table 1 shows the concentration of each component in the etching concentrate and the result of each evaluation item. Table 3 shows the concentration of each component in the entire etching solution.
  • Example 3 0.18% by mass of nitric acid, 1.30% by weight of glycolic acid, 0.87 mass% malic acid, 0.91% by mass of ⁇ -alanine, 0.86% by mass of 1 amino 2-propanol, 0.11% by mass of phenylurea, 1.16% by mass of 1-propanol 1.28 mass% of 2-butoxyethanol
  • the etching liquid raw material consisting of was mixed with 93.33% by mass of water to prepare an etching concentrated liquid.
  • Hydrogen peroxide and etching concentrate were mixed to prepare an etching solution having a hydrogen peroxide concentration of 4.50% by mass. Further, copper sulfate and molybdenum powder were added to prepare a copper ion concentration of 2000 ppm and a molybdenum ion concentration of 200 ppm. The liquid temperature was 30 ° C. Table 1 shows the concentration of each component in the etching concentrate and the result of each evaluation item. Table 3 shows the concentration of each component in the entire etching solution.
  • Example 4 1.29 mass% nitric acid, 1.14% by weight of glycolic acid, 0.85% by mass of malic acid, ⁇ -alanine 1.42% by mass, 1.71% by mass of 1 amino 2-propanol, 0.11% by mass of phenylurea, 1.16% by mass of 1-propanol
  • the etching liquid raw material which consists of was mixed with water 92.32 mass%, and the etching concentrated liquid was prepared.
  • Hydrogen peroxide and etching concentrate were mixed to prepare an etching solution having a hydrogen peroxide concentration of 4.50% by mass. Further, copper sulfate and molybdenum powder were added to prepare a copper ion concentration of 2000 ppm and a molybdenum ion concentration of 200 ppm. The liquid temperature was 30 ° C. Table 1 shows the concentration of each component in the etching concentrate and the result of each evaluation item. Table 3 shows the concentration of each component in the entire etching solution.
  • Example 5 1.29 mass% nitric acid, 1.14% by weight of glycolic acid, 0.85% by mass of malic acid, ⁇ -alanine 1.42% by mass, 1.71% by mass of 1 amino 2-propanol, 1.16% by mass of 1-propanol 1.29 mass% of 2-butoxyethanol An etching solution raw material consisting of 91.14% by mass of water was prepared to prepare an etching concentrate.
  • Hydrogen peroxide and etching concentrate were mixed to prepare an etching solution having a hydrogen peroxide concentration of 4.50% by mass. Further, copper sulfate and molybdenum powder were added to prepare a copper ion concentration of 2000 ppm and a molybdenum ion concentration of 200 ppm. The liquid temperature was 30 ° C. Table 1 shows the concentration of each component in the etching concentrate and the result of each evaluation item. Table 3 shows the concentration of each component in the entire etching solution.
  • Example 6 1.29 mass% nitric acid, 1.14% by weight of glycolic acid, 0.85% by mass of malic acid, ⁇ -alanine 1.42% by mass, 1.71% by mass of 1 amino 2-propanol, 0.11% by mass of phenylurea, 1.29 mass% of 2-butoxyethanol An etching liquid raw material consisting of 92.19% by mass of water was prepared to prepare an etching concentrated liquid.
  • Hydrogen peroxide and etching concentrate were mixed to prepare an etching solution having a hydrogen peroxide concentration of 4.50% by mass. Further, copper sulfate and molybdenum powder were added to prepare a copper ion concentration of 2000 ppm and a molybdenum ion concentration of 200 ppm. The liquid temperature was 30 ° C. Table 1 shows the concentration of each component in the etching concentrate and the result of each evaluation item. Table 3 shows the concentration of each component in the entire etching solution.
  • Example 7 1.29 mass% nitric acid, 1.14% by weight of glycolic acid, 0.85% by mass of malic acid, ⁇ -alanine 1.42% by mass, 1.71% by mass of 1 amino 2-propanol, 1.16% by mass of 1-propanol
  • the etching liquid raw material which consists of was mixed with 92.43 mass% of water, and the etching concentrated liquid was prepared.
  • Hydrogen peroxide and etching concentrate were mixed to prepare an etching solution having a hydrogen peroxide concentration of 4.50% by mass. Further, copper sulfate and molybdenum powder were added to prepare a copper ion concentration of 2000 ppm and a molybdenum ion concentration of 200 ppm. The liquid temperature was 30 ° C. Table 1 shows the concentration of each component in the etching concentrate and the result of each evaluation item. Table 3 shows the concentration of each component in the entire etching solution.
  • Example 8 1.29 mass% nitric acid, 1.14% by weight of glycolic acid, 0.85% by mass of malic acid, ⁇ -alanine 1.42% by mass, 1.71% by mass of 1 amino 2-propanol, 1.29 mass% of 2-butoxyethanol
  • the etching liquid raw material which consists of was mixed with 92.30 mass% of water, and the etching concentrated liquid was prepared.
  • Hydrogen peroxide and etching concentrate were mixed to prepare an etching solution having a hydrogen peroxide concentration of 4.50% by mass. Further, copper sulfate and molybdenum powder were added to prepare a copper ion concentration of 2000 ppm and a molybdenum ion concentration of 200 ppm. The liquid temperature was 30 ° C. Table 1 shows the concentration of each component in the etching concentrate and the result of each evaluation item. Table 3 shows the concentration of each component in the entire etching solution.
  • Hydrogen peroxide and etching concentrate were mixed to prepare an etching solution having a hydrogen peroxide concentration of 4.50% by mass. Further, copper sulfate and molybdenum powder were added to prepare a copper ion concentration of 2000 ppm and a molybdenum ion concentration of 200 ppm. The liquid temperature was 30 ° C. Table 2 shows the concentration of each component in the etching concentrate and the result of each evaluation item. Table 4 shows the concentration of each component in the entire etching solution.
  • Hydrogen peroxide and etching concentrate were mixed to prepare an etching solution having a hydrogen peroxide concentration of 4.50% by mass. Further, copper sulfate and molybdenum powder were added to prepare a copper ion concentration of 2000 ppm and a molybdenum ion concentration of 200 ppm. The liquid temperature was 25 ° C. Table 2 shows the concentration of each component in the etching concentrate and the result of each evaluation item. Table 4 shows the concentration of each component in the entire etching solution.
  • Hydrogen peroxide and etching concentrate were mixed to prepare an etching solution having a hydrogen peroxide concentration of 4.50% by mass. Further, copper sulfate and molybdenum powder were added to prepare a copper ion concentration of 2000 ppm and a molybdenum ion concentration of 200 ppm. The liquid temperature was 27.5 ° C. Table 2 shows the concentration of each component in the etching concentrate and the result of each evaluation item. Table 4 shows the concentration of each component in the entire etching solution.
  • Hydrogen peroxide and etching concentrate were mixed to prepare an etching solution having a hydrogen peroxide concentration of 4.50% by mass. Further, copper sulfate and molybdenum powder were added to prepare a copper ion concentration of 2000 ppm and a molybdenum ion concentration of 200 ppm. The liquid temperature was 25 ° C. Table 2 shows the concentration of each component in the etching concentrate and the result of each evaluation item. Table 4 shows the concentration of each component in the entire etching solution.
  • Hydrogen peroxide and etching concentrate were mixed to prepare an etching solution having a hydrogen peroxide concentration of 4.50% by mass. Further, copper sulfate and molybdenum powder were added to prepare a copper ion concentration of 2000 ppm and a molybdenum ion concentration of 200 ppm. The liquid temperature was 30 ° C. Table 2 shows the concentration of each component in the etching concentrate and the result of each evaluation item. Table 4 shows the concentration of each component in the entire etching solution.
  • Examples 1 to 8 are etching solutions according to the present invention. Since no azole compound is contained, no reaction product is formed with hydrogen peroxide, and there is no precipitate. Two kinds of glycolic acid and malic acid were used simultaneously as the acidic organic acid. These samples have no precipitates, and have a taper angle, Mo undercut, Mo residue, O.D. E. All items of resistance were rated as maru. Furthermore, the hydrogen peroxide decomposition rate was less than 0.96% by mass / day, and desirable results could be obtained.
  • the over-etching resistance was good, it was possible to perform etching while maintaining a good taper angle from the time spent for just etching to twice the time.
  • the etching ratios of these examples are 0.01 to 0.2 even if the film thickness ratio of Mo and Cu (t0 / t1) is different from that of the example (20/300). In the meantime, a taper angle of 30 ° or more and 60 ° or less could be realized.
  • the hydrogen peroxide decomposition inhibitor As the hydrogen peroxide decomposition inhibitor, phenylurea, 1-propanol, and 2-butoxyethanol were used, but the decomposition rate of hydrogen peroxide was suppressed if at least one of 1-propanol and 2-butoxyethanol was included. . However, even if 1-propanol was included as in Comparative Example 1, decomposition of hydrogen peroxide could not be suppressed if malic acid was not included. From this, it can be concluded that the hydrogen peroxide decomposition inhibitor was able to effectively suppress hydrogen peroxide decomposition when used with malic acid.
  • Comparative Example 5 is an example using phenylurea and malic acid, but the hydrogen peroxide decomposition could not be suppressed as much as each sample of the example. However, as can be seen from the results of each example, it can be used with 1-propanol and / or 2-butoxyethanol.
  • the etching solution according to the present invention can be handled as an etching concentrate without adding hydrogen peroxide. That is, the etching solution can be used as an etching solution according to the present invention as shown in Table 3 (Table 4 for the comparative example) by mixing a hydrogen peroxide solution having a concentration of 35 wt% and an etching concentrated solution.
  • Table 1 Table 2 for the comparative example shows the composition ratio in the etching concentrate containing no hydrogen peroxide.
  • composition ratio of each constituent material as an etching solution and the composition ratio as an etching concentrate can be reread using Tables 1, 2, and 3, 4, respectively.
  • nitric acid is 1.29% by mass in the etching concentrate in Table 1, but 1.13% in the etching solution in Table 3 (in a state where hydrogen peroxide is added). %.
  • the etching solution of the present invention can be applied to a substrate such as a glass substrate, a silicon substrate, an amorphous silicon substrate, or a metal oxide substrate, or a base layer made of these materials, regardless of products such as liquid crystal displays, plasma displays, and organic EL FPDs. It can be widely used in a situation where a wiring in which a molybdenum layer and a copper layer formed on each other are used.

Abstract

When an etching liquid for etching, with a single liquid, a multilayer film formed of a copper layer and a molybdenum layer is to be used in mass production, it is important that the post-etching cross-sectional shape of the edge meets the morphological demand of having a forward tapered shape without any undercuts and that a precipitate does not develop in the etching liquid. This etching liquid for multilayer films including a copper layer and a molybdenum layer contains hydrogen peroxide, an inorganic acid, an acidic organic acid, a neutral organic acid, an amine compound, and a hydrogen peroxide decomposition inhibitor. Since the etching liquid does not contain an azole compound, the etching liquid does not generate a reactant with hydrogen peroxide and a precipitate is not produced in the etching liquid. In addition, the cross-sectional shape of the edge after the etching can be formed in a preferable forward tapered shape. Furthermore, since the etching liquid also does not contain a phosphorus compound or a fluorine compound, the etching liquid has a small environmental load upon being discarded.

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 concentrated 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層およびモリブデン層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 a multilayer film etching solution, an etching concentrate, and an etching method used when etching a multilayer film of a copper layer and a molybdenum layer 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 (FPD) such as liquid crystal and organic EL (Electro-Luminescence). In recent years, large-screen, high-definition FPDs have become widespread, and the wiring material used has been required to have a resistance lower than that of aluminum. In recent years, therefore, copper, which has a lower resistance than aluminum, has 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, there are two problems, namely, adhesive strength with the substrate and diffusion to the semiconductor substrate. That is, in the case of using the gate wiring, there is a case where the adhesive force between the substrates such as glass is not sufficient even when the sputtering method that has a relatively high collision energy to the base material is used. In addition, when used for source / drain wiring, there arises a problem that the deposited copper diffuses into the underlying silicon and changes the electrical design value of the semiconductor.
　この問題を解決するため、現在では、基板や半導体基材上にモリブデン層を最初に形成しておき、その上に銅層を形成する多層構造が採用されている。 In order to solve this problem, a multilayer structure in which a molybdenum layer is first formed on a substrate or a semiconductor substrate and then a copper layer is formed thereon is employed.
　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には、以下の点が重要とされている。
（１）加工精度が高く一様であること。
（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）エッチング液中に銅イオンが含まれることでエッチング性能が劣化しにくい（バスライフが長い）こと。
（４）析出物の発生が少ないこと。 The FPD wiring is formed by wet etching a multilayer film formed by a sputtering method. This is because a large area can be formed at a stretch, and the process can be shortened. Here, the following points are important for wet etching of wiring.
(1) Processing accuracy is high and uniform.
(2) The wiring cross section after processing is a forward taper of a predetermined angle.
(3) Etching performance is unlikely to deteriorate due to copper ions contained in the etching solution (long bath life).
(4) There is little generation of precipitates.
　第１の項目である、加工精度が高く一様であることは、ウエットエッチングだけでなく、微小領域の加工を行う場合は、必須に求められる項目である。第２の項目である配線断面の形状は、大面積のＦＰＤの配線を一括形成する際に、確実な配線形成を行うために必要な形状である。これは、銅層とモリブデン層の多層膜のエッチングされたエッジの部分が、基板から３０～６０度の順テーパーで形成できていれば、仮にエッチング不良が発生し、銅およびモリブデンのエッチングレートのバランスが異なってしまっても、製品品質を確保できるマージンを確保することができるからである。 The first item, high processing accuracy and uniformity, is an essential item when processing not only wet etching but also micro regions. The shape of the wiring cross section, which is the second item, is a shape necessary for performing reliable wiring formation when forming large-area FPD wirings at once. This is because, if the etched edge portion of the multilayer film of the copper layer and the molybdenum layer can be formed with a forward taper of 30 to 60 degrees from the substrate, an etching failure will occur, and the etching rate of copper and molybdenum will increase. This is because a margin for ensuring product quality can be secured even if the balance is different.
　第３の項目は、エッチング液自体のライフの問題である。大面積の基板をエッチングするためには、大量のエッチング液が必要である。これらのエッチング液は、コストの観点からも、循環使用される。そのエッチング性能を維持できる期間（ライフ）ができるだけ長い方がコストは安くなる。 The third item is the life problem of the etching solution itself. In order to etch a large area substrate, a large amount of etching solution is required. These etching solutions are circulated from the viewpoint of cost. The cost is lower when the period (life) in which the etching performance can be maintained is as long as possible.
　また第４の項目は、エッチング装置の維持のための問題だけでなく、製品の品質問題にも係る問題である。エッチングによって、析出物が発生すると、エッチング装置の配管詰まりを生じさせたり、エッチング液を散布するシャワーノズルの孔を詰まらせたりする。これらの現象は、エッチング装置の運転を停止する原因となり、コストの上昇につながる。また、析出物が、エッチング液を介して製品上に付着すると、ショートや断線の原因となり、製品の品質に直接係る問題となる。 The fourth item is not only a problem for maintaining the etching apparatus but also a problem related to the quality problem of the product. When precipitates are generated by etching, the piping of the etching apparatus may be clogged, or the holes of the shower nozzle for spraying the etching solution may be clogged. These phenomena cause the operation of the etching apparatus to stop, leading to an increase in cost. In addition, if the deposit adheres to the product via the etching solution, it causes a short circuit or disconnection, which directly affects the quality of the product.
　銅層とモリブデン層の多層膜のエッチング液に関しては、中性塩と有機酸の中から選択された少なくとも１つと過酸化水素を含むエッチング液の報告がある（特許文献１）。 Regarding the etching solution for the multilayer film of copper layer and molybdenum layer, there is a report of an etching solution containing at least one selected from a neutral salt and an organic acid and hydrogen peroxide (Patent Document 1).
　また、過酸化水素と、有機酸と、リン酸塩と、第１添加剤として水溶性サイクリックアミン化合物と、第２添加剤としてアミノ基及びカルボキシル基のうちの一つを含む水溶性化合物と、フッ素化合物と、脱イオン水をそれぞれ所定量含む銅モリブデン膜のエッチング溶液が報告されている（特許文献２）。 Further, hydrogen peroxide, an organic acid, a phosphate, a water-soluble cyclic amine compound as a first additive, and a water-soluble compound containing one of an amino group and a carboxyl group as a second additive, An etching solution of a copper molybdenum film containing a predetermined amount of each of a fluorine compound and deionized water has been reported (Patent Document 2).
　また、過酸化水素と、有機酸と、トリアゾール系化合物と、フッ素化合物と、超純水を含むモリブデン／銅／窒化モリブデン多重膜配線用エッチング液の報告がある（特許文献３）。 Also, there is a report of an etching solution for molybdenum / copper / molybdenum nitride multilayer film containing hydrogen peroxide, organic acid, triazole compound, fluorine compound, and ultrapure water (Patent Document 3).
　さらに、（Ａ）過酸化水素、（Ｂ）フッ素原子を含有しない無機酸、（Ｃ）コハク酸、グリコール酸、乳酸、マロン酸及びリンゴ酸から選ばれる少なくとも一種である有機酸、（Ｄ）炭素数２～１０であり、かつアミノ基と水酸基とをその合計基数が二以上となるように有するアミン化合物、（Ｅ）５－アミノ－１Ｈ－テトラゾール、及び（Ｆ）過酸化水素安定剤を含み、ｐＨが２．５～５である銅層及びモリブデン層を含む多層薄膜用エッチング液が報告されている（特許文献４）。 Furthermore, (A) hydrogen peroxide, (B) an inorganic acid not containing a fluorine atom, (C) an organic acid that is at least one selected from succinic acid, glycolic acid, lactic acid, malonic acid, and malic acid, (D) carbon And an amine compound having an amino group and a hydroxyl group so that the total number of groups is 2 or more, (E) 5-amino-1H-tetrazole, and (F) a hydrogen peroxide stabilizer. An etching solution for a multilayer thin film containing a copper layer and a molybdenum layer having a pH of 2.5 to 5 has been reported (Patent Document 4).
特開２００２－３０２７８０号公報（特許４２８２９２７号）JP 2002-302780 A (Patent No. 4282927) 特開２００４－１９３６２０号公報（特許４４４８３２２号）JP 2004-193620 A (Patent No. 4448322) 特開２００７－００５７９０号公報（特許５１１１７９０号）JP 2007-005790 A (Patent No. 5111790) 特許５０５１３２３号Japanese Patent No. 5051323
　特許文献１は、過酸化水素と有機酸の混合液の場合に、過酸化水素の比率を調節すれば、銅とモリブデンを同時にエッチングできるという内容が開示されているだけで、具体的なエッチング液の組成については全く開示されていない。 Patent Document 1 discloses a specific etching solution in the case of a mixed solution of hydrogen peroxide and an organic acid, only that the copper and molybdenum can be etched simultaneously by adjusting the ratio of hydrogen peroxide. The composition of is not disclosed at all.
　特許文献２、３は組成中にフッ素化合物が使用されている。したがって、ガラス基板やシリコン基板をも、エッチングされてしまうという問題があるだけでなく、エッチング液の廃棄の際に環境負荷が大きくなるという問題も発生する。 Patent Documents 2 and 3 use a fluorine compound in the composition. Accordingly, there is a problem that not only the glass substrate or the silicon substrate is etched, but also an environmental load is increased when the etching solution is discarded.
　特許文献４は、銅層とモリブデン層の多層膜のエッチングを細部まで検討している。しかし、特許文献４のエッチング液の組成は、エッチング液中に析出物が大量に発生するという問題が発生する。 Patent Document 4 examines the etching of a multilayer film of a copper layer and a molybdenum layer in detail. However, the composition of the etching solution of Patent Document 4 has a problem that a large amount of precipitates are generated in the etching solution.
　また、リン化合物やフッ素化合物をエッチング液の成分として用いると、エッチング液としての性能は求めやすくなる一方、廃棄の際に環境への負担が大きくなる。 In addition, when a phosphorus compound or a fluorine compound is used as a component of the etching solution, the performance as the etching solution is easily obtained, but the burden on the environment is increased during disposal.
　また、過酸化水素は自己分解する。放置すると過酸化水素の割合が減少し、エッチングレートが大きく変化する。したがって、過酸化水素の分解をある程度に抑制しなければならない。 Also, hydrogen peroxide is self-decomposing. If left untreated, the proportion of hydrogen peroxide decreases and the etching rate changes greatly. Therefore, the decomposition of hydrogen peroxide must be suppressed to some extent.
　本発明は上記の課題に鑑みて想到されたものであり、［背景技術］で述べた配線のウエットエッチングに重要とされる点を満足する銅層とモリブデン層を含む多層膜のエッチング液組成物を提供するものである。特に、エッチング液中に析出物が発生せず、また廃棄の際に環境への負荷も大きくならないエッチング液とその濃縮液およびエッチング方法を提供する。 The present invention has been conceived in view of the above-described problems, and is an etching solution composition for a multilayer film including a copper layer and a molybdenum layer that satisfies the point important for wet etching of wiring described in [Background Art]. Is to provide. In particular, the present invention provides an etching solution, a concentrated solution thereof, and an etching method that do not generate precipitates in the etching solution and that do not increase the environmental load during disposal.
　より具体的に本発明に係る銅層とモリブデン層を含む多層膜用エッチング液は、
過酸化水素と、
無機酸と、
酸性有機酸と、
中性有機酸と、
アミン化合物と、
過酸化水素分解抑制剤を含むことを特徴とする。 More specifically, an etching solution for a multilayer film including a copper layer and a molybdenum layer according to the present invention,
Hydrogen peroxide,
Inorganic acids,
An acidic organic acid,
Neutral organic acids,
An amine compound;
It contains hydrogen peroxide decomposition inhibitor.
　また、本発明に係るエッチング液は、保存の際若しくは移送の際に嵩張らないように、濃縮液の状態で構成することができる。より具体的に本発明に係る銅層とモリブデン層を含む多層膜用エッチング濃縮液は、
無機酸と、
酸性有機酸と、
中性有機酸と、
アミン化合物と、
過酸化水素分解抑制剤と、
水を含むことを特徴とする。 Moreover, the etching liquid which concerns on this invention can be comprised in the state of a concentrate so that it may not become bulky at the time of a preservation | save or a transfer. More specifically, an etching concentrate for a multilayer film comprising a copper layer and a molybdenum layer according to the present invention,
Inorganic acids,
An acidic organic acid,
Neutral organic acids,
An amine compound;
A hydrogen peroxide decomposition inhibitor;
It contains water.
　また、本発明に係る銅層とモリブデン層を含む多層膜のエッチング方法は、
無機酸と、
酸性有機酸と、
中性有機酸と、
アミン化合物と、
過酸化水素分解抑制剤と
水を含むエッチング濃縮液と水と過酸化水素を調合し多層膜用エッチング液を調合する工程と、
前記多層膜用エッチング液を被処理基板に接触させる工程を含むことを特徴とする。 Moreover, the etching method of the multilayer film including the copper layer and the molybdenum layer according to the present invention is as follows:
Inorganic acids,
An acidic organic acid,
Neutral organic acids,
An amine compound;
A step of preparing an etching solution for multilayer film by preparing an etching concentrate containing hydrogen peroxide decomposition inhibitor and water, water and hydrogen peroxide;
The method includes a step of bringing the multilayer film etching solution into contact with a substrate to be processed.
　本発明に係るエッチング液は、エッチングされた配線の断面形状が順テーパーとなり、またオーバーエッチングをしても、その形状は維持される。また、過酸化水素と共に用いると析出物を生成するアゾール化合物を含まない構成であるので、エッチング液中に析出物の発生はなく、配管詰まりやシャワーノズルの孔つまりといった不具合が発生しない。したがって、エッチング装置の運転を析出物の発生を原因として停止させる必要がなく、安定した生産が可能となる。 In the etching solution according to the present invention, the cross-sectional shape of the etched wiring becomes a forward taper, and the shape is maintained even when overetching is performed. Moreover, since it is a structure which does not contain the azole compound which produces | generates a precipitate, when it uses with hydrogen peroxide, there will be no generation | occurrence | production of a precipitate in an etching liquid, and malfunctions, such as piping clogging and a clogging of a shower nozzle, will not generate | occur | produce. Therefore, it is not necessary to stop the operation of the etching apparatus due to the generation of precipitates, and stable production is possible.
　また、本発明に係るエッチング濃縮液は、上記のエッチング液から過酸化水素と所定量の水を含まないので、嵩張らずまた継時変化もほとんど起こさずに、保存若しくは移送することができる。また、エッチング濃縮液と過酸化水素を分けて取り扱えるので、使用によって成分濃度が変化したエッチング液の濃度調整を容易にできる。 In addition, the etching concentrate according to the present invention does not contain hydrogen peroxide and a predetermined amount of water from the above-mentioned etching solution, so that it can be stored or transported without being bulky and causing little change over time. In addition, since the etching concentrate and hydrogen peroxide can be handled separately, it is possible to easily adjust the concentration of the etching liquid whose component concentration has changed due to use.
　また、本発明に係るエッチング方法は、上記のエッチング濃縮液と過酸化水素水を調合してエッチング液を調合し、被処理基板に接触させるので、安定した組成のエッチング液をいつでも調製することができ、形成された配線の断面は、順テーパーを有し、オーバーエッチングしてもテーパー角は好適な角度の範囲を維持したエッチングを行うことができる。 Further, the etching method according to the present invention prepares an etching solution having a stable composition at any time because the etching concentrated solution and the hydrogen peroxide solution are prepared and the etching solution is prepared and brought into contact with the substrate to be processed. In addition, the cross section of the formed wiring has a forward taper, and even when overetching, the taper angle can be etched while maintaining a suitable angle range.
　また、本発明に係るエッチング液は、リン化合物、塩素化合物、フッ素化合物、といった物質が含まれていないため、廃棄する際に環境への負荷が軽いという利点がある。 Moreover, since the etching solution according to the present invention does not contain substances such as phosphorus compounds, chlorine compounds, and fluorine compounds, there is an advantage that the burden on the environment is light when discarded.
エッチングで形成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 wiring formed by the etching.
　以下本発明に係る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。本発明に係るエッチング液は、エッチング液中に析出物が生じない点に特徴がある。後述する実施例でも示されるように、析出物の原因はアゾール化合物と過酸化水素の反応物であることが強く示唆された。そこで、本発明に係るエッチング液は、アゾール化合物を含まない。 Hereinafter, the etching solution according to the present invention will be described. The following description shows an 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 etching solution according to the present invention is characterized in that no precipitate is generated in the etching solution. As shown in the examples described later, it was strongly suggested that the cause of the precipitate was a reaction product of an azole compound and hydrogen peroxide. Therefore, the etching solution according to the present invention does not contain an azole compound.
　また、環境負荷を軽減するため、リン化合物、フッ素化合物、塩素化合物も含まない。ただし、エッチング性能、製品品質に影響を及ぼさない若しくは、廃棄の際の環境負荷が各国で定められた基準以下になるような場合は、含んでいても良い。また、そのような量であれば、含んでいないと解釈してよい。 Also, to reduce environmental burden, phosphorus compounds, fluorine compounds, and chlorine compounds are not included. However, it may be included when it does not affect the etching performance and product quality, or when the environmental load at the time of disposal is below the standard established in each country. Further, such an amount may be interpreted as not including.
　＜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、無機酸により溶解される。また、モリブデンのエッチングは、酸化され酸化モリブデン（ＭｏＯ３）になり、水に溶解する。過酸化水素は、銅とモリブデン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３．５０質量％以上５．８０質量％以下が好ましい。なお、過酸化水素は「過水」とも言う。 <Hydrogen peroxide>
In the etching of copper, copper is oxidized to become copper oxide (CuO), which is dissolved by an inorganic acid. Etching of molybdenum is oxidized to molybdenum oxide (MoO 3 ) and dissolved in water. Hydrogen peroxide is used as an oxidizing agent that oxidizes copper and molybdenum. Hydrogen peroxide is preferably 3.50% by mass or more and 5.80% by mass or less of the total amount of the etching solution. Hydrogen peroxide is also called “overwater”.
　＜無機酸＞
　無機酸は、酸化された銅を溶解するために用いられる。ガラスやシリコンといった基板材料に影響を与えないため、またエッチング液の廃棄の際に環境負荷を軽減するために、リン化合物およびフッ素化合物は用いない。また、塩酸も用いない。硝酸、硫酸が好適に利用できる。無機酸は、エッチング液全量に対して、０．０１質量％以上２．００質量％以下、好ましくは０．０２質量％以上１．５０質量％以下の範囲で含ませる。 <Inorganic acid>
Inorganic acids are used to dissolve oxidized copper. Phosphorus compounds and fluorine compounds are not used in order not to affect the substrate material such as glass or silicon and to reduce the environmental load when discarding the etchant. Also, hydrochloric acid is not used. Nitric acid and sulfuric acid can be suitably used. The inorganic acid is included in the range of 0.01% by mass or more and 2.00% by mass or less, preferably 0.02% by mass or more and 1.50% by mass or less with respect to the total amount of the etching solution.
　＜有機酸＞
　有機酸成分は、主として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。有機酸成分には酸性有機酸と中性有機酸との組み合わせを用いる。また、酸性有機酸および中性有機酸の両方を組み合わせてもよい。 <Organic acid>
The organic acid component mainly serves to adjust the taper angle of the cross section of the etched wiring. It is also considered to have a function to suppress the decomposition of hydrogen peroxide to some extent. As the organic acid component, a combination of an acidic organic acid and a neutral organic acid is used. Moreover, you may combine both an acidic organic acid and a neutral organic acid.
　使用できる有機酸としては、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のアミノ酸などが好ましく挙げられる。 Preferred examples of organic acids that can be used include aliphatic carboxylic acids having 1 to 18 carbon atoms, aromatic carboxylic acids having 6 to 10 carbon atoms, and amino 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、グリコール酸、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、アジピン酸、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, glycolic acid, diglycolic acid, pyruvic acid, malonic acid, butyric acid, hydroxybutyric acid, tartaric acid, succinic acid, malic acid, maleic acid , Fumaric acid, valeric acid, glutaric acid, itaconic acid, adipic acid, caproic acid, adipic acid, citric acid, propanetricarboxylic acid, trans-aconitic acid, enanthic acid, caprylic acid, lauric acid, myristic acid, palmitic acid, stearin Preferred are acid, oleic acid, linoleic acid, linolenic acid and the like.
　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。 Examples of amino acids having 1 to 10 carbon atoms include carbamic acid, alanine, glycine, asparagine, aspartic acid, sarcosine, serine, glutamine, glutamic acid, 4-aminobutyric acid, iminodibutyric acid, arginine, leucine, isoleucine, nitrilotriacetic acid, etc. Are preferred.
　上記有機酸のなかでも、酸性有機酸としてグリコール酸、リンゴ酸が好適に利用できる。特にグリコール酸、リンゴ酸は、二種を同時に併用することで、好適な特性を得ることができる。なお、酸性有機酸は、エッチング液全量に対して１質量％以上７質量％以下含有させるのが好ましい。 Among the above organic acids, glycolic acid and malic acid can be suitably used as the acidic organic acid. In particular, glycolic acid and malic acid can obtain suitable characteristics by simultaneously using two kinds. In addition, it is preferable to contain 1 to 7 mass% of acidic organic acids with respect to the etching liquid whole quantity.
　また、グリコール酸、リンゴ酸を同時に用いる場合は、グリコール酸は、エッチング液全量に対して０．５質量％以上５．００質量％以下が好ましく、より好ましくは１．００質量％以上２．００質量％以下含有させるのがよい。また、リンゴ酸は、エッチング液全量に対して、０．１０質量％以上１．００質量％以下が好ましく、より好ましくは０．５０質量％以上０．８０質量％以下含有させるのがよい。 When glycolic acid and malic acid are used at the same time, glycolic acid is preferably 0.5% by mass or more and 5.00% by mass or less, more preferably 1.00% by mass or more and 2.00% by mass with respect to the total amount of the etching solution. It is good to contain below mass%. Further, malic acid is preferably contained in an amount of 0.10% by mass or more and 1.00% by mass or less, and more preferably 0.50% by mass or more and 0.80% by mass or less based on the total amount of the etching solution.
　また、中性有機酸として、グリシン、アラニン若しくはβアラニンが好適に利用できる。また、中性有機酸はエッチング液全量に対して、０．１０質量％以上３．００質量％以下含有させるのが好ましい。 Moreover, glycine, alanine or β-alanine can be suitably used as the neutral organic acid. The neutral organic acid is preferably contained in an amount of 0.10% by mass to 3.00% by mass with respect to the total amount of the etching solution.
　＜アミン化合物＞
　アミン化合物は主としてエッチング液の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、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、これらを単独で又は複数を組み合わせて用いることができる。これらの中でも、１－アミノ－２－プロパノールが特に好ましい。また、アミン化合物はエッチング液全量に対して、０．５０質量％以上２．００質量％以下含有させるのが好ましく、より好ましくは０．７５質量％以上１．５０質量％以下含有させるのがよい。 <Amine compound>
The amine compound is mainly responsible for adjusting the pH of the etching solution. As the amine compound, those 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) amino , Tetra (aminomethyl) methane, diethylenetriamine, triethylenetetramine, tetraethylpentamine, heptaethyleneoctamine, nonaethylenedecamine, diazabicycloundecene, etc .; ethanolamine, N-methylethanolamine, N-methyldiethanolamine N-ethylethanolamine, N-aminoethylethanolamine, N-propylethanolamine, N-butylethanolamine, diethanolamine, triethanolamine, 1-amino-2-propanol, N-methylisopropanolamine, N-ethylisopropanol Amine, N-propylisopropanolamine, 2-aminopropan-1-ol, N-methyl-2-amino-propan-1-ol, N-ethyl-2-amino Propan-1-ol, 1-aminopropane-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-aminobutane-2-ol, 2-aminobutane-1-ol, N-methyl-2-aminobutan-1-ol, N-ethyl-2-aminobutane- 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-aminobutane -4-ol, N-ethyl-1-aminobutan-4-ol, 1-amino-2-methylpropan-2-ol, 2-amino-2-methylpropa N-1-ol, 1-aminopentan-4-ol, 2-amino-4-methylpentan-1-ol, 2-aminohexane-1-ol, 3-aminoheptan-4-ol, 1-aminooctane -2-ol, 5-aminooctane-4-ol, 1-aminopropane-2,3-diol, 2-aminopropane-1,3-diol, tris (oxymethyl) aminomethane, 1,2-diaminopropane- Preferred examples include alkanolamines such as 3-ol, 1,3-diaminopropan-2-ol, 2- (2-aminoethoxy) ethanol, 2- (2-aminoethylamino) ethanol, and diglycolamine. These can be used alone or in combination. Of these, 1-amino-2-propanol is particularly preferred. Further, the amine compound is preferably contained in an amount of 0.50% by mass or more and 2.00% by mass or less, more preferably 0.75% by mass or more and 1.50% by mass or less based on the total amount of the etching solution. .
　＜過酸化水素分解抑制剤＞
　本発明に係るエッチング液では、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。エッチング液のライフを長くするためである。主たる過酸化水素分解抑制剤としては、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、また２－ブトキシエタノール（エチレングリコールモノブチルエーテル）などのエーテル等が好ましく挙げられる。 <Hydrogen peroxide decomposition inhibitor>
In the etching solution according to the present invention, hydrogen peroxide is used as an oxidizing agent. Since hydrogen peroxide self-decomposes, a decomposition inhibitor that suppresses the decomposition is added. This is for extending the life of the etching solution. The main hydrogen peroxide decomposition inhibitors include phenyl urea, allyl urea, 1,3-dimethylurea, urea-based hydrogen peroxide stabilizers such as thiourea, phenylacetamide, phenylethylene glycol, 1-propanol, Preferred are lower alcohols such as 2-propanol and ethers such as 2-butoxyethanol (ethylene glycol monobutyl ether).
　また、後述する実施例からも明らかになるが、上記の過酸化水素分解抑制剤は、酸性有機酸であるリンゴ酸が共存することで過酸化水素分解抑制効果が向上する。これらの物質は、過酸化水素に作用し、ラジカルの発生を抑制することで過酸化水素の分解を抑制すると考えられる。 Also, as will be apparent from the examples described later, the hydrogen peroxide decomposition inhibitor is improved by the presence of malic acid, which is an acidic organic acid, in combination with the hydrogen peroxide decomposition inhibitor. These substances are considered to suppress the decomposition of hydrogen peroxide by acting on hydrogen peroxide and suppressing the generation of radicals.
　＜銅イオン＞
　本発明に係るエッチング液は、エッチングが進みＣｕイオンやＭｏイオンが含まれるようになると、Ｃｕイオン濃度の増加に応じてエッチングレートは変化することが確認された。エッチング装置の運転は、エッチングレートの変化が一定の許容範囲に収まるようにエッチング濃縮液や過酸化水素水を添加して制御されるので、新液の状態でもこの許容範囲に収まるようにするのが好ましい。そこで、エッチング液には、所定の範囲のＣｕイオンを含有させてもよい。具体的には、エッチング液全量に対してＣｕイオンを５００ｐｐｍ以上７０００ｐｐｍ以下、好ましくは、２０００ｐｐｍ以上４０００ｐｐｍ以下含ませれば、エッチングレートの変化を想定しやすく好ましい。 <Copper ion>
It has been confirmed that the etching rate according to the present invention changes as the Cu ion concentration increases as etching progresses and Cu ions and Mo ions are included. The operation of the etching equipment is controlled by adding an etching concentrate and hydrogen peroxide so that the change in etching rate is within a certain allowable range. Is preferred. Therefore, the etching solution may contain a predetermined range of Cu ions. Specifically, if the Cu ions are contained in an amount of 500 ppm to 7000 ppm, preferably 2000 ppm to 4000 ppm with respect to the total amount of the etching solution, a change in the etching rate is easily assumed.
　また、同様に本発明に係るエッチング液には、モリブデンイオンを含有させてもよい。Ｍｏイオンは、Ｃｕイオンのおよそ１０分の１の割合である。したがって、Ｍｏイオンは５０以上７００ｐｐｍ以下、好ましくは２００ｐｐｍ以上４００ｐｐｍ以下含ませても良い。 Similarly, the etching solution according to the present invention may contain molybdenum ions. Mo ions are approximately one-tenth of the Cu ions. Therefore, Mo ions may be included in the range of 50 to 700 ppm, preferably 200 ppm to 400 ppm.
　＜その他＞
　本発明のエッチング液には、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。 <Others>
In addition to these components, various commonly used additives may be added to the etching solution of the present invention as long as water and etching performance are not impaired. Since water is used for precision processing, it is preferable that water does not exist. Pure water or ultrapure water is preferable.
　＜ｐＨ、温度＞
　本発明に係るエッチング液は、ｐＨ２以上５以下、より好ましくはｐＨ３以上４．５以下、もっとも好ましくはｐＨ３．３以上３．９以下の範囲で使用されるのが好ましい。本発明に係るエッチング液は、１８℃以上４０℃以下の間で使用することができる。より好ましくは１８℃以上３５℃以下であり、最も好ましくは２０℃以上３２℃以下がよい。 <PH, temperature>
The etching solution according to the present invention is preferably used in the range of pH 2 to 5, more preferably pH 3 to 4.5, and most preferably pH 3.3 to 3.9. The etching liquid which concerns on this invention can be used between 18 degreeC or more and 40 degrees C or less. More preferably, it is 18 degreeC or more and 35 degrees C or less, Most preferably, 20 degreeC or more and 32 degrees C or less are good.
　＜保存＞
　本発明に係るエッチング液には、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、過酸化水素と銅イオンを除いた原料（「エッチング液原料」と呼ぶ。）と水を混ぜ合わせ、エッチング液原料の溶液を調合しておいてもよい。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。 <Save>
Hydrogen peroxide is used for the etching solution according to the present invention. Hydrogen peroxide is self-degrading. Therefore, the etchant contains a hydrogen peroxide decomposition inhibitor. However, when storing, the hydrogen peroxide solution and other liquids may be stored separately. Alternatively, a raw material excluding hydrogen peroxide and copper ions (referred to as an “etching liquid raw material”) and water may be mixed to prepare an etching liquid raw material solution. This solution may be water in a proportion smaller than the proportion of water in the etching solution shown in the examples described later.
　エッチング液原料と水を調合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。エッチング濃縮液は、エッチング液と比べると過酸化水素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。また、更に保存や移送の際の体積を減らすために、「エッチング濃縮液」の水を減らした「エッチング高濃縮液」としてもよい。エッチング高濃縮液は水を２０％以上７０％以下含むものをいう。エッチング濃縮液は、水を７０％より多く含む。したがって、本発明のエッチング液は、エッチング濃縮液と過酸化水素水を合わせて完成してもよいし、エッチング高濃縮液と水と過酸化水素水を合わせて完成させてもよい。 The solution of the etchant raw material prepared by mixing the etchant raw material and water is called “etching concentrate”. The etching concentrate has a smaller volume as compared with the etching liquid because there is no hydrogen peroxide, so it is convenient for storage and transport. Further, in order to further reduce the volume during storage and transfer, an “etching highly concentrated solution” in which water of the “etching concentrated solution” is reduced may be used. Etching highly concentrated liquid means what contains 20% or more and 70% or less of water. The etching concentrate contains more than 70% water. Therefore, the etching solution of the present invention may be completed by combining the etching concentrate and hydrogen peroxide solution, or may be completed by combining the etching high concentration solution, water, and hydrogen peroxide solution.
　＜エッチング方法＞
　本発明に係るエッチング液を用いる対象は、モリブデンが下層で、銅が上層となった銅層／モリブデン層の多層膜である。下層のモリブデン層の厚みは、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、ｔ０／ｔ１の範囲が０．０１以上０．２以下の範囲の構成である。ｔ０／ｔ１の範囲がこの範囲を外れて、Ｍｏ層が厚すぎると、Ｍｏ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 target for using the etching solution according to the present invention is a multilayer film of copper layer / molybdenum layer in which molybdenum is a lower layer and copper is an upper layer. The lower molybdenum layer is thinner than the upper copper. When the thickness of the lower layer is t0 and the thickness of the upper layer is t1, the range of t0 / t1 is in the range of 0.01 to 0.2. If the range of t0 / t1 is out of this range and the Mo layer is too thick, the Mo layer residue tends to be generated, and conversely, if it is too thin, the Cu layer can no longer serve as an underlayer.
　また、モリブデン層および銅層が形成される基板および下地層は、特に限定されず、ガラス、シリコン、アモルファスシリコンを始め、ＩＧＺＯ（インジウム（Ｉｎｄｉｕｍ）、ガリウム（Ｇａｌｌｉｕｍ）、亜鉛（Ｚｉｎｃ）、酸素（Ｏｘｉｄｅ）から構成されるアモルファス半導体）等の金属酸化物であってもよい。 The substrate and the base layer on which the molybdenum layer and the copper layer are formed are not particularly limited, and include glass, silicon, amorphous silicon, IGZO (Indium, Gallium, Zinc), oxygen ( It may be a metal oxide such as an amorphous semiconductor composed of Oxide).
　本発明に係るエッチング液は、保存の際に、過酸化水素水とエッチング高濃縮液および水（過酸化水素水とエッチング濃縮液でもよい。）を分けて保存しておくことで保存が可能になる。そこで、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 etching solution according to the present invention can be stored by storing the hydrogen peroxide solution, the highly concentrated etching solution, and water (hydrogen peroxide solution and the etching concentrated solution) separately during storage. Become. Therefore, in actual use, these are mixed to complete the etching solution. The blending method 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合しておく。過酸化水素は通常本発明に係る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を所定量ずつ調合する。この工程は多層膜用エッチング液を調合する工程と呼んでもよい。また、エッチング濃縮液より濃度の高いエッチング高濃縮液と水と過酸化水素水を調合してエッチング液を調製してもよい。 For example, an etching concentrate prepared by mixing an etching solution raw material with a certain amount of water is prepared. Hydrogen peroxide is usually supplied as a hydrogen peroxide solution having a concentration higher than that of the etching solution according to the present invention. Therefore, a predetermined amount of hydrogen peroxide solution and etching concentrate is prepared. This step may be called a step of preparing a multilayer film etching solution. Alternatively, an etching solution may be prepared by preparing a high etching concentration solution, water, and hydrogen peroxide solution having a higher concentration than the etching concentration solution.
　銅イオンは、エッチング液原料と水でエッチング濃縮液（若しくはエッチング高濃縮液）を調合する際、若しくはエッチング濃縮液と過酸化水素水でエッチング液を調合する際のいずれの段階でも混入させることができる。もちろん、エッチング液を調合してから添加しても良い。なお、すでに使用されているエッチング液に、追加でエッチング濃縮液と過酸化水素水を注ぎ足す場合には、銅イオンを入れなくてもよい。すでに、エッチング液中に銅イオンが存在するからである。 Copper ions can be mixed at any stage of preparing an etching concentrate (or highly concentrated etching solution) with an etchant raw material and water, or when preparing an etching solution with an etching concentrate and hydrogen peroxide. it can. Of course, the etching solution may be added after being prepared. In addition, when an etching concentrate and hydrogen peroxide water are additionally added to the etching solution already used, it is not necessary to add copper ions. This is because copper ions are already present in the etching solution.
　エッチングを行う際は、上記の通り、ｐＨ２以上５以下で、１８℃以上４０℃以下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も、この温度に余熱されるのが望ましい。被対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。この工程は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 etching is performed, as described above, the etching solution is used under the conditions of pH 2 to 5 and 18 ° C. to 40 ° C. Therefore, it is desirable that the object to be etched is also preheated to this temperature. The method for bringing the substrate to be treated into contact with the etching solution is not particularly limited. An etching solution may be sprayed on the substrate to be processed from above as in a shower type, or a method of dipping the substrate to be processed into a pool of etching solution may be used. This step may be called a step of bringing the multilayer film etching solution into contact with the substrate to be processed.
　なお、被処理基板とは、ガラス等の基材の上にモリブデン層（Ｍｏ層）と銅層（Ｃｕ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層のパターンが形成されている状態の基板である。 In addition, the substrate to be processed is formed by laminating a molybdenum layer (Mo layer) and a copper layer (Cu layer) on a base material such as glass, and a pattern of a resist layer for pattern formation is formed on the laminated film. It is a substrate in a state of being.
　＜各種評価方法の説明＞
　本発明に係るエッチング液に対しては、銅およびモリブデンのエッチングレート（ｎｍ／ｍｉｎ）、エッチングされた配線の断面のテーパー角（°）、モリブデン層のアンダーカット、基板上に残ったモリブデン層（「Ｍｏ残渣」と呼ぶ。）、オーバーエッチング耐性、析出物の有無、過酸化水素分解速度（質量％／日）の項目で評価を行った。 <Description of various evaluation methods>
For the etching solution according to the present invention, the etching rate of copper and molybdenum (nm / min), the taper angle (°) of the cross section of the etched wiring, the undercut of the molybdenum layer, the molybdenum layer remaining on the substrate ( Evaluation was performed on the items of “Mo residue”), over-etching resistance, presence of precipitates, and hydrogen peroxide decomposition rate (mass% / day).
　エッチングレートは、以下のようにして測定した。まず、熱酸化膜１００ｎｍが形成されたシリコンウエハー上にスパッタ法により、銅は３００ｎｍ、モリブデンは１５０ｎｍの厚みでそれぞれ単層膜を形成した。この銅膜およびモリブデン膜を３０℃（比較例によっては３５℃の場合もある。）のエッチング液に２０から６０秒間接触させた。 The etching rate was measured as follows. First, a single layer film having a thickness of 300 nm for copper and 150 nm for molybdenum was formed on a silicon wafer on which a thermal oxide film of 100 nm was formed by sputtering. The copper film and the molybdenum film were brought into contact with an etching solution at 30 ° C. (may be 35 ° C. in some comparative examples) for 20 to 60 seconds.
　エッチング前後の膜の抵抗値を、定電流印加方式の４端子４探針法抵抗率計（三菱化学アナリテック製：ＭＣＰ－Ｔ６１０型）用いて測定した。この抵抗値の変化より膜厚変化を算出し、エッチングレートを算出した。 The resistance value of the film before and after etching was measured using a constant current application type 4-terminal 4-probe resistivity meter (manufactured by Mitsubishi Chemical Analytech: MCP-T610 type). The change in film thickness was calculated from the change in resistance value, and the etching rate was calculated.
　テーパー角（以下の表では「テーパー角」と記す。）は以下のようにして測定した。まず、ガラス基板上にスパッタ法でモリブデン層を２０ｎｍの厚みで成膜し、その上に続けて銅層を３００ｎｍの厚みで成膜し、Ｃｕ／Ｍｏの多層膜サンプルを作製した。この銅層の上に配線形状にパターン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、テーパー角評価用基材は、基板とモリブデン層とその上の銅層と、銅層上のパターンニングされたレジスト層からなる。このテーパー角評価用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、配線部分を切断し、切断面を観察した。 The taper angle (referred to as “taper angle” in the table below) was measured as follows. First, a molybdenum layer having a thickness of 20 nm was formed on a glass substrate by a sputtering method, and a copper layer having a thickness of 300 nm was subsequently formed thereon to prepare a Cu / Mo multilayer film sample. A resist patterned into a wiring shape was formed on the copper layer, and a substrate for taper angle evaluation was obtained. That is, the taper angle evaluation base material includes a substrate, a molybdenum layer, a copper layer thereon, and a patterned resist layer on the copper layer. Etching was performed by immersing this base for taper angle evaluation in an etching solution for the time of just etching. After the etching sample was washed and dried, the wiring portion was cut and the cut surface was observed.
　切断面の観測は、ＳＥＭ（Ｓｃａｎｎｉｎｇ　Ｅｌｅｃｔｒｏｎ　Ｍｉｃｒｏｓｃｏｐｅ）（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。 The observation of the cut surface was performed using SEM (Scanning Electron Microscope) (manufactured by Hitachi: SU8020 type) under the conditions of an acceleration voltage of 1 kV and 30,000 to 50,000 times. Note that just etching is the time from the start of etching until the film transmits light. The time when the film transmitted light was visually confirmed.
　切断面形状を図１に示す。図１（ａ）に示すように、基板１とエッチングされた傾斜面６のなす角度５をテーパー角（°）とする。テーパー角５は３０°以上６０°以下であればマル（○）と判断した。この角度の範囲外であれば、バツ（×）と判断した。なお、「マル」は成功若しくは合格を意味し、「バツ」は失敗若しくは不合格を意味する。以下の評価でも同じである。なお、図１（ａ）では、Ｍｏ層は符号３、Ｃｕ層は符号２、レジスト層は符号４で表した。また、Ｃｕ層２の厚みはｔ１、Ｍｏ層３の厚みをｔ０で示した。 The cut surface shape is shown in FIG. As shown in FIG. 1A, an angle 5 formed by the substrate 1 and the etched inclined surface 6 is a taper angle (°). When the taper angle 5 is 30 ° or more and 60 ° or less, it is judged as a circle (◯). If it was out of the range of this angle, it was judged as X (x). “Mal” means success or success, and “X” means failure or failure. The same applies to the following evaluations. In FIG. 1A, the Mo layer is indicated by reference numeral 3, the Cu layer is indicated by reference numeral 2, and the resist layer is indicated by reference numeral 4. The thickness of the Cu layer 2 is indicated by t1, and the thickness of the Mo layer 3 is indicated by t0.
　モリブデン層３のアンダーカット（以下の表では「Ｍｏアンダーカット」と記す。）は、図１（ｂ）の符号１０で示すように、モリブデン層３と基板１の間が銅層２より早くエッチングされた状態（逆テーパー）を言う。評価は、テーパー角５の評価の際に同時にできる。モリブデン層３のアンダーカット１０は、ＳＥＭの３０，０００倍から５０，０００倍の観測で発見されなかったらマル（○）と判断し、発見されたらバツ（×）と判断した。 Undercut of the molybdenum layer 3 (referred to as “Mo undercut” in the following table) is etched faster than the copper layer 2 between the molybdenum layer 3 and the substrate 1 as indicated by reference numeral 10 in FIG. State (reverse taper). The evaluation can be performed simultaneously with the evaluation of the taper angle 5. If the undercut 10 of the molybdenum layer 3 was not found by observation at 30,000 to 50,000 times the SEM, it was judged as a circle (◯), and if found, it was judged as a cross (×).
　Ｍｏ残渣（以下の表では「Ｍｏ残渣」と記す。）は、光学顕微鏡とＳＥＭによる観察で、残渣が確認されたらバツ（×）、確認されなければマル（○）と判定した。なお、光学顕微鏡は１００倍程度の倍率で、明視野観察と暗視野観察で観察した。またＳＥＭでは３０，０００倍から５０，０００倍で観察した。 The Mo residue (referred to as “Mo residue” in the following table) was determined to be “X” when the residue was confirmed by observation with an optical microscope and SEM, and “M” when the residue was not confirmed. The optical microscope was observed with bright field observation and dark field observation at a magnification of about 100 times. Moreover, in SEM, it observed by 30,000 times to 50,000 times.
　オーバーエッチング耐性（以下の表では「Ｏ．Ｅ．耐性」と記す。）とは、ジャストエッチングにかかる時間の２倍の時間エッチングした時のテーパー角５、モリブデン層３のアンダーカット１０、Ｍｏ残渣を観測し、全て「マル」評価ならマル（○）と判断した。どれか１つでも「バツ」判断があればバツ（×）とした。 Over-etching resistance (referred to as “OE resistance” in the table below) refers to taper angle 5 when etching is twice the time required for just etching, undercut 10 of molybdenum layer 3, Mo residue Was observed, and if all were "Mal" evaluation, it was judged as Mull (○). If any one of them is judged as “X”, it is X (X).
　析出物の有無は、エッチング液を調合後、ボトルにて所定時間（数日）室温放置しておき、ボトル内に析出物が生じるかどうかを目視で判断した。析出物が発生した場合は、ろ紙でエッチング液をろ過し、ろ紙上に残った異物を純水洗浄、室温乾燥させて、得られた結晶物や粉体をＦＴ－ＩＲ（島津製作所製ＩＲ　ａｆｆｉｎｉｔｙ）やＳＥＭ－ＥＤＸ（堀場製作所製）で分析した。析出物が目視観測されなければ、マル（○）と判断し、目視確認された場合はバツ（×）と判断した。 Presence / absence of precipitates was determined by visually determining whether or not precipitates were formed in the bottle after the etching solution was prepared and left in the bottle at room temperature for a predetermined time (several days). When precipitates are generated, the etching solution is filtered with a filter paper, the foreign matter remaining on the filter paper is washed with pure water and dried at room temperature, and the obtained crystals and powder are converted into FT-IR (Shimadzu IR affinity). ) And SEM-EDX (Horiba Seisakusho). If the precipitate was not visually observed, it was judged as round (◯), and if it was visually confirmed, it was judged as X (x).
　エッチング液は、析出物が発生しない点と、配線の断面形状が適切であることが重要であるが、バスライフを長くするためには、過酸化水素の分解速度も重要な項目となる。ここでは参考として過酸化水素分解速度も評価項目として調べた。 In the etching solution, it is important that no precipitate is generated and that the cross-sectional shape of the wiring is appropriate. However, in order to lengthen the bath life, the decomposition rate of hydrogen peroxide is also an important item. For reference, the hydrogen peroxide decomposition rate was also examined as an evaluation item.
　過酸化水素分解速度（以下の表では「過水分解速度」と記す。）は、エッチング液調合直後及び所定時間経過後（約２４ｈ）の過酸化水素濃度を、滴定試薬を過マンガン酸カリウムとし、自動滴定装置（三菱化学アナリテック製ＧＰ－２００）を用いて測定した。そして、過酸化水素濃度の変化量から分解速度を算出した。 The hydrogen peroxide decomposition rate (referred to as “perhydrolysis rate” in the table below) is the hydrogen peroxide concentration immediately after the preparation of the etchant and after the lapse of a predetermined time (about 24 hours), and the titration reagent is potassium permanganate. The measurement was performed using an automatic titrator (GP-200 manufactured by Mitsubishi Chemical Analytech). Then, the decomposition rate was calculated from the amount of change in the hydrogen peroxide concentration.
　２４時間後の過酸化水素濃度の減少量が、０．２４質量％未満であれば二重丸（◎）と評価し、０．２４質量％以上、０．９６質量％以下であればマル（○）と評価し、０．９６質量％を超えるとバツ（×）と評価した。２４時間後の過酸化水素濃度の減少量を例えば「０．２４質量％／日」と記す。なお、ここで、二重丸というのは、合格基準の中でもとりわけ望ましい結果であることを表す。また、全ての評価に関して、マル評価の条件を満たさないものの、境界値に極めて近い値の場合は、三角（△）と評価した。 If the decrease amount of the hydrogen peroxide concentration after 24 hours is less than 0.24% by mass, it is evaluated as a double circle (◎), and if it is 0.24% by mass or more and 0.96% by mass or less, ○), and when it exceeded 0.96 mass%, it was evaluated as X (x). The amount of decrease in the hydrogen peroxide concentration after 24 hours is described as, for example, “0.24 mass% / day”. Here, the double circle represents a particularly desirable result among the acceptance criteria. Moreover, regarding all the evaluations, although the conditions for the round evaluation were not satisfied, a value extremely close to the boundary value was evaluated as a triangle (Δ).
　（実施例１）
　硝酸を１．２９質量％、
グリコール酸を１．１４質量％、
リンゴ酸を０．８５質量％、
βアラニンを１．４２質量％、
１アミノ２プロパノールを１．７１質量％、
フェニル尿素を０．１１質量％、
１－プロパノールを１．１６質量％
２－ブトキシエタノールを１．２９質量％
からなるエッチング液原料を水９１．０３質量％と調合し、エッチング濃縮液を調製した。 (Example 1)
1.29 mass% nitric acid,
1.14% by weight of glycolic acid,
0.85% by mass of malic acid,
β-alanine 1.42% by mass,
1.71% by mass of 1 amino 2-propanol,
0.11% by mass of phenylurea,
1.16% by mass of 1-propanol
1.29 mass% of 2-butoxyethanol
The etching liquid raw material which consists of was mixed with water 91.03 mass%, and the etching concentrated liquid was prepared.
　過酸化水素とエッチング濃縮液を混合し、過酸化水素濃度が４．５０質量％のエッチング液を調製した。さらに、硫酸銅とモリブデン粉末を加えて銅イオン濃度が２０００ｐｐｍ、モリブデンイオン濃度が２００ｐｐｍになるように調製した。また、液温は３０℃で用いた。エッチング濃縮液に占める各成分濃度と、各評価事項の結果を表１に示す。また、エッチング液全体に占める各成分濃度を表３に示す。 Hydrogen peroxide and etching concentrate were mixed to prepare an etching solution having a hydrogen peroxide concentration of 4.50% by mass. Further, copper sulfate and molybdenum powder were added to prepare a copper ion concentration of 2000 ppm and a molybdenum ion concentration of 200 ppm. The liquid temperature was 30 ° C. Table 1 shows the concentration of each component in the etching concentrate and the result of each evaluation item. Table 3 shows the concentration of each component in the entire etching solution.
　なお、表１ないし表４において、２－ブトキシエタノールを「ＢＧ（２－ブトキシエタノール）」と記した。また、表１および表２で示す過酸化水素濃度は、エッチング液全体に対する過酸化水素濃度を表す。 In Tables 1 to 4, 2-butoxyethanol was described as “BG (2-butoxyethanol)”. Moreover, the hydrogen peroxide concentration shown in Table 1 and Table 2 represents the hydrogen peroxide concentration with respect to the whole etching solution.
　（実施例２）
　硝酸を０．０９質量％、
グリコール酸を１．４４質量％、
リンゴ酸を０．８６質量％、
βアラニンを０．９１質量％、
１アミノ２プロパノールを０．８７質量％、
フェニル尿素を０．１１質量％、
１－プロパノールを１．１５質量％
２－ブトキシエタノールを１．２８質量％
からなるエッチング液原料を水９３．２９質量％と調合し、エッチング濃縮液を調製した。 (Example 2)
0.09 mass% nitric acid,
1.44% by weight of glycolic acid,
0.86% by mass of malic acid,
0.91% by mass of β-alanine,
0.87% by mass of 1 amino 2-propanol,
0.11% by mass of phenylurea,
1.15% by mass of 1-propanol
1.28 mass% of 2-butoxyethanol
An etching solution raw material consisting of 93.29% by mass of water was prepared to prepare an etching concentrate.
　過酸化水素とエッチング濃縮液を混合し、過酸化水素濃度が４．５０質量％のエッチング液を調製した。さらに、硫酸銅とモリブデン粉末を加えて銅イオン濃度が２０００ｐｐｍ、モリブデンイオン濃度が２００ｐｐｍになるように調製した。また、液温は３０℃で用いた。エッチング濃縮液に占める各成分濃度と、各評価事項の結果を表１に示す。また、エッチング液全体に占める各成分濃度を表３に示す。 Hydrogen peroxide and etching concentrate were mixed to prepare an etching solution having a hydrogen peroxide concentration of 4.50% by mass. Further, copper sulfate and molybdenum powder were added to prepare a copper ion concentration of 2000 ppm and a molybdenum ion concentration of 200 ppm. The liquid temperature was 30 ° C. Table 1 shows the concentration of each component in the etching concentrate and the result of each evaluation item. Table 3 shows the concentration of each component in the entire etching solution.
　（実施例３）
　硝酸を０．１８質量％、
グリコール酸を１．３０質量％、
リンゴ酸を０．８７質量％、
βアラニンを０．９１質量％、
１アミノ２プロパノールを０．８６質量％、
フェニル尿素を０．１１質量％、
１－プロパノールを１．１６質量％
２－ブトキシエタノールを１．２８質量％
からなるエッチング液原料を水９３．３３質量％と調合し、エッチング濃縮液を調製した。 (Example 3)
0.18% by mass of nitric acid,
1.30% by weight of glycolic acid,
0.87 mass% malic acid,
0.91% by mass of β-alanine,
0.86% by mass of 1 amino 2-propanol,
0.11% by mass of phenylurea,
1.16% by mass of 1-propanol
1.28 mass% of 2-butoxyethanol
The etching liquid raw material consisting of was mixed with 93.33% by mass of water to prepare an etching concentrated liquid.
　過酸化水素とエッチング濃縮液を混合し、過酸化水素濃度が４．５０質量％のエッチング液を調製した。さらに、硫酸銅とモリブデン粉末を加えて銅イオン濃度が２０００ｐｐｍ、モリブデンイオン濃度が２００ｐｐｍになるように調製した。また、液温は３０℃で用いた。エッチング濃縮液に占める各成分濃度と、各評価事項の結果を表１に示す。また、エッチング液全体に占める各成分濃度を表３に示す。 Hydrogen peroxide and etching concentrate were mixed to prepare an etching solution having a hydrogen peroxide concentration of 4.50% by mass. Further, copper sulfate and molybdenum powder were added to prepare a copper ion concentration of 2000 ppm and a molybdenum ion concentration of 200 ppm. The liquid temperature was 30 ° C. Table 1 shows the concentration of each component in the etching concentrate and the result of each evaluation item. Table 3 shows the concentration of each component in the entire etching solution.
　（実施例４）
　硝酸を１．２９質量％、
グリコール酸を１．１４質量％、
リンゴ酸を０．８５質量％、
βアラニンを１．４２質量％、
１アミノ２プロパノールを１．７１質量％、
フェニル尿素を０．１１質量％、
１－プロパノールを１．１６質量％
からなるエッチング液原料を水９２．３２質量％と調合し、エッチング濃縮液を調製した。 Example 4
1.29 mass% nitric acid,
1.14% by weight of glycolic acid,
0.85% by mass of malic acid,
β-alanine 1.42% by mass,
1.71% by mass of 1 amino 2-propanol,
0.11% by mass of phenylurea,
1.16% by mass of 1-propanol
The etching liquid raw material which consists of was mixed with water 92.32 mass%, and the etching concentrated liquid was prepared.
　過酸化水素とエッチング濃縮液を混合し、過酸化水素濃度が４．５０質量％のエッチング液を調製した。さらに、硫酸銅とモリブデン粉末を加えて銅イオン濃度が２０００ｐｐｍ、モリブデンイオン濃度が２００ｐｐｍになるように調製した。また、液温は３０℃で用いた。エッチング濃縮液に占める各成分濃度と、各評価事項の結果を表１に示す。また、エッチング液全体に占める各成分濃度を表３に示す。 Hydrogen peroxide and etching concentrate were mixed to prepare an etching solution having a hydrogen peroxide concentration of 4.50% by mass. Further, copper sulfate and molybdenum powder were added to prepare a copper ion concentration of 2000 ppm and a molybdenum ion concentration of 200 ppm. The liquid temperature was 30 ° C. Table 1 shows the concentration of each component in the etching concentrate and the result of each evaluation item. Table 3 shows the concentration of each component in the entire etching solution.
　（実施例５）
　硝酸を１．２９質量％、
グリコール酸を１．１４質量％、
リンゴ酸を０．８５質量％、
βアラニンを１．４２質量％、
１アミノ２プロパノールを１．７１質量％、
１－プロパノールを１．１６質量％
２－ブトキシエタノールを１．２９質量％
からなるエッチング液原料を水９１．１４質量％と調合し、エッチング濃縮液を調製した。 (Example 5)
1.29 mass% nitric acid,
1.14% by weight of glycolic acid,
0.85% by mass of malic acid,
β-alanine 1.42% by mass,
1.71% by mass of 1 amino 2-propanol,
1.16% by mass of 1-propanol
1.29 mass% of 2-butoxyethanol
An etching solution raw material consisting of 91.14% by mass of water was prepared to prepare an etching concentrate.
　過酸化水素とエッチング濃縮液を混合し、過酸化水素濃度が４．５０質量％のエッチング液を調製した。さらに、硫酸銅とモリブデン粉末を加えて銅イオン濃度が２０００ｐｐｍ、モリブデンイオン濃度が２００ｐｐｍになるように調製した。また、液温は３０℃で用いた。エッチング濃縮液に占める各成分濃度と、各評価事項の結果を表１に示す。また、エッチング液全体に占める各成分濃度を表３に示す。 Hydrogen peroxide and etching concentrate were mixed to prepare an etching solution having a hydrogen peroxide concentration of 4.50% by mass. Further, copper sulfate and molybdenum powder were added to prepare a copper ion concentration of 2000 ppm and a molybdenum ion concentration of 200 ppm. The liquid temperature was 30 ° C. Table 1 shows the concentration of each component in the etching concentrate and the result of each evaluation item. Table 3 shows the concentration of each component in the entire etching solution.
　（実施例６）
　硝酸を１．２９質量％、
グリコール酸を１．１４質量％、
リンゴ酸を０．８５質量％、
βアラニンを１．４２質量％、
１アミノ２プロパノールを１．７１質量％、
フェニル尿素を０．１１質量％、
２－ブトキシエタノールを１．２９質量％
からなるエッチング液原料を水９２．１９質量％と調合し、エッチング濃縮液を調製した。 (Example 6)
1.29 mass% nitric acid,
1.14% by weight of glycolic acid,
0.85% by mass of malic acid,
β-alanine 1.42% by mass,
1.71% by mass of 1 amino 2-propanol,
0.11% by mass of phenylurea,
1.29 mass% of 2-butoxyethanol
An etching liquid raw material consisting of 92.19% by mass of water was prepared to prepare an etching concentrated liquid.
　過酸化水素とエッチング濃縮液を混合し、過酸化水素濃度が４．５０質量％のエッチング液を調製した。さらに、硫酸銅とモリブデン粉末を加えて銅イオン濃度が２０００ｐｐｍ、モリブデンイオン濃度が２００ｐｐｍになるように調製した。また、液温は３０℃で用いた。エッチング濃縮液に占める各成分濃度と、各評価事項の結果を表１に示す。また、エッチング液全体に占める各成分濃度を表３に示す。 Hydrogen peroxide and etching concentrate were mixed to prepare an etching solution having a hydrogen peroxide concentration of 4.50% by mass. Further, copper sulfate and molybdenum powder were added to prepare a copper ion concentration of 2000 ppm and a molybdenum ion concentration of 200 ppm. The liquid temperature was 30 ° C. Table 1 shows the concentration of each component in the etching concentrate and the result of each evaluation item. Table 3 shows the concentration of each component in the entire etching solution.
　（実施例７）
　硝酸を１．２９質量％、
グリコール酸を１．１４質量％、
リンゴ酸を０．８５質量％、
βアラニンを１．４２質量％、
１アミノ２プロパノールを１．７１質量％、
１－プロパノールを１．１６質量％
からなるエッチング液原料を水９２．４３質量％と調合し、エッチング濃縮液を調製した。 (Example 7)
1.29 mass% nitric acid,
1.14% by weight of glycolic acid,
0.85% by mass of malic acid,
β-alanine 1.42% by mass,
1.71% by mass of 1 amino 2-propanol,
1.16% by mass of 1-propanol
The etching liquid raw material which consists of was mixed with 92.43 mass% of water, and the etching concentrated liquid was prepared.
　過酸化水素とエッチング濃縮液を混合し、過酸化水素濃度が４．５０質量％のエッチング液を調製した。さらに、硫酸銅とモリブデン粉末を加えて銅イオン濃度が２０００ｐｐｍ、モリブデンイオン濃度が２００ｐｐｍになるように調製した。また、液温は３０℃で用いた。エッチング濃縮液に占める各成分濃度と、各評価事項の結果を表１に示す。また、エッチング液全体に占める各成分濃度を表３に示す。 Hydrogen peroxide and etching concentrate were mixed to prepare an etching solution having a hydrogen peroxide concentration of 4.50% by mass. Further, copper sulfate and molybdenum powder were added to prepare a copper ion concentration of 2000 ppm and a molybdenum ion concentration of 200 ppm. The liquid temperature was 30 ° C. Table 1 shows the concentration of each component in the etching concentrate and the result of each evaluation item. Table 3 shows the concentration of each component in the entire etching solution.
　（実施例８）
　硝酸を１．２９質量％、
グリコール酸を１．１４質量％、
リンゴ酸を０．８５質量％、
βアラニンを１．４２質量％、
１アミノ２プロパノールを１．７１質量％、
２－ブトキシエタノールを１．２９質量％
からなるエッチング液原料を水９２．３０質量％と調合し、エッチング濃縮液を調製した。 (Example 8)
1.29 mass% nitric acid,
1.14% by weight of glycolic acid,
0.85% by mass of malic acid,
β-alanine 1.42% by mass,
1.71% by mass of 1 amino 2-propanol,
1.29 mass% of 2-butoxyethanol
The etching liquid raw material which consists of was mixed with 92.30 mass% of water, and the etching concentrated liquid was prepared.
　過酸化水素とエッチング濃縮液を混合し、過酸化水素濃度が４．５０質量％のエッチング液を調製した。さらに、硫酸銅とモリブデン粉末を加えて銅イオン濃度が２０００ｐｐｍ、モリブデンイオン濃度が２００ｐｐｍになるように調製した。また、液温は３０℃で用いた。エッチング濃縮液に占める各成分濃度と、各評価事項の結果を表１に示す。また、エッチング液全体に占める各成分濃度を表３に示す。 Hydrogen peroxide and etching concentrate were mixed to prepare an etching solution having a hydrogen peroxide concentration of 4.50% by mass. Further, copper sulfate and molybdenum powder were added to prepare a copper ion concentration of 2000 ppm and a molybdenum ion concentration of 200 ppm. The liquid temperature was 30 ° C. Table 1 shows the concentration of each component in the etching concentrate and the result of each evaluation item. Table 3 shows the concentration of each component in the entire etching solution.
　（比較例１）
　硝酸を０．１７質量％、
グリコール酸を２．３８質量％、
グルタミン酸を０．８５質量％
アスパラギン酸を０．４２質量％、
βアラニンを０．６５質量％、
１アミノ２プロパノールを１．５５質量％、
フェニル尿素を０．１１質量％、
１－プロパノールを１．１３質量％
からなるエッチング液原料を水９２．７４質量％と調合し、エッチング濃縮液を調製した。 (Comparative Example 1)
0.17% by mass of nitric acid,
2.38% by mass of glycolic acid,
0.85% by mass of glutamic acid
0.42% by mass of aspartic acid,
β-alanine 0.65% by mass,
1.55% by mass of 1 amino 2-propanol,
0.11% by mass of phenylurea,
1.13% by mass of 1-propanol
The etching liquid raw material which consists of with 92.74 mass% of water was prepared, and the etching concentrated liquid was prepared.
　過酸化水素とエッチング濃縮液を混合し、過酸化水素濃度が４．５０質量％のエッチング液を調製した。さらに、硫酸銅とモリブデン粉末を加えて銅イオン濃度が２０００ｐｐｍ、モリブデンイオン濃度が２００ｐｐｍになるように調製した。また、液温は３０℃で用いた。エッチング濃縮液に占める各成分濃度と、各評価事項の結果を表２に示す。また、エッチング液全体に占める各成分濃度を表４に示す。 Hydrogen peroxide and etching concentrate were mixed to prepare an etching solution having a hydrogen peroxide concentration of 4.50% by mass. Further, copper sulfate and molybdenum powder were added to prepare a copper ion concentration of 2000 ppm and a molybdenum ion concentration of 200 ppm. The liquid temperature was 30 ° C. Table 2 shows the concentration of each component in the etching concentrate and the result of each evaluation item. Table 4 shows the concentration of each component in the entire etching solution.
　（比較例２）
　硝酸を０．３５質量％、
グリコール酸を２．９０質量％、
βアラニンを０．６６質量％、
１アミノ２プロパノールを１．７７質量％、
フェニル尿素を０．１１質量％、
１－プロパノールを１．１７質量％
からなるエッチング液原料を水９３．０４質量％と調合し、エッチング濃縮液を調製した。 (Comparative Example 2)
0.35 mass% nitric acid,
2.90% by mass of glycolic acid,
0.66% by mass of β-alanine,
1.77% by mass of 1 amino 2-propanol,
0.11% by mass of phenylurea,
1.17% by mass of 1-propanol
The etching liquid raw material which consists of was mixed with 93.04 mass% of water, and the etching concentrated liquid was prepared.
　過酸化水素とエッチング濃縮液を混合し、過酸化水素濃度が４．５０質量％のエッチング液を調製した。さらに、硫酸銅とモリブデン粉末を加えて銅イオン濃度が２０００ｐｐｍ、モリブデンイオン濃度が２００ｐｐｍになるように調製した。また、液温は２５℃で用いた。エッチング濃縮液に占める各成分濃度と、各評価事項の結果を表２に示す。また、エッチング液全体に占める各成分濃度を表４に示す。 Hydrogen peroxide and etching concentrate were mixed to prepare an etching solution having a hydrogen peroxide concentration of 4.50% by mass. Further, copper sulfate and molybdenum powder were added to prepare a copper ion concentration of 2000 ppm and a molybdenum ion concentration of 200 ppm. The liquid temperature was 25 ° C. Table 2 shows the concentration of each component in the etching concentrate and the result of each evaluation item. Table 4 shows the concentration of each component in the entire etching solution.
　（比較例３）
　硝酸を１．３０質量％、
グリコール酸を０．６５質量％、
乳酸を３．５７質量％
βアラニンを１．４３質量％、
１アミノ２プロパノールを２．５５質量％、
フェニル尿素を０．１１質量％、
１－プロパノールを１．１４質量％
からなるエッチング液原料を水８９．２５質量％と調合し、エッチング濃縮液を調製した。 (Comparative Example 3)
1.30% by mass of nitric acid,
0.65% by mass of glycolic acid,
3.57% by mass of lactic acid
β-alanine 1.43% by mass,
2.55% by mass of 1 amino 2-propanol,
0.11% by mass of phenylurea,
1.14% by mass of 1-propanol
An etching solution raw material consisting of 89.25% by mass of water was prepared to prepare an etching concentrate.
　過酸化水素とエッチング濃縮液を混合し、過酸化水素濃度が４．５０質量％のエッチング液を調製した。さらに、硫酸銅とモリブデン粉末を加えて銅イオン濃度が２０００ｐｐｍ、モリブデンイオン濃度が２００ｐｐｍになるように調製した。また、液温は２７．５℃で用いた。エッチング濃縮液に占める各成分濃度と、各評価事項の結果を表２に示す。また、エッチング液全体に占める各成分濃度を表４に示す。 Hydrogen peroxide and etching concentrate were mixed to prepare an etching solution having a hydrogen peroxide concentration of 4.50% by mass. Further, copper sulfate and molybdenum powder were added to prepare a copper ion concentration of 2000 ppm and a molybdenum ion concentration of 200 ppm. The liquid temperature was 27.5 ° C. Table 2 shows the concentration of each component in the etching concentrate and the result of each evaluation item. Table 4 shows the concentration of each component in the entire etching solution.
　（比較例４）
　硝酸を０．５３質量％、
グリコール酸を２．７４質量％、
コハク酸を１．４５質量％
βアラニンを１．４４質量％、
１アミノ２プロパノールを１．７５質量％、
フェニル尿素を０．１１質量％、
１－プロパノールを１．１４質量％
からなるエッチング液原料を水９０．８４質量％と調合し、エッチング濃縮液を調製した。 (Comparative Example 4)
0.53 mass% nitric acid,
2.74% by mass of glycolic acid,
1.45% by mass of succinic acid
1.44% by mass of β-alanine,
1.75% by mass of 1 amino 2-propanol
0.11% by mass of phenylurea,
1.14% by mass of 1-propanol
An etching solution raw material consisting of 90.84% by mass of water was prepared to prepare an etching concentrate.
　過酸化水素とエッチング濃縮液を混合し、過酸化水素濃度が４．５０質量％のエッチング液を調製した。さらに、硫酸銅とモリブデン粉末を加えて銅イオン濃度が２０００ｐｐｍ、モリブデンイオン濃度が２００ｐｐｍになるように調製した。また、液温は２５℃で用いた。エッチング濃縮液に占める各成分濃度と、各評価事項の結果を表２に示す。また、エッチング液全体に占める各成分濃度を表４に示す。 Hydrogen peroxide and etching concentrate were mixed to prepare an etching solution having a hydrogen peroxide concentration of 4.50% by mass. Further, copper sulfate and molybdenum powder were added to prepare a copper ion concentration of 2000 ppm and a molybdenum ion concentration of 200 ppm. The liquid temperature was 25 ° C. Table 2 shows the concentration of each component in the etching concentrate and the result of each evaluation item. Table 4 shows the concentration of each component in the entire etching solution.
　（比較例５）
　硝酸を１．２９質量％、
グリコール酸を１．１４質量％、
リンゴ酸を０．８５質量％
βアラニンを１．４２質量％、
１アミノ２プロパノールを１．７１質量％、
フェニル尿素を０．１１質量％、
からなるエッチング液原料を水９３．４８質量％と調合し、エッチング濃縮液を調製した。 (Comparative Example 5)
1.29 mass% nitric acid,
1.14% by weight of glycolic acid,
0.85 mass% of malic acid
β-alanine 1.42% by mass,
1.71% by mass of 1 amino 2-propanol,
0.11% by mass of phenylurea,
The etching liquid raw material which consists of was mixed with water 93.48 mass%, and the etching concentrated liquid was prepared.
　過酸化水素とエッチング濃縮液を混合し、過酸化水素濃度が４．５０質量％のエッチング液を調製した。さらに、硫酸銅とモリブデン粉末を加えて銅イオン濃度が２０００ｐｐｍ、モリブデンイオン濃度が２００ｐｐｍになるように調製した。また、液温は３０℃で用いた。エッチング濃縮液に占める各成分濃度と、各評価事項の結果を表２に示す。また、エッチング液全体に占める各成分濃度を表４に示す。 Hydrogen peroxide and etching concentrate were mixed to prepare an etching solution having a hydrogen peroxide concentration of 4.50% by mass. Further, copper sulfate and molybdenum powder were added to prepare a copper ion concentration of 2000 ppm and a molybdenum ion concentration of 200 ppm. The liquid temperature was 30 ° C. Table 2 shows the concentration of each component in the etching concentrate and the result of each evaluation item. Table 4 shows the concentration of each component in the entire etching solution.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
　＜結果＞
　実施例１から実施例８は、本発明に係るエッチング液である。アゾール化合物を含んでいないため、過酸化水素との間で反応物を生じず、析出物はない。酸性有機酸にグリコール酸、リンゴ酸の２種を同時に使用した。これらのサンプルは、析出物が無いうえに、テーパー角、Ｍｏアンダーカット、Ｍｏ残渣、Ｏ．Ｅ．耐性のいずれの項目もマル評価であった。さらに、過酸化水素分解速度も０．９６質量％／日未満であり、望ましい結果を得ることができた。 <Result>
Examples 1 to 8 are etching solutions according to the present invention. Since no azole compound is contained, no reaction product is formed with hydrogen peroxide, and there is no precipitate. Two kinds of glycolic acid and malic acid were used simultaneously as the acidic organic acid. These samples have no precipitates, and have a taper angle, Mo undercut, Mo residue, O.D. E. All items of resistance were rated as maru. Furthermore, the hydrogen peroxide decomposition rate was less than 0.96% by mass / day, and desirable results could be obtained.
　また、オーバーエッチング耐性が良好であったので、ジャストエッチングに費やす時間から２倍の時間までは良好なテーパー角を維持してエッチングすることができた。また、これらの実施例のエッチング液は、ＭｏとＣｕの膜厚比（ｔ０／ｔ１）が実施例の場合（２０／３００）と異なっても、膜厚比が０．０１以上０．２以下までの間にあれば、３０°以上６０°以下のテーパー角度を実現することができた。 Moreover, since the over-etching resistance was good, it was possible to perform etching while maintaining a good taper angle from the time spent for just etching to twice the time. In addition, the etching ratios of these examples are 0.01 to 0.2 even if the film thickness ratio of Mo and Cu (t0 / t1) is different from that of the example (20/300). In the meantime, a taper angle of 30 ° or more and 60 ° or less could be realized.
　実施例１、５、６、８は、過酸化水素分解速度が極めて小さく、長いポットライフを実現することができた。この時の組成との対応を見ると、硝酸濃度がエッチング液全量に対して１．０質量％以上であって、２－ブトキシエタノールが含まれていたとき（酸性有機酸、中性有機酸、アミン化合物はもちろん含まれる）に過酸化水素の分解速度が抑制されていた。 In Examples 1, 5, 6, and 8, the decomposition rate of hydrogen peroxide was extremely small, and a long pot life could be realized. Looking at the correspondence with the composition at this time, when the nitric acid concentration was 1.0% by mass or more with respect to the total amount of the etching solution and 2-butoxyethanol was contained (acidic organic acid, neutral organic acid, The decomposition rate of hydrogen peroxide was suppressed in (including amine compounds of course).
　過酸化水素分解抑制剤は、フェニル尿素、１－プロパノール、２－ブトキシエタノールを用いたが、少なくとも１－プロパノールと２－ブトキシエタノールの何れかを含めば、過酸化水素の分解速度は抑制された。しかし、比較例１のように１－プロパノールが含まれていてもリンゴ酸が含まれていないと過酸化水素の分解を抑制できなかった。これより、過酸化水素分解抑制剤はリンゴ酸と共に使用することで、過酸化水素分解を効果的に抑制できたと結論できる。 As the hydrogen peroxide decomposition inhibitor, phenylurea, 1-propanol, and 2-butoxyethanol were used, but the decomposition rate of hydrogen peroxide was suppressed if at least one of 1-propanol and 2-butoxyethanol was included. . However, even if 1-propanol was included as in Comparative Example 1, decomposition of hydrogen peroxide could not be suppressed if malic acid was not included. From this, it can be concluded that the hydrogen peroxide decomposition inhibitor was able to effectively suppress hydrogen peroxide decomposition when used with malic acid.
　また、比較例５は、フェニル尿素とリンゴ酸を用いた例であるが、実施例の各サンプルほど過酸化水素分解を抑制できなかった。しかし実施例各サンプルの結果からわかるように、１－プロパノールおよびまたは２－ブトキシエタノールと共に利用することができる。 Further, Comparative Example 5 is an example using phenylurea and malic acid, but the hydrogen peroxide decomposition could not be suppressed as much as each sample of the example. However, as can be seen from the results of each example, it can be used with 1-propanol and / or 2-butoxyethanol.
　比較例２および４は析出物が観測された。したがって、比較例２については、析出物以外の物性について測定を行っていない。析出物の発生原因は明確ではない。しかし、エッチング液全量に対してグリコール酸の濃度が２．１質量％を超えると、析出物が生じる結果となった。 In Comparative Examples 2 and 4, precipitates were observed. Therefore, about the comparative example 2, it has not measured about physical properties other than a precipitate. The cause of the precipitate is not clear. However, when the concentration of glycolic acid with respect to the total amount of the etching solution exceeds 2.1% by mass, precipitates are generated.
　すでに記載しているように、本発明に係るエッチング液は、過酸化水素を加えないエッチング濃縮液として、取り扱うことができる。つまり、エッチング液は、３５ｗｔ％の濃度の過酸化水素溶液とエッチング濃縮液を混合して、表３（比較例について表４）に示すような本発明に係るエッチング液として利用することができる。表１（比較例については表２）は、過酸化水素を含まないエッチング濃縮液での組成比を示している。 As already described, the etching solution according to the present invention can be handled as an etching concentrate without adding hydrogen peroxide. That is, the etching solution can be used as an etching solution according to the present invention as shown in Table 3 (Table 4 for the comparative example) by mixing a hydrogen peroxide solution having a concentration of 35 wt% and an etching concentrated solution. Table 1 (Table 2 for the comparative example) shows the composition ratio in the etching concentrate containing no hydrogen peroxide.
　したがって、各構成材料同士のエッチング液としての組成比とエッチング濃縮液としての組成比は、表１、２と表３、４を用いてそれぞれ読み直すことができる。例えば、実施例１を例にとると、表１のエッチング濃縮液において硝酸は１．２９質量％であるが、表３のエッチング液（過酸化水素が加えられた状態）では、１．１３質量％となる。 Therefore, the composition ratio of each constituent material as an etching solution and the composition ratio as an etching concentrate can be reread using Tables 1, 2, and 3, 4, respectively. For example, taking Example 1 as an example, nitric acid is 1.29% by mass in the etching concentrate in Table 1, but 1.13% in the etching solution in Table 3 (in a state where hydrogen peroxide is added). %.
　本発明のエッチング液は、液晶ディスプレイ、プラズマディスプレイ、有機ＥＬなどＦＰＤといった製品を問わず、ガラス基板、シリコン基板、アモルファスシリコン基板、金属酸化物基板等の基板上若しくは、これらの材質からなる下地層上に形成されたモリブデン層と銅層が積層された配線を用いる局面において、広く利用することができる。 The etching solution of the present invention can be applied to a substrate such as a glass substrate, a silicon substrate, an amorphous silicon substrate, or a metal oxide substrate, or a base layer made of these materials, regardless of products such as liquid crystal displays, plasma displays, and organic EL FPDs. It can be widely used in a situation where a wiring in which a molybdenum layer and a copper layer formed on each other are used.
１　基板
２　銅層
３　モリブデン層
４　レジスト（層）
５　テーパー角
６　傾斜面
１０　アンダーカット部分 1 Substrate 2 Copper layer 3 Molybdenum layer 4 Resist (layer)
5 Taper angle 6 Slope 10 Undercut part

Claims (11)

  1. 　過酸化水素と、
    　無機酸と、
    　酸性有機酸と、
    　中性有機酸と、
    　アミン化合物と、
    　過酸化水素分解抑制剤を含むことを特徴とする銅層とモリブデン層を含む多層膜用エッチング液。     Hydrogen peroxide,
    Inorganic acids,
    An acidic organic acid,
    Neutral organic acids,
    An amine compound;
    A multilayer film etching solution comprising a copper layer and a molybdenum layer, characterized by comprising a hydrogen peroxide decomposition inhibitor.
  2. 　アゾール化合物と、リン化合物と、フッ素化合物を含まないことを特徴とする請求項１に記載された銅層とモリブデン層を含む多層膜用エッチング液。 2. The multilayer film etching solution comprising a copper layer and a molybdenum layer according to claim 1, which does not contain an azole compound, a phosphorus compound, and a fluorine compound.
  3. 　前記無機酸は硝酸であることを特徴とする請求項１または２の何れかの請求項に記載された銅層とモリブデン層を含む多層膜用エッチング液。 3. The multilayer film etching solution comprising a copper layer and a molybdenum layer according to claim 1 or 2, wherein the inorganic acid is nitric acid.
  4. 　前記酸性有機酸は、グリコール酸、リンゴ酸の２種を含むことを特徴とする請求項１乃至３の何れか１の請求項に記載された銅層とモリブデン層を含む多層膜用エッチング液。 The etching solution for a multilayer film including a copper layer and a molybdenum layer according to any one of claims 1 to 3, wherein the acidic organic acid includes two types of glycolic acid and malic acid.
  5. 　前記中性有機酸は、βアラニンであることを特徴とする請求項１乃至４の何れか１の請求項に記載された銅層とモリブデン層を含む多層膜用エッチング液。 5. The multilayer film etching solution comprising a copper layer and a molybdenum layer according to any one of claims 1 to 4, wherein the neutral organic acid is β-alanine.
  6. 　前記アミン化合物が、１－アミノ－２－プロパノールであることを特徴とする請求項１乃至５の何れか１の請求項に記載された銅層とモリブデン層を含む多層膜用エッチング液。 6. The multilayer film etching solution comprising a copper layer and a molybdenum layer according to any one of claims 1 to 5, wherein the amine compound is 1-amino-2-propanol.
  7. 　前記過酸化水素分解抑制剤は少なくとも低級アルコールとエーテルの何れかを含むことを特徴とする請求項１乃至６の何れか１の請求項に記載された銅層とモリブデン層を含む多層膜用エッチング液。 The etching for multilayer film including a copper layer and a molybdenum layer according to any one of claims 1 to 6, wherein the hydrogen peroxide decomposition inhibitor includes at least one of a lower alcohol and an ether. liquid.
  8. 　さらに銅イオンを５００ｐｐｍ以上７０００ｐｐｍ以下含むことを特徴とする請求項１乃至７の何れか１の請求項に記載された銅層とモリブデン層を含む多層膜用エッチング液。 Furthermore, copper ion is contained 500 ppm or more and 7000 ppm or less, The etching liquid for multilayer films containing the copper layer and molybdenum layer described in any one of Claims 1 thru | or 7 characterized by the above-mentioned.
  9. 　無機酸と、
    　酸性有機酸と、
    　中性有機酸と、
    　アミン化合物と、
    　過酸化水素分解抑制剤と、
    　水を含むことを特徴とする銅層とモリブデン層を含む多層膜用エッチング濃縮液。     Inorganic acids,
    An acidic organic acid,
    Neutral organic acids,
    An amine compound;
    A hydrogen peroxide decomposition inhibitor;
    An etching concentrate for a multilayer film comprising a copper layer and a molybdenum layer, characterized by comprising water.
  10. 　無機酸と、
    　酸性有機酸と、
    　中性有機酸と、
    　アミン化合物と、
    　過酸化水素分解抑制剤と
    　水を含むエッチング濃縮液と水と過酸化水素を調合し多層膜用エッチング液を調合する工程と、
    　前記多層膜用エッチング液を被処理基板に接触させる工程を含むことを特徴とする銅層とモリブデン層を含む多層膜のエッチング方法。     Inorganic acids,
    An acidic organic acid,
    Neutral organic acids,
    An amine compound;
    A step of preparing an etching solution for multilayer film by preparing an etching concentrate containing hydrogen peroxide decomposition inhibitor, water, water and hydrogen peroxide,
    A method for etching a multilayer film including a copper layer and a molybdenum layer, comprising a step of bringing the multilayer film etching solution into contact with a substrate to be processed.
  11. 　前記多層膜用エッチング液を被処理基板に接触させる工程では、
    　前記多層膜用エッチング液のｐＨが２から５の範囲であり、液温が１８℃から３５℃の条件で行なわれることを特徴とする請求項１０に記載された銅層とモリブデン層を含む多層膜のエッチング方法。

          In the step of bringing the multilayer film etching solution into contact with the substrate to be processed,
    11. The multilayer including a copper layer and a molybdenum layer according to claim 10, wherein the multilayer etchant has a pH of 2 to 5 and a temperature of 18 ° C. to 35 ° C. 11. Method for etching the film.

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