WO2019064506A1 - Solution de gravure et concentré de gravure pour film multicouches et procédé de gravure - Google Patents

Solution de gravure et concentré de gravure pour film multicouches et procédé de gravure Download PDF

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

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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
    • H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having 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 an etching solution for a multilayer film, an etching solution and an etching method used for etching a multilayer film of copper and titanium used for wiring of flat panel displays such as liquid crystal and organic EL.
  • Aluminum has been used as a wiring material for TFTs (Thin Film Transistors) of flat panel displays (FPDs) such as liquid crystal and organic EL (Electro-Luminescence).
  • FPDs Thin Film Transistors
  • LCDs flat panel displays
  • Electro-Luminescence Electro-Luminescence
  • large-screen, high-definition FPDs have become widespread, and wiring materials to be used have been required to have lower resistance than aluminum. Therefore, copper having a resistance lower than that of aluminum has recently been used as a wiring material.
  • adhesion to the substrate and diffusion to the semiconductor substrate. That is, in the case of using for gate wiring, adhesion may not be sufficient between substrates such as glass even when using a sputtering method that is considered to have a relatively high impact energy to the substrate. In addition, in the case of using in source / drain wiring, there is a problem that the adhered copper is diffused to the underlying silicon, and the electrical design value of the semiconductor is changed.
  • a multilayer structure was employed in which a molybdenum film is first formed on a semiconductor substrate, and a copper film is formed thereon.
  • titanium has been adopted as a base layer of a copper film in order to further ensure the isolation and adhesion to the base.
  • the wiring of FPD is formed by wet etching a multilayer film formed by sputtering. This is because a large area can be formed at once, which makes it possible to shorten the process.
  • the following points are considered important for the etching solution for wet etching of the wiring.
  • (2) The wiring cross section after processing is a forward taper of a predetermined angle.
  • the etching rate does not change by containing copper ions (the bath life is long). (4) There should be little generation of precipitates.
  • Patent Document 1 as an etching solution for a copper / titanium laminated film, (A) hydrogen peroxide, (B) Nitric acid, (C) ammonium fluoride and / or ammonium acid fluoride as a fluoride ion source, (D) 5-amino-1H-tetrazole, (E) containing tetraalkylammonium hydroxide and / or (hydroxyalkyl) trialkylammonium hydroxide as quaternary ammonium hydroxide and (F) phenyl urea and / or phenol sulfonic acid, An etchant for a multilayer film having a pH of 1.5 to 2.5 is disclosed.
  • Patent Document 1 It has been shown that the etching solution of Patent Document 1 can be etched in a suitable range with respect to top CD loss, bottom CD loss, barrier film tailing, taper angle, etc. which are indicators of side etching of the lower titanium film and upper copper film. There is.
  • the range (bath life) in which the above-mentioned characteristics can be maintained is set to 4000 ppm.
  • the amount of metal ions exceeds this value, decomposition of hydrogen peroxide and nitric acid proceeds, and the performance can not be maintained.
  • the present invention is conceived to solve the above-mentioned problems, and even if the metal ion concentration in the etching solution becomes high, the change in etching performance can be kept within an acceptable range, and it takes time for composition control. It is an object of the present invention to provide a copper / titanium etching solution which can be reduced.
  • the etching solution for a multilayer film according to the present invention is An etching solution for etching a multilayer film of copper and titanium, (A) hydrogen peroxide, (B) a fluorine ion supply source, (C) azoles, (D) hydrogen peroxide stabilizer, (E) with an organic acid, (F) amines, (G) contains water,
  • the organic acid is selected from methanesulfonic acid and lactic acid based on the total amount of etching solution.
  • the methanesulfonic acid contains 0.2% by mass to 1.5% by mass with respect to the total amount of the etching solution
  • at least one type of organic acid of lactic acid, succinic acid, glutaric acid and malonic acid is used in combination,
  • lactic acid is contained in the organic acid used in combination
  • the lactic acid is 2.0% by mass to 10.0% by mass with respect to the total amount of the etching solution
  • succinic acid is contained in the organic acid used in combination
  • the succinic acid is 4.5% by mass to 5.5% by mass with respect to the total amount of the etching solution
  • glutaric acid is contained in the organic acid used in combination
  • the glutaric acid is 9.5% by mass to 10.5% by mass with respect to the total amount of the etching solution
  • malonic acid is contained in the organic acid used in combination
  • the malonic acid is 4.5% by mass to 5.5% by mass with respect to the total amount of the etching solution
  • the organic acid is only lactic acid
  • the etching method according to the present invention is Bringing the above etching solution into contact with a substrate to be treated in which a resist pattern is disposed on a multilayer film of copper and titanium;
  • the method is characterized by including the step of maintaining the contact state for a predetermined time.
  • the etching solution according to the present invention can maintain each parameter of the side etching in a suitable range even if the metal ion concentration in the etching solution is 8,000 ppm. Therefore, even when etching a substrate with a thick copper film, it is possible to carry out the conventional composition control (determination of the amount and timing of addition of components, total amount, etc.).
  • etching solution for copper and titanium multilayer films according to the present invention will be described below.
  • the following description shows one embodiment of the etching solution according to the present invention, and the following embodiments and examples may be modified without departing from the spirit of the present invention.
  • the numerical range is indicated by “A to B”, it means “more than A and less than B”. That is, it means a large range including the numerical value A and a small range including the numerical value B.
  • the etching solution for a multilayer film according to the present invention contains hydrogen peroxide, a fluorine ion supply source, an azole, a hydrogen peroxide stabilizer, an organic acid, an amine and water. Each component will be described in detail below.
  • ⁇ Hydrogen peroxide> copper is oxidized to form copper oxide (CuO), which is dissolved by an acid (organic acid). Hydrogen peroxide is used as an oxidizing agent to oxidize copper. Hydrogen peroxide is preferably 4.0% by mass to 8.8% by mass, more preferably 5.0% by mass to 7.0% by mass, and 5.5% by mass to 6.5% by mass of the etching solution. % Is most preferable.
  • Fluoride ion is useful for dissolving titanium.
  • the source of fluorine ions is not particularly limited as long as fluorine is ionized in the etching solution. Hydrofluoric acid, ammonium fluoride, ammonium hydrogen fluoride and the like can be suitably used. In particular, ammonium fluoride (NH 4 F: CAS No. 12125-01-8) can be suitably used.
  • the fluorine ion source corrodes the substrate itself if the content is too high to corrode the glass. 0.2% by mass to 1.0% by mass is preferable based on the total amount of the etching solution.
  • the etching solution for a multilayer film according to the present invention contains azoles in order to suppress the etching rate of Cu.
  • azoles triazoles, tetrazoles, imidazoles, thiazoles etc. can be used suitably. More specifically, the following can be listed.
  • triazoles 1H-benzotriazole, 5-methyl-1H-benzotriazole, 3-amino-1H-triazole and the like can be suitably used.
  • tetrazole 1H-tetrazole, 5-methyl-1H-tetrazole, 5-phenyl-1H-tetrazole, 5-amino-1H-tetrazole and the like can be suitably used.
  • imidazoles 1H-imidazole, 1H-benzimidazole and the like can be suitably used.
  • thiazoles 1,3-thiazole, 4-methylthiazole and the like can be suitably used.
  • 5-amino-1H-tetrazole (CAS No. 4418-61-5: hereinafter also referred to as "5A1HT”) is particularly preferable.
  • the content of these azoles is preferably 0.005% by mass to 1.0% by mass, more preferably 0.01% by mass to 0.5% by mass, and most preferably 0.01% by mass with respect to the total amount of the etching solution. It is preferable to contain up to 0.10 mass%.
  • the etching solution for a multilayer film according to the present invention utilizes hydrogen peroxide as an oxidant. Since hydrogen peroxide is self-decomposable, a decomposition inhibitor that suppresses its decomposition is added. Hydrogen peroxide decomposition inhibitors are also referred to as hydrogen peroxide stabilizers.
  • urea-based hydrogen peroxide stabilizers such as phenylurea, allylurea, 1,3-dimethylurea and thiourea, phenylacetic acid amide, phenylethylene glycol, 1-propanol, Lower alcohols such as 2-propanol are often used.
  • BG exerts a remarkable effect of suppressing the decomposition of hydrogen peroxide even when the Cu concentration is as high as 8,000 ppm or more.
  • BG is effective when it is added to the etching solution at a certain level or more, and even if it is added in a large amount, the effect is saturated. If the amount of other necessary components can be secured, the effect as an etching solution can be exhibited even if it is added in a large amount. However, adding more BG increases the cost. Considering the effect and the price, there is no point in adding more than 5.0% by mass to the total amount of the etching solution.
  • BG as a hydrogen peroxide stabilizer may be contained in an amount of 0.1% by mass to 5.0% by mass, based on the total amount of the etching solution, from 0.5% by mass to 2.5% by mass. It is more preferable that the content is 0.7% by mass to 1.5% by mass.
  • phenyl urea and hydrogen peroxide react with each other to cause azoles and excess, when used conventionally as a hydrogen peroxide decomposition inhibitor. A precipitate different from the hydrogen oxide reactant was produced. On the other hand, BG does not generate such precipitates. Therefore, BG is a suitable hydrogen peroxide stabilizer also in terms of the formation of precipitates.
  • Organic acid serves to etch the copper film and to adjust the taper angle of the cross section of the etched interconnection. In addition, it is considered that it also has a function of suppressing the decomposition of hydrogen peroxide to some extent.
  • An acidic organic acid is used as the organic acid.
  • organic acid examples include aliphatic carboxylic acids having 1 to 18 carbon atoms, aromatic carboxylic acids having 6 to 10 carbon atoms, amino acids having 1 to 10 carbon atoms, and sulfonic acids having 1 to 10 carbon atoms. .
  • Examples of aliphatic carboxylic acids having 1 to 18 carbon atoms include formic acid, acetic acid, propionic acid, lactic acid, diglycolic acid, pyruvic acid, malic acid, butyric acid, hydroxybutyric acid, tartaric acid, succinic acid, malic acid, maleic acid and fumaric acid , Valeric acid, glutaric acid, itaconic acid, adipic acid, caproic acid, citric acid, propane tricarboxylic acid, trans-aconitic acid, enanthate, caprylic acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linole Preferred are acid and linolenic acid.
  • Preferred examples of the aromatic carboxylic acid having 6 to 10 carbon atoms include benzoic acid, salicylic acid, mandelic acid, phthalic acid, isophthalic acid and terephthalic acid.
  • amino acid having 1 to 10 carbon atoms carbamic acid, alanine, glycine, asparagine, aspartic acid, sarcosine, serine, glutamine, glutamic acid, 4-aminobutyric acid, iminodibutyric acid, arginine, leucine, isoleucine, nitrilotriacetic acid, etc. Is preferably mentioned.
  • sulfonic acid having 1 to 10 carbon atoms methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid and the like are preferable.
  • lactic acid, succinic acid, glutaric acid, malonic acid and methanesulfonic acid can be suitably used as the acidic organic acid.
  • Methanesulfonic acid (CAS number: 75-75-2) is not used alone, but is always used in combination with other acidic organic acids.
  • the amount of methanesulfonic acid is preferably 0.2% by mass to 1.5% by mass with respect to the total amount of the etching solution.
  • the acid organic acid to be used in combination is lactic acid (mixed state (DL-lactic acid) CAS number: 50-21-5), the range of 2.0 mass% to 10.0 mass% of lactic acid with respect to the total amount of the etching solution is preferable.
  • L-lactic acid or D-lactic acid may be used alone as lactic acid.
  • succinic acid (CAS No. 11015-6)
  • succinic acid is preferably in the range of 4.5% by mass to 5.5% by mass with respect to the total amount of the etching solution.
  • the acid organic acid used in combination is glutaric acid (CAS number: 110-94-1), and the glutaric acid is preferably in the range of 9.5% by mass to 10.5% by mass with respect to the total amount of the etching solution.
  • the acid organic acid used in combination is malonic acid (CAS number: 141-82-2)
  • the malonic acid is preferably in the range of 4.5% by mass to 5.5% by mass with respect to the total amount of the etching solution.
  • Lactic acid can be used alone.
  • the range of 4.0% by mass to 5.0% by mass is preferable with respect to the total amount of the etching solution.
  • the amine compound is responsible for adjusting the pH of the etching solution.
  • the amine compound one having 2 to 10 carbon atoms can be suitably used. More specifically, ethylenediamine, trimethylenediamine, tetramethylenediamine, 1,2-propanediamine, 1,3-propanediamine, N, N-dimethyl-1,3-propanediamine, N, N-diethyl-1 , 3-propanediamine, 1,3-diaminobutane, 2,3-diaminobutane, pentamethylenediamine, 2,4-diaminopentane, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, N-methyl Ethylenediamine, N, N-dimethylethylenediamine, trimethylethylenediamine, N-ethylethylenediamine, N, N-diethylethylenediamine, triethyl
  • triisopropanolamine (CAS No. 122-20-3) is particularly preferable.
  • the amine compound is preferably contained in an amount of 0.5% by mass to 3.0% by mass, more preferably 0.6% by mass to 2.5% by mass, based on the total amount of the etching solution. It is most preferable if it is 2.0 mass%.
  • the etching solution for dilution is additionally added to the usual etching solution for multilayer film so that the Cu ion concentration becomes about 2,000 ppm to 4,000 ppm. Because the decomposition rate of hydrogen peroxide is increased, the hydrogen peroxide concentration is reduced. However, since the etching solution according to the present invention suppresses the decomposition rate of hydrogen peroxide, it is not necessary to add the etching solution for dilution of Cu ions even when the Cu ion concentration becomes higher. More specifically, it is not necessary to add an etching solution for dilution to a Cu concentration of the etching solution of at least 8,000 ppm.
  • ⁇ Others> water and various additives generally used in the range that does not inhibit the etching performance may be added to the etching solution for a multilayer film of the present invention. Since water is intended for precision processing, it is desirable that there be no foreign matter present. Pure water or ultrapure water is preferred. Further, it goes without saying that the range of the content ratio of each component described above is appropriately adjusted to be 100% by mass in the total amount of the etching solution.
  • the etching solution for a multilayer film according to the present invention is preferably used in the range of pH 1 to 4, more preferably pH 1.5 to 2.5. Also, the etching solution can be used between 20 ° C. and 60 ° C. The temperature is more preferably 30 ° C. to 55 ° C., and most preferably 35 ° C. to 50 ° C.
  • Hydrogen peroxide is used in the multilayer film etching solution according to the present invention. Hydrogen peroxide self decomposes. Therefore, the etching solution contains a hydrogen peroxide decomposition inhibitor. However, for storage, hydrogen peroxide (or hydrogen peroxide solution) and other liquids may be stored separately. Alternatively, only the hydrogen peroxide (or hydrogen peroxide water), water, and the raw material from which copper ions are removed (referred to as "etching liquid raw material”) may be stored collectively. In addition, the thing of a liquid and the thing of forms other than a liquid may exist in an etching liquid raw material. That is, the etching solution for a multilayer film according to the present invention may be completed by combining an etching solution raw material, water, and hydrogen peroxide (or hydrogen peroxide water).
  • the etching solution raw material and water may be mixed to prepare a solution of the etching liquid raw material.
  • This solution may be water in a proportion smaller than the proportion of water in the etching solution shown in the examples described later.
  • the solution of the etching solution raw material produced with the etching solution raw material and water is called "etching concentrate.”
  • the etching solution completed by mixing hydrogen peroxide in a predetermined ratio may be called “complete etching solution”.
  • the etching concentrate is convenient for storage and transfer since it has a smaller volume due to the absence of a portion of hydrogen peroxide and water as compared to a complete etching solution. Therefore, the etching solution for a multilayer film (complete etching solution) of the present invention may be completed by combining the etching solution, water and hydrogen peroxide.
  • the etching concentrate is composed of the components obtained by removing hydrogen peroxide from the complete etching solution according to the present invention, and adding hydrogen peroxide and water to a predetermined concentration completes the etching solution of the present invention.
  • the etching concentrate can be expressed by defining the composition ratio of each component when the hydrogen peroxide is a complete etching solution prepared to have a predetermined concentration.
  • the water of the etching concentrate may have an amount sufficient to dissolve the etching solution raw material. That is, considering that hydrogen peroxide is supplied as a hydrogen peroxide solution which is an aqueous solution, the etching solution for a multilayer film of the present invention should be completed by combining the etching concentrate, water, and hydrogen peroxide water. Can.
  • each component ratio of the etching concentrate is represented by a ratio to the total amount when the etching solution is completed. Therefore, the sum of the respective components of the etching concentrate does not reach 100% by mass.
  • the object using the etching solution for a multilayer film according to the present invention is that titanium or a titanium alloy (also referred to simply as “titanium” including titanium alloy) is a lower layer, and copper or a copper alloy (also referred to simply as "copper” including a copper alloy) Is a multilayer film of copper / titanium with an upper layer.
  • the thickness of the lower layer titanium is thinner than the thickness of the upper layer copper. Assuming that the thickness of the lower layer is t0 and the thickness of the upper layer is t1, the range of t1 / t0 is in the range of 16 to 32.
  • the etchant for a multilayer film according to the present invention can be stored for a long time by storing hydrogen peroxide, an etching solution raw material and water separately during storage. Then, in actual use, these are mixed to complete the etching solution.
  • the method of preparation is not limited as long as the concentration of hydrogen peroxide finally reaches a predetermined concentration.
  • an etching concentrate is prepared by mixing a predetermined amount of water with the etching solution raw material.
  • Hydrogen peroxide is usually supplied as a hydrogen peroxide solution having a concentration higher than the hydrogen peroxide concentration of the etching solution for a multilayer film according to the present invention. Therefore, a predetermined amount of hydrogen peroxide solution and etching concentrate (which may further contain water) are prepared.
  • This process may be called a process of preparing an etching solution for multilayer film. Note that this step does not have to be performed immediately before etching, and etching may be performed using an etching solution that has been prepared in advance including hydrogen peroxide.
  • the etching solution When the etching is performed, the etching solution is used under the conditions of pH 1 to 4 and 20 ° C. to 60 ° C. as described above. Therefore, it is desirable that the object to be etched (substrate to be processed) be also preheated to this temperature.
  • the method of bringing the substrate to be treated into contact with the etching solution is not particularly limited. As in the shower type, the etching solution may be dispersed to the substrate to be processed from above, or a method of dipping the substrate to be processed in a pool of etching solution may be used. This may be called a step of bringing the etching solution for multilayer film into contact with the substrate to be treated.
  • the etching must maintain the contact between the substrate to be processed and the etching solution for a predetermined time. This is a step of maintaining the contact between the substrate to be processed and the etching solution for a predetermined time.
  • the substrate to be treated is a substrate in a state in which a titanium layer and a copper layer are laminated on a base material such as glass, and a resist pattern for pattern formation is formed on this laminated film.
  • titanium was deposited to a thickness of 25 nm by sputtering on a glass substrate, copper was subsequently deposited to a thickness of 600 nm, and a Cu / Ti multilayer film sample was produced. .
  • a resist patterned in a wiring shape was formed on this copper film, and used as a substrate for taper angle evaluation. That is, the substrate comprises a glass substrate, a titanium film, a copper film thereon, and a patterned resist layer on the copper film.
  • Etching was performed by immersing the substrate in an etching solution for the time of just etching. After the sample after etching was washed and dried, the wiring portion was cut at right angles to the wiring direction, and the cut surface was observed.
  • FIG. 1 A schematic view of the cross-sectional shape is shown in FIG. Referring to FIG. 1, the cut surface is formed of a glass substrate 10, a titanium layer 12, a copper layer 14, and a resist layer 16.
  • a virtual surface 18 perpendicular to the glass substrate 10 formed between the end 16 a of the resist layer 16 and the glass substrate 10 is an ideal edge surface.
  • the actual edge surface has different etching rates on the upper and lower surfaces of the film, and is an inclined surface as shown in the figure.
  • the copper layer 14 directly below the end 16 a of the resist layer 16 is not present because the etching proceeds. Therefore, the end 16a of the resist layer 16 is wedge-shaped.
  • the copper layer 14 is deeply eroded from the virtual surface 18 in a direction closer to the resist layer 16 than in a direction closer to the glass substrate 10.
  • the titanium layer 12 which is the lower layer of the copper layer 14 has a slight degree of erosion from the virtual surface 18 due to the difference in etching rate with copper.
  • top CD critical dimension: line width
  • bottom CD loss The angle ⁇ of the slope from the end 14 ba of the lower surface 14 b of the copper layer 14 to the end 14 aa of the upper surface 14 a.
  • the top CD loss, the bottom CD loss, and the taper angle are represented by symbols “a”, “b”, and “ ⁇ ”, respectively. Since the top CD loss and the bottom CD loss usually occur on both sides of the line width, a value twice as large as the measured value is used as the evaluation value. That is, if the top CD loss is 0.5 ⁇ m when observing the cross section of a certain sample, the evaluation value of the top CD loss is 1.0 ⁇ m. However, here, the measured values of the top CD loss a and the bottom CD loss b of only one side of the wiring are shown in the table.
  • the top CD loss a is preferably 0.5 ⁇ m to 2.0 ⁇ m, and the bottom CD loss b is preferably 0.3 ⁇ m to 1.0 ⁇ m.
  • the taper angle ⁇ may be 30 ° to 80 °.
  • the “glass corrosion rate” was determined by measuring the level difference between the eroded portion and the non-eroded portion of the sample subjected to the etching experiment with a step measuring device.
  • the unit is nm / min.
  • the glass corrosion rate may be 30 to 60 nm / min.
  • “Evaluation Cu concentration” is a case where etching is performed while dissolving a predetermined amount of copper in the etching solution as a sample, and the taper angle ⁇ , the top CD loss a, or the bottom CD loss b is out of the preferable range Alternatively, the concentration immediately before the concentration at which etching could not be continued due to other causes was used. If the "evaluation Cu concentration" is high, it may be said that the bus life is long.
  • Example 1 As an acidic organic acid, 0.3% by mass of methanesulfonic acid, 9.0% by mass of lactic acid, As an amine compound, 0.75% by mass of triisopropanolamine, As a hydrogen peroxide stabilizer 0.90% by mass of 2-butoxyethanol, As azoles, 0.04 mass% of 5-amino-1H-tetrazole As a fluoride ion source, 0.4 mass% of ammonium fluoride The etching liquid raw material which consists of these is mixed with 72.04 mass% of water, and the etching concentrate was prepared. In addition, each component ratio in an etching concentrate is mixed with the hydrogen-peroxide solution mentioned later, and is represented by the ratio with respect to the total amount when the etching liquid is completed. The same applies to the following examples and comparative examples.
  • the etching concentrate is mixed with 16.57% by weight of 35% hydrogen peroxide water (5.8% by weight of hydrogen peroxide and 10.77% by weight of water based on the total amount of etching solution), and the hydrogen peroxide concentration is A 5.8% by mass etchant was prepared.
  • the total amount of water is 82.81% by mass.
  • the solution temperature was 35 ° C.
  • the concentration of each component in the entire etching solution and the result of each evaluation item are shown in Table 1. In Table 1, the total amount of water is described as "the balance”. The same applies to Table 2 below.
  • Example 2 As an acidic organic acid, 1.0% by mass of methanesulfonic acid, 2.7% by mass of lactic acid, As an amine compound, 2.0% by mass of triisopropanolamine, As a hydrogen peroxide stabilizer 0.90% by mass of 2-butoxyethanol, As azoles, 0.04 mass% of 5-amino-1H-tetrazole As a fluoride ion source, 0.8 mass% of ammonium fluoride The etching liquid raw material which consists of these is mixed with 75.99 mass% of water, and the etching concentrate was prepared.
  • the etching concentrate is mixed with 16.57% by weight of 35% hydrogen peroxide water (5.8% by weight of hydrogen peroxide and 10.77% by weight of water based on the total amount of etching solution), and the hydrogen peroxide concentration is A 5.8% by mass etchant was prepared.
  • the total amount of water is 86.76% by mass.
  • the solution temperature was 35 ° C.
  • the concentration of each component in the entire etching solution and the result of each evaluation item are shown in Table 1.
  • Example 3 As an acidic organic acid, 0.3% by mass of methanesulfonic acid, 5.0% by mass of succinic acid, As an amine compound, 0.75% by mass of triisopropanolamine, As a hydrogen peroxide stabilizer 0.90% by mass of 2-butoxyethanol, As azoles, 0.04 mass% of 5-amino-1H-tetrazole As a fluoride ion source, 0.4 mass% of ammonium fluoride The etching liquid raw material which consists of these is mixed with 76.04 mass% of water, and the etching concentrate was prepared.
  • the etching concentrate is mixed with 16.57% by weight of 35% hydrogen peroxide water (5.8% by weight of hydrogen peroxide and 10.77% by weight of water based on the total amount of etching solution), and the hydrogen peroxide concentration is A 5.8% by mass etchant was prepared.
  • the total amount of water is 86.81% by mass.
  • the solution temperature was 35 ° C.
  • the concentration of each component in the entire etching solution and the result of each evaluation item are shown in Table 1.
  • Example 4 As an acidic organic acid, 0.5% by mass of methanesulfonic acid, 10.0% by mass of glutaric acid, As an amine compound, 0.75% by mass of triisopropanolamine, As a hydrogen peroxide stabilizer 0.90% by mass of 2-butoxyethanol, As azoles, 0.04 mass% of 5-amino-1H-tetrazole As a fluoride ion source, 0.4 mass% of ammonium fluoride The etching liquid raw material which consists of these is mixed with 70.84 mass% of water, and the etching concentrate was prepared.
  • the etching concentrate is mixed with 16.57% by weight of 35% hydrogen peroxide water (5.8% by weight of hydrogen peroxide and 10.77% by weight of water based on the total amount of etching solution), and the hydrogen peroxide concentration is A 5.8% by mass etchant was prepared.
  • the total amount of water is 81.61% by mass.
  • the solution temperature was 35 ° C.
  • the concentration of each component in the entire etching solution and the result of each evaluation item are shown in Table 1.
  • Example 5 As an acidic organic acid, 0.3% by mass of methanesulfonic acid, 5.0% by mass of malonic acid, As an amine compound, 1.5% by mass of triisopropanolamine, As a hydrogen peroxide stabilizer 0.90% by mass of 2-butoxyethanol, As azoles, 0.04 mass% of 5-amino-1H-tetrazole As a fluoride ion source, 0.4 mass% of ammonium fluoride The etching liquid raw material which consists of these is mixed with 75.29 mass% of water, and the etching concentrate was prepared.
  • the etching concentrate is mixed with 16.57% by weight of 35% hydrogen peroxide water (5.8% by weight of hydrogen peroxide and 10.77% by weight of water based on the total amount of etching solution), and the hydrogen peroxide concentration is A 5.8% by mass etchant was prepared.
  • the total amount of water is 86.06% by mass.
  • the solution temperature was 35 ° C.
  • the concentration of each component in the entire etching solution and the result of each evaluation item are shown in Table 1.
  • Example 6 As an acidic organic acid, 4.5% by mass of lactic acid, As an amine compound, 0.75% by mass of triisopropanolamine, As a hydrogen peroxide stabilizer 0.90% by mass of 2-butoxyethanol, As azoles, 0.04 mass% of 5-amino-1H-tetrazole As a fluoride ion source, 0.4 mass% of ammonium fluoride
  • the etching liquid raw material which consists of these is mixed with 76.84 mass% of water, and the etching concentrate was prepared.
  • the etching concentrate is mixed with 16.57% by weight of 35% hydrogen peroxide water (5.8% by weight of hydrogen peroxide and 10.77% by weight of water based on the total amount of etching solution), and the hydrogen peroxide concentration is A 5.8% by mass etchant was prepared.
  • the total amount of water is 87.61% by mass.
  • the solution temperature was 35 ° C.
  • the concentration of each component in the entire etching solution and the result of each evaluation item are shown in Table 1.
  • the etching concentrate is mixed with 16.57% by weight of 35% hydrogen peroxide water (5.8% by weight of hydrogen peroxide and 10.77% by weight of water based on the total amount of etching solution), and the hydrogen peroxide concentration is A 5.8% by mass etchant was prepared.
  • the total amount of water is 67.14% by mass.
  • the solution temperature was 35 ° C.
  • the concentration of each component in the entire etching solution and the result of each evaluation item are shown in Table 2.
  • the etching concentrate is mixed with 16.57% by weight of 35% hydrogen peroxide water (5.8% by weight of hydrogen peroxide and 10.77% by weight of water based on the total amount of etching solution), and the hydrogen peroxide concentration is A 5.8% by mass etchant was prepared.
  • the total amount of water is 77.34% by mass.
  • the solution temperature was 35 ° C.
  • the concentration of each component in the entire etching solution and the result of each evaluation item are shown in Table 2.
  • the etching concentrate is mixed with 16.57% by weight of 35% hydrogen peroxide water (5.8% by weight of hydrogen peroxide and 10.77% by weight of water based on the total amount of etching solution), and the hydrogen peroxide concentration is A 5.8% by mass etchant was prepared.
  • the total amount of water is 77.59% by mass.
  • the solution temperature was 35 ° C.
  • the concentration of each component in the entire etching solution and the result of each evaluation item are shown in Table 2.
  • the etching concentrate is mixed with 16.57% by weight of 35% hydrogen peroxide water (5.8% by weight of hydrogen peroxide and 10.77% by weight of water based on the total amount of etching solution), and the hydrogen peroxide concentration is A 5.8% by mass etchant was prepared.
  • the total amount of water is 91.61% by mass.
  • the solution temperature was 35 ° C.
  • the concentration of each component in the entire etching solution and the result of each evaluation item are shown in Table 2.
  • the etching concentrate is mixed with 16.57% by weight of 35% hydrogen peroxide water (5.8% by weight of hydrogen peroxide and 10.77% by weight of water based on the total amount of etching solution), and the hydrogen peroxide concentration is A 5.8% by mass etchant was prepared.
  • the total amount of water is 82.81% by mass.
  • the solution temperature was 35 ° C.
  • the concentration of each component in the entire etching solution and the result of each evaluation item are shown in Table 2.
  • Example 6 is only lactic acid as the organic acid.
  • the organic acid was able to suitably etch the copper / titanium multilayer film with only lactic acid.
  • Table 2 lists comparative examples.
  • the amount of ammonium fluoride is 0.26% by mass, which is less than the examples shown in Table 1.
  • Comparative Examples 1 and 2 the state of just etching could not be achieved within the specified time, and an etching residue occurred. Therefore, the index of side etching such as taper angle could not be measured.
  • time out was described.
  • Comparative Example 3 is a composition containing methanesulfonic acid and lactic acid as the organic acid.
  • the index for the side etching is the value, but the tapered portion was not tapered, and the etching surface was very irregular in shape. In the remarks of Table 2, it described as "(theta) defect.”
  • the comparative example 4 is a thing of only methanesulfonic acid as an organic acid.
  • methanesulfonic acid and glycolic acid are used in combination as the organic acid. In either case, the state of just etching did not occur within the specified time, and there was unmelted material. In the remarks of Table 2, "time out" was described.
  • methanesulfonic acid is in the range of 0.2 mass% to 1.5 mass% with respect to the total amount, and when lactic acid is used in combination, lactic acid is 2.0 mass% to 10.0 mass%. desirable.
  • succinic acid When succinic acid is used in combination, 4.5% by mass to 5.5% by mass of succinic acid is preferable, and when glutaric acid is used in combination, glutaric acid is preferably 9.5% by mass to 10.5% by mass, When malonic acid is used in combination, malonic acid is preferably 4.5% by mass to 5.5% by mass.
  • lactic acid can also be used alone as an organic acid.
  • the content of lactic acid at that time is preferably 4.0% by mass to 5.0% by mass.
  • the etching solution is composed of hydrogen peroxide, a fluorine ion source, an azole, a hydrogen peroxide stabilizer, an organic acid, an amine and water, and the organic acid is methanesulfonic acid.
  • those containing at least one selected from lactic acid, succinic acid, glutanoic acid and malonic acid can suitably etch a copper / titanium multilayer film, and also have a long bath life. Therefore, even if the film thickness of copper is increased, it is not necessary to adjust the composition of the etching solution frequently.
  • the etching solution according to the present invention can be suitably used when etching a multilayer film of titanium and copper.
  • the characteristics of the side etching can be maintained, so that the predetermined etching rate range can be maintained for a long time even if the copper film thickness becomes large.

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Abstract

L'invention concerne une solution de gravure qui est destinée à la gravure d'un film multicouches composé d'une couche de cuivre ayant une grande épaisseur de film et d'une couche de base en titane et qui peut être utilisée même lorsque la concentration d'ions métalliques est supérieure ou égale à 8 000 ppm. La solution de gravure comprend (a) du peroxyde d'hydrogène, (b) une source d'apport d'ions fluor, (c) des azoles, (d) un stabilisant de peroxyde d'hydrogène, (e) un acide organique, (f) des amines et (g) de l'eau, un acide méthanesulfonique et un acide organique parmi l'acide lactique, l'acide succinique, l'acide glutarique et l'acide malonique étant utilisés en tant qu'acide organique ou l'acide lactique étant utilisé seul en tant qu'acide organique.
PCT/JP2017/035529 2017-09-29 2017-09-29 Solution de gravure et concentré de gravure pour film multicouches et procédé de gravure WO2019064506A1 (fr)

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JP2019544111A JP6793312B2 (ja) 2017-09-29 2017-09-29 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
CN201780094862.7A CN111094627B (zh) 2017-09-29 2017-09-29 多层膜用蚀刻液和蚀刻浓缩液以及蚀刻方法

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CN110904456A (zh) * 2019-12-28 2020-03-24 苏州天承化工有限公司 一种铜蚀刻液及其制备方法和应用
CN111286738A (zh) * 2020-01-17 2020-06-16 江阴江化微电子材料股份有限公司 一种酸性铜蚀刻液的生产工艺
CN114751385A (zh) * 2022-04-21 2022-07-15 盛隆资源再生（无锡）有限公司 一种硫酸微蚀刻废液的再生方法

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CN112663064A (zh) * 2020-12-16 2021-04-16 江苏艾森半导体材料股份有限公司 一种铜钼金属蚀刻液及其制备方法和应用
CN112981404B (zh) * 2021-02-05 2022-10-28 四川和晟达电子科技有限公司 一种钛合金蚀刻液组合物及其使用方法

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CN111286738A (zh) * 2020-01-17 2020-06-16 江阴江化微电子材料股份有限公司 一种酸性铜蚀刻液的生产工艺
CN114751385A (zh) * 2022-04-21 2022-07-15 盛隆资源再生（无锡）有限公司 一种硫酸微蚀刻废液的再生方法
CN114751385B (zh) * 2022-04-21 2024-02-06 盛隆资源再生（无锡）有限公司 一种硫酸微蚀刻废液的再生方法

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