WO2016152091A1 - 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 - Google Patents

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 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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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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Panasonic Intellectual Property Management Co Ltd
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Panasonic Intellectual Property Management Co Ltd
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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 potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table 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.

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CN114014771A (zh) * 2021-06-30 2022-02-08 安徽华恒生物科技股份有限公司 一种超高纯度的氨基酸及其制备方法和其应用
WO2024038697A1 (ja) * 2022-08-19 2024-02-22 株式会社Adeka 組成物、エッチング方法、及び積層体の製造方法
US20240229217A9 (en) * 2021-02-24 2024-07-11 Imec Vzw A method for etching molybdenum

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CN108930037B (zh) * 2017-05-22 2021-02-26 东友精细化工有限公司 金属膜蚀刻液组合物及利用其的导电图案形成方法
CN107151795A (zh) * 2017-06-02 2017-09-12 苏州晶瑞化学股份有限公司 一种铜钼合金膜用蚀刻液
JP6822985B2 (ja) 2018-01-05 2021-01-27 フタバ産業株式会社 消音装置
JP7595273B2 (ja) * 2020-09-24 2024-12-06 パナソニックＩｐマネジメント株式会社 エッチング液
KR20230075433A (ko) 2020-09-29 2023-05-31 미쯔비시 가스 케미칼 컴파니, 인코포레이티드 반도체기판 세정용 조성물 및 세정방법
CN114318340B (zh) * 2021-12-22 2023-09-29 惠州达诚微电子材料有限公司 一种蚀刻液组合物及其制备方法

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