WO2012064001A1 - Composition for etching metal films - Google Patents

Composition for etching metal films Download PDF

Info

Publication number
WO2012064001A1
WO2012064001A1 PCT/KR2011/003427 KR2011003427W WO2012064001A1 WO 2012064001 A1 WO2012064001 A1 WO 2012064001A1 KR 2011003427 W KR2011003427 W KR 2011003427W WO 2012064001 A1 WO2012064001 A1 WO 2012064001A1
Authority
WO
WIPO (PCT)
Prior art keywords
acid
etching
composition
ammonium
metal film
Prior art date
Application number
PCT/KR2011/003427
Other languages
French (fr)
Korean (ko)
Inventor
장욱
박종희
김지찬
한지현
양세인
Original Assignee
오씨아이 주식회사
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 오씨아이 주식회사 filed Critical 오씨아이 주식회사
Priority to JP2013531466A priority Critical patent/JP5827336B2/en
Priority to CN201180047122.0A priority patent/CN103282549B/en
Publication of WO2012064001A1 publication Critical patent/WO2012064001A1/en

Links

Images

Classifications

    • 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
    • H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
    • H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
    • H01L21/321—After treatment
    • H01L21/3213—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer
    • H01L21/32133—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only
    • H01L21/32134—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only by liquid etching only
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L29/00—Semiconductor devices adapted for rectifying, amplifying, oscillating or switching, or capacitors or resistors with at least one potential-jump barrier or surface barrier, e.g. PN junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof  ; Multistep manufacturing processes therefor
    • H01L29/66—Types of semiconductor device ; Multistep manufacturing processes therefor
    • H01L29/66007—Multistep manufacturing processes
    • H01L29/66075—Multistep manufacturing processes of devices having semiconductor bodies comprising group 14 or group 13/15 materials
    • H01L29/66227—Multistep manufacturing processes of devices having semiconductor bodies comprising group 14 or group 13/15 materials the devices being controllable only by the electric current supplied or the electric potential applied, to an electrode which does not carry the current to be rectified, amplified or switched, e.g. three-terminal devices
    • H01L29/66409—Unipolar field-effect transistors
    • H01L29/66477—Unipolar field-effect transistors with an insulated gate, i.e. MISFET
    • H01L29/66742—Thin film unipolar transistors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L29/00—Semiconductor devices adapted for rectifying, amplifying, oscillating or switching, or capacitors or resistors with at least one potential-jump barrier or surface barrier, e.g. PN junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof  ; Multistep manufacturing processes therefor
    • H01L29/40—Electrodes ; Multistep manufacturing processes therefor
    • H01L29/43—Electrodes ; Multistep manufacturing processes therefor characterised by the materials of which they are formed
    • H01L29/45—Ohmic electrodes
    • H01L29/456—Ohmic electrodes on silicon
    • H01L29/458—Ohmic electrodes on silicon for thin film silicon, e.g. source or drain electrode
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L29/00—Semiconductor devices adapted for rectifying, amplifying, oscillating or switching, or capacitors or resistors with at least one potential-jump barrier or surface barrier, e.g. PN junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof  ; Multistep manufacturing processes therefor
    • H01L29/40—Electrodes ; Multistep manufacturing processes therefor
    • H01L29/43—Electrodes ; Multistep manufacturing processes therefor characterised by the materials of which they are formed
    • H01L29/49—Metal-insulator-semiconductor electrodes, e.g. gates of MOSFET
    • H01L29/4908—Metal-insulator-semiconductor electrodes, e.g. gates of MOSFET for thin film semiconductor, e.g. gate of TFT

Definitions

  • the present invention relates to a method for collectively wet-etching a single film or a multi-film including at least one selected from a metal film used as a gate electrode and a data electrode in a thin film transistor for flat panel display, in particular, copper, molybdenum, titanium and molybdenum- To an etching composition.
  • Thin film transistors are fabricated by forming various metal wirings on a substrate.
  • a thin film having patterns formed through metal thin film formation using a physical adsorption method, a pattern formation through an exposure process of a photoresist, and an etching process is completed.
  • a metal thin film having a low resistance has been required for fast driving.
  • a metal material such as copper or silver is used as a metal wiring material for the thin film transistor process.
  • the metal being used is copper.
  • a multi-layer structure is generally applied in which molybdenum, titanium, or a molybdenum-titanium alloy is first deposited and then copper is deposited due to deposition problems on the substrate.
  • Korean Patent Publication No. 10-2006-0134380 and Korean Patent No. 10-0839428 disclose that hydrofluoric acid is added to the etchant in order to remove the molybdenum film residue, but the bottom glass substrate is etched by hydrofluoric acid to greatly change the thickness uniformity of the thin film transistor .
  • Korean Patent Laid-Open No. 10-2007-0097922 has achieved the etching rate of the glass substrate lower than that of hydrofluoric acid by using a flame retardant.
  • Korean Patent Laid-Open Publication No. 10-2004-0051502 discloses an organic acid such as glycolic acid as an etching control agent, but has a disadvantage in that the etching angle of the etched thin film is high and the reaction inhibiting effect of copper ions and hydrogen peroxide is inferior.
  • Korean Patent Laid-Open Publication No. 10-2006-0099089 discloses an etching solution comprising sulfate as an etching control agent, phosphate as an undercut inhibitor, and acetic acid chelating agent as a chelating agent, but the reaction inhibition effect between copper ion and hydrogen peroxide is excellent There is a problem that productivity is deteriorated due to generation of precipitates in the exhaust port and rinse portion when applied to etching equipment.
  • the present inventors have found that a metal film used as a metal electrode of a thin film transistor for flat panel display, particularly a single film or a multilayer film containing at least one selected from copper, molybdenum, titanium and molybdenum-titanium alloys is excellent in etching profile,
  • the present inventors have made efforts to develop a batch etchant composition which has high stability between copper ions and hydrogen peroxide and has few residues of molybdenum, titanium, and molybdenum-titanium alloys, and which improves precipitation and foreign matter generation in etching equipment.
  • composition of the present invention is a composition containing copper, molybdenum, titanium And a molybdenum-titanium alloy. The present invention has been completed based on this finding.
  • the present invention is a.
  • a balance of water such that the total weight of the total composition is 100% by weight
  • the present invention also provides a composition for etching a metal film.
  • the composition for etching a metal film of the present invention may be applied to various types of single-layer or multi-layered films including at least one selected from copper, molybdenum, titanium and molybdenum-titanium alloys used as gate and data electrodes constituting thin- It is possible to ensure an excellent etching profile, characteristics and uniformity. Further, when a volatilization inhibitor is further included, foreign matter and precipitates in the equipment are not generated well, and the productivity can be improved. In addition, the copper ion concentration is higher than that of conventional copper etchant, so that the stability of the etchant increases, the number of metal film substrates processed increases, the cost can be reduced, and a low inclination angle with respect to the etchant is obtained, It is expected.
  • the protrusion of the lower film to be etched on the multilayer film made of copper on the upper part and molybdenum, titanium or molybdenum-titanium alloy on the lower side can be controlled to secure a good etch profile, and even if there is a change in the film thickness in the thin film deposition process, An etching profile can be expressed.
  • FIG. 1 is a photograph of a precipitate generated in an etching apparatus exhaust hole by a conventional composition for copper, molybdenum, and titanium batch etching.
  • FIG. 2 is a photograph showing the difference in improvement of precipitates when the composition for etching a metal film containing the volatilization inhibitor of the present invention and the conventional etching composition are applied to an etching process.
  • FIG. 3 is an electron micrograph showing the etching profile of a thin film obtained by etching a copper / molybdenum-titanium alloy multilayer film (copper film 2000 ⁇ , alloy film 300 ⁇ ) with the metal film etching composition of the present invention (Example 12).
  • the present invention relates to a metal film etching composition
  • a metal film etching composition comprising an oxidizing agent, an etching control agent, a chelating agent, an undercut inhibitor, a copper etching inhibitor, a residue remover and a residual amount of water.
  • the oxidizing agent serves to oxidize the copper thin film surface, and hydrogen peroxide is preferably used.
  • the content of the composition of the present invention is preferably 7 to 30% by weight. If the content is less than 7% by weight, the etching rate of copper may be lowered and the process efficiency may deteriorate. When the content exceeds 30% by weight, There may be a problem that the maximum throughput of the etchant is limited.
  • the etch control agent serves to ionize the oxidized copper to form ions on the surface of the thin film, and it is preferable to use an organic acid.
  • the organic acid include at least one acid containing at least one carboxyl group such as acetic acid, citric acid, oxalic acid, maleic acid, glycolic acid, succinic acid, tartaric acid, fumaric acid, salicylic acid, malic acid, and pivalic acid .
  • the content of the etching control agent in the composition of the present invention is preferably 0.1 to 5% by weight.
  • the content of the etching control agent is less than 0.1% by weight, there may be a problem of lowering the etching rate, and if it exceeds 5% by weight, the critical dimension loss (CD) and the etching profile of the tilt angle may become poor.
  • CD critical dimension loss
  • the chelating agent chelates the copper ions dissolved in the etching solution to prevent the reaction between the copper ions and the oxidizing agent and to enhance the stability of the oxidizing agent and the etching solution.
  • the maximum amount of etching solution can be increased and the rapid decomposition of hydrogen peroxide can be prevented to improve safety.
  • Representative examples include acetate chelating agents, phosphonic acid chelating agents and amino acids, and they may be used in combination.
  • examples of the acetic acid chelating agent include nitrilotriacetic acid (NTA), iminodiacetic acid (IDA), methyl iminodiacetic acid (MIDA), hydroxy Hydroxyethyl iminodiacetic acid (HIDA), diethylenetriamine pentaacetic acid (DPTA), ethylenediamine tetraacetic acid (EDTA), N-hydroxyethylethylene (N-hydroxyethyl ethylenediamine tetraacetic acid (HEDTA), methyl ethylenediamine tetraacetic acid (MEDTA), triethylene tetraamine hexaacetic acid (TTHA), and the like.
  • NTA nitrilotriacetic acid
  • IDA iminodiacetic acid
  • MIDA methyl iminodiacetic acid
  • HIDA diethylenetriamine pentaacetic acid
  • EDTA ethylenediamine tetraacetic acid
  • HEDTA N-hydroxyethylethylene
  • HEDTA
  • Examples of phosphonic acid chelating agents include ethylenediamine tetramethylenephosphonic acid But are not limited to, ethylene diamine tetramethylene phosphonic acid (EDTPA), diethylene triamine pentamethylene phosphonic acid (DTPMPA), hydroxy ethylidene diphosphonic acid (HEDP) And examples of amino acids include glycine, arginine, glutamic acid, alanine, cysteine, glutamine, glyphosphate, and glacial acetic acid, and the like. . If the content of the chelating agent is less than 0.1% by weight, an abrupt reaction may occur between the oxidizing agent and the copper ion and the stability may be deteriorated. When the content of the chelating agent is less than 0.1% by weight, Exceeding% by weight may cause problems with the CD loss and the etching profile of the inclination angle.
  • EDTPA ethylene diamine tetramethylene phosphonic acid
  • DTPMPA diethylene triamine
  • the undercut inhibitor prevents the occurrence of local cell development by adjusting the redox potential of the metal and plays a role in obtaining a uniform etch rate between the metal films in a multilayer structure of copper, molybdenum, titanium, and the like.
  • inorganic phosphate and organic acid-based ammonium salt are used as an undercut inhibitor.
  • inorganic phosphate is mainly used, but there is a problem that foreign substances are generated in the etching equipment by bonding with other organic additives.
  • the use of the organic acid-based ammonium salt together with the inorganic phosphate can significantly reduce the generation of foreign matter.
  • the inorganic phosphate which can be used in the present invention may be at least one selected from ammonium phosphate, ammonium hydrogen phosphate, ammonium dihydrogen phosphate, sodium phosphate, sodium hydrogen phosphate and sodium dihydrogen phosphate, ammonium acetate in the case of an organic acid ammonium salt, Ammonium acetate, ammonium acetate, and ammonium citrate.
  • the weight ratio of the inorganic phosphate to the organic acid-based ammonium salt is preferably 1: 0.25 to 2. If the weight ratio of the organic acid-based ammonium salt is too small, foreign matter may be generated in the etching equipment.
  • the CD loss may be reduced and the etching profile may become poor.
  • the content of the undercut inhibitor is too small, an undercut phenomenon may occur in the lower molybdenum, titanium and molybdenum-titanium films, and if the content of the undercut inhibitor exceeds 3 wt% It is difficult to obtain a desired etching profile.
  • the copper etching inhibitor is used to obtain an excellent etching profile by adjusting the etching rate of copper having a higher etching rate than that of molybdenum and titanium.
  • Typical examples thereof include heterocyclic amines. Specific examples thereof include aminotetrazole, imidazole, indole, purine, pyrazole, pyridine, pyrimidine, pyrrole, pyrrolidine, pyrroline, benzotriazole or a mixture thereof.
  • the content of the copper etching inhibitor in the composition of the present invention is preferably from 0.01 to 5% by weight. If the content is too low, the copper etching rate becomes faster and the etching profile may become poor when the multilayer film is applied. The productivity may drop.
  • the residue removing agent functions to prevent residues of molybdenum, titanium and molybdenum-titanium alloy, and inorganic flame retarding agent is used in the present invention. Specifically, at least one selected from ammonium fluoride, ammonium hydrogen fluoride, sodium fluoride, potassium fluoride, ammonium fluoride, sodium fluoride, and potassium fluoride may be used.
  • the content of the residue remover in the composition for etching a metal film is preferably 0.01 to 5% by weight. If the content is less than 0.01% by weight, there may be a problem of residue of molybdenum and the like. If the content is more than 5% And a problem that the glass substrate is etched may occur.
  • the composition for etching a metal film of the present invention may further comprise a volatilization inhibitor if necessary.
  • the volatilization inhibitor suppresses the volatilization of the etching solution and maintains the solubility of the precipitate due to the etching.
  • the addition of the volatilization inhibitor can dramatically improve the generation of deposits near the exhaust port of the etching apparatus generated in the conventional etching solution.
  • Usable volatile inhibitors include polyhydric alcohols having two or more hydroxy groups, such as ethylene glycol, propylene glycol, polyethylene glycol, or mixtures thereof.
  • the addition amount is preferably from 0.1 to 7% by weight. If the addition amount is less than 0.1% by weight, the effect of suppressing the volatilization of the etching solution is insufficient. It is good to do.
  • composition for etching a metal film of the present invention can be obtained by constituting the composition in such a manner that the total weight of the composition is 100 wt% together with the remaining amount of water.
  • composition for etching a metal film of the present invention can obtain an excellent etching profile when applied to an etching process of a single film or a multilayer film containing at least one selected from copper, molybdenum, titanium and molyidden-titanium alloy, Can be suppressed and the productivity can be improved. In addition, it is possible to secure a low inclination angle in comparison with the conventional etching solution.
  • etching composition comprising an oxidizing agent, an etching control agent, a chelating agent, an undercut inhibitor, a copper etching inhibitor, a residue remover and a residual amount of water was prepared. Specific constituent materials and composition ratios are shown in Table 1 below.
  • a double-layered substrate of copper / molybdenum-titanium alloy was prepared. Molybdenum and titanium alloys were formed at a weight ratio of 1: 1. Copper and molybdenum-titanium alloys were deposited on a substrate by sputtering in the same manner as LCD glass substrates. Copper films and molybdenum-titanium alloy films were deposited in two thicknesses: copper 2000 ⁇ / molybdenum-titanium 300 ⁇ , copper 2500 ⁇ / molybdenum-titanium 100 ⁇ , respectively.
  • compositions of Examples 1 to 18 and Comparative Examples 1 and 2 were placed in an experimental equipment of a spray-type wet etching system (manufactured by KCTECH, model name: ETCHER (TFT)) and heated. When the temperature was maintained at 33 ⁇ 0.5 ° C, The etching process of the film substrate was performed. The over-etch (O / E) ratio was etched by 60% film thickness based on EPD (End Point Detection) of pad part. After the etching was completed, the substrate was cleaned with ultrapure water, dried using a drying device, and then photoresist was removed using a photoresist stripper.
  • TFT spray-type wet etching system
  • the photoresist was removed using a scanning electron microscope (SEM, manufactured by Phillips, model NOVA-200)
  • SEM scanning electron microscope
  • CD critical dimension
  • Table 2 shows the etching performance of the conventional batch etching composition of the present invention and the composition for etching including the oxidizing agent, the etching control agent, the chelating agent, the undercut preventing agent, the copper etching inhibiting agent, the residue removing agent and the residual water proposed in the present invention And a copper / molybdenum-titanium alloy film having a thickness of 2000 ⁇ / 300 ⁇ , respectively.
  • the maximum soluble copper ion concentration is about 4,000 ppm.
  • Table 3 shows the etching performance of the composition for etching a metal film of the present invention, which further includes a volatilization inhibitor, on the basis of a bilayer substrate having a thickness of 2000 ⁇ / 300 ⁇ of a copper film / molybdenum-titanium alloy film, No foreign bodies and precipitation of the etching equipment were found, and the maximum soluble copper ion concentration exceeded 6,000 ppm.
  • the inclination angle was 5 ° or lower, which is advantageous for subsequent thin film deposition and pattern fabrication.
  • Table 4 shows the etching profile according to the thickness of the lower alloy film in the copper / molybdenum-titanium alloy double film.
  • the performance of the etching regulator is lowered due to the difference in the electron mobility between the multilayer films.
  • the etching composition of the present invention there is no residue or protrusion of the lower alloy film A good etching profile can be obtained. Therefore, it is expected that it will be a great advantage in the process operation by showing a robust etching profile even when the film thickness is changed in the thin film deposition process.

Abstract

The present invention relates to a composition for etching metal films, and more specifically, to an etchant composition comprising an oxidant, an etching controller, a chelating agent, an undercut inhibitor, a copper corrosion inhibitor, a residue remover and the balance of water, for collectively wet etching metal films used as a gate electrode and a data electrode within a thin film transistor for a flat display, particularly, a single-layered film or a multilayered film consisting of one or more materials selected from copper, molybdenum, titanium and a molybdenum-titanium alloy. The composition of the present invention inhibits the rapid reaction of an oxidant and a copper ion when applied to an etching process through the use of a novel chelating agent, thereby providing an etchant with excellent lifetime and stability, an etched metal film with a gentle slope angle, suitable control of CD loss, and a good etching profile inhibiting the residue of a lower molybdenum, titanium or molybdenum-titanium alloy film. In addition, if a volatilization inhibitor is further added, precipitate and foreign matter generation is greatly reduced in etching equipment, and thus it is possible to improve productivity with respect to etching equipment operation and to reduce failure rates.

Description

금속막 식각용 조성물Composition for etching metal film
본 발명은 평판디스플레이용 박막트랜지스터내 게이트 전극 및 데이터 전극으로 사용되는 금속막, 특히 구리, 몰리브덴, 티타늄 및 몰리브텐-티타늄 합금 중에서 선택한 1 종 이상을 포함한, 단일막 또는 다중막을 일괄 습식 식각하는 식각용 조성물에 관한 것이다.The present invention relates to a method for collectively wet-etching a single film or a multi-film including at least one selected from a metal film used as a gate electrode and a data electrode in a thin film transistor for flat panel display, in particular, copper, molybdenum, titanium and molybdenum- To an etching composition.

박막트랜지스터는 기판 위에 여러가지 금속 배선을 형성하여 만들어지는데 통상적으로 물리 흡착법을 이용한 금속 박막 형성과 포토레지스트의 노광 공정을 통한 패턴 형성, 식각 공정을 통하여 패턴이 형성된 박막이 완성되며 그 중에서 식각 공정은 노광 공정을 통해 형성된 패턴에 따라 선택적으로 금속 박막을 남기는 공정이다.Thin film transistors are fabricated by forming various metal wirings on a substrate. Typically, a thin film having patterns formed through metal thin film formation using a physical adsorption method, a pattern formation through an exposure process of a photoresist, and an etching process is completed. Among them, Is a process of selectively leaving a metal thin film according to a pattern formed through the process.
박막트랜지스터 액정표시장치의 사양이 높아짐에 따라 빠른 구동을 위해 저항이 낮은 금속 박막이 필요하게 되었고, 이를 위해 박막트랜지스터 공정의 금속 배선 재료로 구리, 은과 같은 금속 재료를 사용하고 있으나 현재 상업화되어 널리 사용되고 있는 금속은 구리이다. 순수 구리의 경우 기판 위의 증착 문제로 인해 일반적으로 몰리브덴, 티타늄, 또는 몰리브덴-티타늄 합금을 먼저 증착한 후 구리를 증착하는 다층막 구조가 적용되고 있다. 이러한 다층막 구조에서 과산화수소를 주성분으로 하는 구리 식각액을 사용하여 습식 식각을 하는 경우 구리와 몰리브덴, 티타늄 금속 박막간 식각 속도 차이로 인해 불량한 식각 프로파일을 얻는 경우가 많다. 예를 들어 하부 몰리브덴, 티타늄 막의 잔사는 후속 모듈 공정시 배선 합선으로 인한 구동 불량등의 원인이 되어 수율 저하의 원인이 된다.As the specifications of the thin film transistor liquid crystal display device have been increased, a metal thin film having a low resistance has been required for fast driving. To this end, a metal material such as copper or silver is used as a metal wiring material for the thin film transistor process. However, The metal being used is copper. In the case of pure copper, a multi-layer structure is generally applied in which molybdenum, titanium, or a molybdenum-titanium alloy is first deposited and then copper is deposited due to deposition problems on the substrate. In such a multi-layered structure, when a wet etching is performed using a copper etching solution containing hydrogen peroxide as a main component, a poor etch profile is often obtained due to the difference in etch rate between copper, molybdenum and titanium metal thin film. For example, the residues of the lower molybdenum and titanium film may cause defective driving due to the wiring short-circuit during the subsequent module process, which may cause a decrease in the yield.
대한민국 공개특허 제 10-2006-0134380 호, 대한민국 등록특허 제 10-0839428 호 등에서는 몰리브덴 막잔사를 없애기 위해 식각액에 불산을 첨가하였으나 불산은 하부 글라스 기판을 식각시켜 박막트랜지스터의 두께 균일성을 크게 변화시키는 문제점이 있다. 이를 해결하기 위해 대한민국 공개특허 제 10-2007-0097922 호에서는 불화염을 사용하여 불산에 비해 저하된 글라스 기판의 식각률을 달성하였다.Korean Patent Publication No. 10-2006-0134380 and Korean Patent No. 10-0839428 disclose that hydrofluoric acid is added to the etchant in order to remove the molybdenum film residue, but the bottom glass substrate is etched by hydrofluoric acid to greatly change the thickness uniformity of the thin film transistor . In order to solve this problem, Korean Patent Laid-Open No. 10-2007-0097922 has achieved the etching rate of the glass substrate lower than that of hydrofluoric acid by using a flame retardant.
구리, 몰리브덴, 티타늄 및 몰리드덴-티타늄 합금 중에서 선택한 1 종 이상을 포함한 단일막 또는 다층막을 습식 식각하는 기술과 관련하여 금속 다층막간 식각 속도 차이를 균일하게 유지시켜야 하는 문제, 기판 및 패턴별 식각 균일성 문제, 식각된 박막의 경사각 문제, 구리 이온과 과산화수소간의 급격한 반응성 문제 등를 개선하기 위해서 물에 과산화수소와 함께 다양한 첨가제를 추가하는 방법이 시도되고 있다.In order to wet-etch single or multi-layer films containing at least one selected from copper, molybdenum, titanium and molyodden-titanium alloys, it is necessary to uniformly maintain the etching rate difference between metal multilayers, In order to improve the uniformity problem, the problem of the inclination angle of the etched thin film, and the sudden reactivity problem between copper ions and hydrogen peroxide, various methods of adding various additives together with hydrogen peroxide to water have been attempted.
대한민국 공개특허 제 10-2004-0051502 호에서는 식각 조정제로 글리콜산 등의 유기산을 사용하였으나, 식각된 박막의 경사각이 높고, 구리이온과 과산화수소의 반응 억제 효과가 떨어지는 단점이 있다. 대한민국 공개특허 제 10-2006-0099089 호에서는 식각 조정제로 황산염, 언더컷(undercut) 억제제로 인산염, 킬레이트제로 아세트산계 킬레이트제를 첨가한 식각액을 제시하고 있으나, 구리이온과 과산화수소간의 반응 억제 효과는 뛰어나나 식각 장비에 적용시 배기구와 린스부에서 석출물이 발생되어 생산성이 떨어지는 문제점이 있다.Korean Patent Laid-Open Publication No. 10-2004-0051502 discloses an organic acid such as glycolic acid as an etching control agent, but has a disadvantage in that the etching angle of the etched thin film is high and the reaction inhibiting effect of copper ions and hydrogen peroxide is inferior. Korean Patent Laid-Open Publication No. 10-2006-0099089 discloses an etching solution comprising sulfate as an etching control agent, phosphate as an undercut inhibitor, and acetic acid chelating agent as a chelating agent, but the reaction inhibition effect between copper ion and hydrogen peroxide is excellent There is a problem that productivity is deteriorated due to generation of precipitates in the exhaust port and rinse portion when applied to etching equipment.
대부분의 구리, 몰리브덴, 티타늄 및 몰리브덴-티타늄 합금용 일괄 식각액들은 몰리브덴, 티타늄 및 몰리브덴-티타늄 합금막의 잔사 개선과 구리의 식각 속도를 조정하여 좋은 식각 프로파일을 얻고 구리 이온과 과산화수소간 안정성을 개선하기 위해 노력하여 왔다. 이러한 노력의 결과로 잔사 및 안정성 문제에서는 많은 개선이 이루어져 왔으나 실제 식각 장비에 적용시 장비내 석출물이 발생되는 문제점이 발생되고 있으며 더 높은 안정성을 확보하여 생산성을 높여야 하는 과제가 있기 때문에 이에 부합되는 식각액 개발이 요구된다.Batch etchings for most copper, molybdenum, titanium and molybdenum-titanium alloys improve the residue of molybdenum, titanium and molybdenum-titanium alloy films and adjust the etch rate of copper to obtain good etch profiles and improve stability between copper and hydrogen peroxide I have tried. As a result of these efforts, many improvements have been made in terms of residue and stability problems. However, when applied to actual etching equipment, problems arise in the deposition of the equipment, and since there is a problem of securing higher stability and increasing productivity, Development is required.

본 발명자들은 평판디스플레이용 박막트랜지스터의 금속 전극으로 사용되는 금속막, 특히 구리, 몰리브덴, 티타늄 및 몰리브덴-티타늄 합금 중에서 선택한 1종 이상을 포함한 단일막 또는 다층막을 우수한 식각 프로파일과 특성, 균일성이 보장되고, 구리 이온과 과산화수소간 안정성이 높으며, 몰리브덴, 티타늄, 몰리브덴-티타늄 합금의 잔사가 적고, 식각 장비내 석출 및 이물 발생 문제를 개선한 일괄 식각액 조성물을 개발하고자 노력하였다. 상기의 목적을 이루기 위해 산화제, 식각 조정제, 킬레이트제, 언더컷(undercut) 방지제, 구리식각 억제제, 잔사 제거제 및 물을 포함하는 조성물을 개발하였으며, 본 발명의 조성물은 별도의 처리 없이 구리, 몰리브덴, 티타늄 및 몰리브덴-티타늄 합금 중에서 선택한 1종 이상을 포함한 단일막 또는 다층막의 식각에 통합하여 사용할 수 있음을 알게 되어 본 발명을 완성하였다.The present inventors have found that a metal film used as a metal electrode of a thin film transistor for flat panel display, particularly a single film or a multilayer film containing at least one selected from copper, molybdenum, titanium and molybdenum-titanium alloys is excellent in etching profile, The present inventors have made efforts to develop a batch etchant composition which has high stability between copper ions and hydrogen peroxide and has few residues of molybdenum, titanium, and molybdenum-titanium alloys, and which improves precipitation and foreign matter generation in etching equipment. In order to achieve the above object, a composition comprising an oxidizing agent, an etching control agent, a chelating agent, an undercut inhibitor, a copper etching inhibitor, a residue remover and water has been developed. The composition of the present invention is a composition containing copper, molybdenum, titanium And a molybdenum-titanium alloy. The present invention has been completed based on this finding.

본 발명은The present invention
산화제 7 ~ 30 중량%;7 to 30% by weight of an oxidizing agent;
식각 조정제 0.1 ~ 5 중량%;0.1 to 5% by weight of an etching regulator;
킬레이트제 0.1 ~ 5 중량%;0.1 to 5 wt% chelating agent;
언더컷 방지제 0.01 ~ 3 중량%;0.01 to 3% by weight of an undercut inhibitor;
구리식각 억제제 0.01 ~ 5 중량%;0.01 to 5% by weight of a copper etching inhibitor;
잔사 제거제 0.01 ~ 5 중량%; 및0.01 to 5% by weight of a residue remover; And
전체 조성물 총 중량이 100 중량%가 되도록 하는 잔량의 물;A balance of water such that the total weight of the total composition is 100% by weight;
을 포함하는 금속막 식각용 조성물을 그 특징으로 한다.The present invention also provides a composition for etching a metal film.

본 발명의 금속막 식각용 조성물은 평판디스플레이의 박막트랜지스터를 구성하는 게이트 및 데이터 전극으로 사용되는 구리, 몰리브덴, 티타늄 및 몰리브덴-티타늄 합금 중에서 선택한 1종 이상을 포함하는 다양한 종류의 단일막 또는 다층막 기판의 식강 공정에 적용할 경우, 우수한 식각 프로파일과 특성과 균일성이 보장되고, 휘발 억제제를 추가로 포함할 경우 장비 내의 이물과 석출물이 잘 발생되지 않아 생산성을 높일 수 있다. 또한, 기존 구리 식각액 대비 용해 가능한 구리 이온 농도가 높아 식각액의 안정성이 높아지고 금속막 기판의 처리매수가 늘어 비용을 절감할 수 있으며, 기존 식각액 대비 낮은 경사각을 확보해 후속 공정에서의 불량율을 낮추는 효과가 기대된다. 더불어 상부에 구리, 하부에 몰리브덴, 티타늄 또는 몰리브덴-티타늄 합금으로 이루어진 다층막을 식각할 하부 박막의 돌출이 제어되며 이로 인해 양호한 식각 프로파일을 확보할 수 있으며, 박막 증착 공정에서 막두께의 변화가 있더라도 강건한 식각 프로파일을 발현시킬 수 있다.The composition for etching a metal film of the present invention may be applied to various types of single-layer or multi-layered films including at least one selected from copper, molybdenum, titanium and molybdenum-titanium alloys used as gate and data electrodes constituting thin- It is possible to ensure an excellent etching profile, characteristics and uniformity. Further, when a volatilization inhibitor is further included, foreign matter and precipitates in the equipment are not generated well, and the productivity can be improved. In addition, the copper ion concentration is higher than that of conventional copper etchant, so that the stability of the etchant increases, the number of metal film substrates processed increases, the cost can be reduced, and a low inclination angle with respect to the etchant is obtained, It is expected. In addition, the protrusion of the lower film to be etched on the multilayer film made of copper on the upper part and molybdenum, titanium or molybdenum-titanium alloy on the lower side can be controlled to secure a good etch profile, and even if there is a change in the film thickness in the thin film deposition process, An etching profile can be expressed.

도 1은 기존의 구리, 몰리브덴, 티타늄 일괄 식각용 조성물에 의해 식각 장비 배기구에서 발생되는 석출물의 사진이다.FIG. 1 is a photograph of a precipitate generated in an etching apparatus exhaust hole by a conventional composition for copper, molybdenum, and titanium batch etching.
도 2는 본 발명의 휘발억제제를 포함한 금속막 식각용 조성물과 기존 식각용 조성물을 식각 공정에 적용시 석출물 개선의 유의차를 보여주는 사진이다.FIG. 2 is a photograph showing the difference in improvement of precipitates when the composition for etching a metal film containing the volatilization inhibitor of the present invention and the conventional etching composition are applied to an etching process.
도 3 은 본 발명의 금속막 식각용 조성물(실시예 12)로 구리/몰리브덴-티타늄 합금 다층막(구리막 2000Å, 합금막 300Å)을 식각한 박막의 식각 프로파일을 나타내는 전자 현미경 사진이다.3 is an electron micrograph showing the etching profile of a thin film obtained by etching a copper / molybdenum-titanium alloy multilayer film (copper film 2000 Å, alloy film 300 Å) with the metal film etching composition of the present invention (Example 12).

이하에서는 본 발명을 더욱 자세하게 설명하겠다.Hereinafter, the present invention will be described in detail.
본 발명은 산화제, 식각 조정제, 킬레이트제, 언더컷(undercut) 방지제, 구리식각 억제제, 잔사 제거제 및 잔량의 물을 포함하는 금속막 식각용 조성물에 관한 것이다.The present invention relates to a metal film etching composition comprising an oxidizing agent, an etching control agent, a chelating agent, an undercut inhibitor, a copper etching inhibitor, a residue remover and a residual amount of water.
상기 산화제는 구리 박막 표면을 산화시키는 역할을 하며, 과산화수소를 사용하는 것이 바람직하다. 본 발명의 조성물 중 함량은 7 ~ 30 중량%가 바람직한데, 함량이 7 중량% 미만이면 구리의 식각속도가 저하되어 공정효율이 떨어질 수 있으며, 30 중량%를 초과하면 구리 이온과의 안정성이 떨어져 식각액의 최대 처리량이 제한되는 문제가 있을 수 있다.The oxidizing agent serves to oxidize the copper thin film surface, and hydrogen peroxide is preferably used. The content of the composition of the present invention is preferably 7 to 30% by weight. If the content is less than 7% by weight, the etching rate of copper may be lowered and the process efficiency may deteriorate. When the content exceeds 30% by weight, There may be a problem that the maximum throughput of the etchant is limited.
상기 식각 조정제는 표면이 산화된 구리를 이온화하여 박막표면에서 이온의 형태로 떨어 뜨리는 역할을 하며, 유기산을 사용하는 것이 바람직하다. 유기산의 구체적인 예로서 아세트산, 시트르산, 옥살산, 말레익산, 글리콜산, 호박산, 타르타르산, 퓨마릭산, 살리실산, 말릭산, 피바릭(Pivalic)산 등의 카르복실기가 1개 이상 들어 있는 산을 1종 이상 사용할 수 있다. 본 발명의 조성물 중 식각 조정제의 함량은 0.1 ~ 5 중량%가 바람직하다. 식각 조정제의 함량이 0.1 중량% 미만이면 식각속도 저하의 문제가 있을 수 있고, 5 중량%를 초과하면 CD(Critical Dimension) 손실, 경사각의 식각 프로파일이 불량해 질 수 있다.The etch control agent serves to ionize the oxidized copper to form ions on the surface of the thin film, and it is preferable to use an organic acid. Specific examples of the organic acid include at least one acid containing at least one carboxyl group such as acetic acid, citric acid, oxalic acid, maleic acid, glycolic acid, succinic acid, tartaric acid, fumaric acid, salicylic acid, malic acid, and pivalic acid . The content of the etching control agent in the composition of the present invention is preferably 0.1 to 5% by weight. If the content of the etching control agent is less than 0.1% by weight, there may be a problem of lowering the etching rate, and if it exceeds 5% by weight, the critical dimension loss (CD) and the etching profile of the tilt angle may become poor.
상기 킬레이트제는 식각액에 용해된 구리이온을 킬레이션하여 구리이온과 산화제 사이의 반응을 막아주며, 산화제 및 식각액의 안정성을 높여주는 역할을 한다. 식각액내 구리 이온의 킬레이션 능력에 따라 식각액의 최대 처리양을 늘릴수 있으며 과산화수소의 급격한 분해를 막아 안전성 향상에 도움을 준다. 대표적인 예로는 아세트산계 킬레이트제, 포스폰산(phosphonic acid)계 킬레이트제, 아미노산 등을 들 수 있으며, 이들의 혼합하여 사용할 수도 있다. 보다 구체적으로 아세트산계 킬레이트제의 예로는 니트릴로트리아세틱 에시드(Nitrilotriacetic acid, NTA), 이미노디아세틱 에시드(Iminodiacetic acid, IDA), 메틸 이미노디아세틱 에시드(Methyl iminodiacetic acid, MIDA), 히드록시에틸 이미노디아세틱 에시드(Hydroxyethyl iminodiacetic acid, HIDA), 디에틸렌트리아민 펜타아세틱 에시드(Diethylenetriamine pentaacetic acid, DPTA), 에틸렌디아민 테트라아세틱 에시드(Ethylenediamine tetraacetic acid, EDTA), N-히드록시에틸 에틸렌디아민 테트라아세틱 에시드(N-hydroxyethyl ethylenediamine tetraacetic acid, HEDTA), 메틸 에틸렌디아민 테트라아세틱 에시드(Methyl ethylenediamine tetraacetic acid, MEDTA), 트리에틸렌 테트라아민 헥사아세틱 에시드(Triethylene tetraamine hexaacetic acid, TTHA) 등을 들 수 있고, 포스폰산계 킬레이트제의 예로는 에틸렌 디아민 테트라메틸렌 포스포닉 에시드(Ethylene diamine tetramethylene phosphonic acid, EDTPA), 디에틸렌 트리아민 펜타메틸렌 포스포닉 에시드(Diethylene triamine pentamethylene phosphonic acid, DTPMPA), 히드록시 에틸리덴 디포스포닉 에시드(Hydroxy ethylidene diphosphonic acid, HEDP), 아미노 트리메틸렌 포스포닉 에시드(Amino trimethylene phosphonic acid, ATMP) 등을 들 수 있으며, 아미노산의 예로는 글리신, 아르기닌(Arginie), 글루타민산, 알라닌, 시스테인, 글루타민, 글리포스페이트(Glyphosphate), 글라이실릭산 등을 들 수 있다. 본 발명의 금속막 식각용 조성물 중 상기 킬레이트제의 함량은 0.1 ~ 5 중량%가 바람직한데, 킬레이트제의 함량이 0.1 중량% 미만이면 산화제와 구리 이온간 급격한 반응이 일어나 안정성이 떨어질 수 있으며, 5 중량%를 초과하면 CD 손실, 경사각의 식각 프로파일에 문제가 있을 수 있다.The chelating agent chelates the copper ions dissolved in the etching solution to prevent the reaction between the copper ions and the oxidizing agent and to enhance the stability of the oxidizing agent and the etching solution. Depending on the chelating ability of the copper ions in the etchant, the maximum amount of etching solution can be increased and the rapid decomposition of hydrogen peroxide can be prevented to improve safety. Representative examples include acetate chelating agents, phosphonic acid chelating agents and amino acids, and they may be used in combination. More specifically, examples of the acetic acid chelating agent include nitrilotriacetic acid (NTA), iminodiacetic acid (IDA), methyl iminodiacetic acid (MIDA), hydroxy Hydroxyethyl iminodiacetic acid (HIDA), diethylenetriamine pentaacetic acid (DPTA), ethylenediamine tetraacetic acid (EDTA), N-hydroxyethylethylene (N-hydroxyethyl ethylenediamine tetraacetic acid (HEDTA), methyl ethylenediamine tetraacetic acid (MEDTA), triethylene tetraamine hexaacetic acid (TTHA), and the like. Examples of phosphonic acid chelating agents include ethylenediamine tetramethylenephosphonic acid But are not limited to, ethylene diamine tetramethylene phosphonic acid (EDTPA), diethylene triamine pentamethylene phosphonic acid (DTPMPA), hydroxy ethylidene diphosphonic acid (HEDP) And examples of amino acids include glycine, arginine, glutamic acid, alanine, cysteine, glutamine, glyphosphate, and glacial acetic acid, and the like. . If the content of the chelating agent is less than 0.1% by weight, an abrupt reaction may occur between the oxidizing agent and the copper ion and the stability may be deteriorated. When the content of the chelating agent is less than 0.1% by weight, Exceeding% by weight may cause problems with the CD loss and the etching profile of the inclination angle.
상기 언더컷(undercut) 방지제는 금속의 산화 환원 전위를 조정하여 국부 전지 현상의 발생을 방지하고 구리, 몰리브덴, 티타늄 등으로 이루어진 다층막 구조에서 금속막간 균등한 식각 속도를 얻게 하는 역할을 한다. 본 발명에서는 무기 인산염 및 유기산계 암모늄염을 언더컷 방지제로 사용한다. 기존 식각액의 경우 무기 인산염을 주로 사용하였으나 다른 유기계 첨가제와 함께 결합하여 식각 장비에 이물이 발생하는 문제점이 있었다. 본 발명에서는 무기 인산염과 함께 유기산계 암모늄염을 사용함으로써 이물 발생을 현저히 줄일 수 있었다. 본 발명에서 사용가능한 무기 인산염은 인산암모늄, 인산수소암모늄, 인산이수소암모늄, 인산나트륨, 인산수소나트륨 및 인산이수소나트륨 중에서 선택한 1종 이상을, 유기산계 암모늄염의 경우에는 암모늄 아세테이트, 할로겐 유도된 암모늄 아세테이트, 초산암모늄 및 구연산암모늄 중에서 선택한 1종 이상을 들 수 있다. 이때, 무기 인산염과 유기산계 암모늄염의 중량비는 1 : 0.25 ~ 2 인 것이 좋다. 유기산계 암모늄염의 중량비가 너무 작으면 식각 장비내 이물 발생이 있을 수 있고, 반대로 너무 크면 CD 손실이 적어져 식각 프로파일이 불량해 질 수 있다. 본 발명의 조성물 중 언더컷 방지제의 함량은 0.01 ~ 3 중량%가 바람직한데, 언더컷 방지제의 함량이 너무 적으면 하부 몰리브덴, 티타늄 및 몰리브덴-티타늄 막에서 언더컷 현상이 발생될 수 있고, 3 중량%를 초과하면 원하는 식각 프로파일을 얻기 어렵다.The undercut inhibitor prevents the occurrence of local cell development by adjusting the redox potential of the metal and plays a role in obtaining a uniform etch rate between the metal films in a multilayer structure of copper, molybdenum, titanium, and the like. In the present invention, inorganic phosphate and organic acid-based ammonium salt are used as an undercut inhibitor. In the case of the conventional etching solution, inorganic phosphate is mainly used, but there is a problem that foreign substances are generated in the etching equipment by bonding with other organic additives. In the present invention, the use of the organic acid-based ammonium salt together with the inorganic phosphate can significantly reduce the generation of foreign matter. The inorganic phosphate which can be used in the present invention may be at least one selected from ammonium phosphate, ammonium hydrogen phosphate, ammonium dihydrogen phosphate, sodium phosphate, sodium hydrogen phosphate and sodium dihydrogen phosphate, ammonium acetate in the case of an organic acid ammonium salt, Ammonium acetate, ammonium acetate, and ammonium citrate. At this time, the weight ratio of the inorganic phosphate to the organic acid-based ammonium salt is preferably 1: 0.25 to 2. If the weight ratio of the organic acid-based ammonium salt is too small, foreign matter may be generated in the etching equipment. Conversely, if it is too large, the CD loss may be reduced and the etching profile may become poor. If the content of the undercut inhibitor is too small, an undercut phenomenon may occur in the lower molybdenum, titanium and molybdenum-titanium films, and if the content of the undercut inhibitor exceeds 3 wt% It is difficult to obtain a desired etching profile.
상기 구리식각 억제제는 몰리브덴, 티타늄에 비해 식각속도가 빠른 구리의 식각속도를 조정함으로서 우수한 식각 프로파일을 얻고자 사용하며, 대표적으로 헤테로사이클릭 아민(heterocyclic amine) 들이 이에 해당된다. 구체적인 예로 아미노테트라졸(Aminotetrazole), 이미다졸, 인돌, 퓨린, 피라졸, 피리딘, 피리미딘, 피롤, 피롤리딘, 피롤린, 벤조트리아졸 또는 이들의 혼합물을 사용할 수 있다. 본 발명의 조성물 중 구리식각 억제제의 함량은 0.01 ~ 5 중량%가 바람직한데, 함량이 너무 적으면 구리 식각 속도가 빨라져서 다층막 적용시 식각 프로파일이 불량해 질 수 있으며, 5 중량%를 초과하면 식각 속도가 떨어져서 생산성이 떨어질 수 있다.The copper etching inhibitor is used to obtain an excellent etching profile by adjusting the etching rate of copper having a higher etching rate than that of molybdenum and titanium. Typical examples thereof include heterocyclic amines. Specific examples thereof include aminotetrazole, imidazole, indole, purine, pyrazole, pyridine, pyrimidine, pyrrole, pyrrolidine, pyrroline, benzotriazole or a mixture thereof. The content of the copper etching inhibitor in the composition of the present invention is preferably from 0.01 to 5% by weight. If the content is too low, the copper etching rate becomes faster and the etching profile may become poor when the multilayer film is applied. The productivity may drop.
상기 잔사 제거제는 몰리브덴, 티타늄 및 몰리브덴-티타늄 합금의 잔사를 방지하는 기능을 하며, 본 발명에서는 무기 불화염을 사용한다. 구체적으로 불화암모늄, 불화수소암모늄, 불화나트륨, 불화칼륨, 중불화암모늄, 중불화나트륨 및 중불화칼륨 중에서 선택한 1종 이상을 사용할 수 있다. 금속막 식각용 조성물 중 상기 잔사 제거제의 함량은 0.01 ~ 5 중량%가 좋은데, 함량이 0.01 중량% 미만이면 몰리브덴 등의 잔사현상이 나타나는 문제가 있을 수 있고, 함량이 5 중량%를 초과하면 하부 기저막 및 유리 기판이 식각되는 문제가 발생될 수 있다.The residue removing agent functions to prevent residues of molybdenum, titanium and molybdenum-titanium alloy, and inorganic flame retarding agent is used in the present invention. Specifically, at least one selected from ammonium fluoride, ammonium hydrogen fluoride, sodium fluoride, potassium fluoride, ammonium fluoride, sodium fluoride, and potassium fluoride may be used. The content of the residue remover in the composition for etching a metal film is preferably 0.01 to 5% by weight. If the content is less than 0.01% by weight, there may be a problem of residue of molybdenum and the like. If the content is more than 5% And a problem that the glass substrate is etched may occur.
본 발명의 금속막 식각용 조성물은 필요에 따라 휘발 억제제를 추가로 포함할 수 있다. 휘발 억제제는 식각액의 휘발을 억제하여 식각에 따른 석출물의 용해도를 유지시켜 주는 효과로 인해 석출물이 잘 발생되지 않는다. 휘발억제제의 첨가로 기존 식각액에서 발생되는 식각 장비 배기구 인근의 석출물 발생 현상을 획기적으로 개선할 수 있다. 사용 가능한 휘발 억제제로는 히드록시기가 2개 이상 있는 다가 알코올, 예를 들면 에틸렌 글리콜, 프로필렌 글리콜, 폴리에틸렌글리콜 또는 이들의 혼합물을 들 수 있다. 휘발 억제제를 첨가하는 경우 첨가량은 0.1 ~ 7 중량%가 바람직한데, 첨가량이 0.1 중량% 미만이면 식각액의 휘발 억제 효과가 불충분하며, 7 중량%를 초과하여도 효과상의 실익이 미미하므로 상기 범위를 선택하는 것이 좋다.The composition for etching a metal film of the present invention may further comprise a volatilization inhibitor if necessary. The volatilization inhibitor suppresses the volatilization of the etching solution and maintains the solubility of the precipitate due to the etching. The addition of the volatilization inhibitor can dramatically improve the generation of deposits near the exhaust port of the etching apparatus generated in the conventional etching solution. Usable volatile inhibitors include polyhydric alcohols having two or more hydroxy groups, such as ethylene glycol, propylene glycol, polyethylene glycol, or mixtures thereof. When the volatilization inhibitor is added, the addition amount is preferably from 0.1 to 7% by weight. If the addition amount is less than 0.1% by weight, the effect of suppressing the volatilization of the etching solution is insufficient. It is good to do.
상기와 같은 구성물질과 함께 잔량의 물을 조성물 총 중량이 100 중량%가 되도록 구성함으로써 본 발명의 금속막 식각용 조성물을 얻을 수 있다.The composition for etching a metal film of the present invention can be obtained by constituting the composition in such a manner that the total weight of the composition is 100 wt% together with the remaining amount of water.
본 발명의 금속막 식각용 조성물은 구리, 몰리브덴, 티타늄 및 몰리드덴-티타늄 함금 중에서 선택한 1종 이상을 포함한 단일막 또는 다층막의 식각공정에 적용시 우수한 식각 프로파일을 얻을 수 있으며, 이물과 석출물 발생이 억제되어 생산성을 향상시킬 수 있다. 또한, 종래의 식각액과 대비하여 낮은 경사각을 확보할 수 있다.The composition for etching a metal film of the present invention can obtain an excellent etching profile when applied to an etching process of a single film or a multilayer film containing at least one selected from copper, molybdenum, titanium and molyidden-titanium alloy, Can be suppressed and the productivity can be improved. In addition, it is possible to secure a low inclination angle in comparison with the conventional etching solution.

이하 본 발명을 실시예에 의거하여 더욱 상세히 설명하겠는바, 본 발명이 다음 실시예에 의해 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited by the following Examples.
(실시예)(Example)
실시예 1 ~ 18 및 비교예 1 ~ 2Examples 1 to 18 and Comparative Examples 1 to 2
산화제, 식각 조정제, 킬레이트제, 언더컷 방지제, 구리식각 억제제, 잔사 제거제 및 잔량의 물을 포함하는 식각용 조성물을 제조하였다. 구체적인 구성물질 및 조성비는 하기 표 1과 같다.An etching composition comprising an oxidizing agent, an etching control agent, a chelating agent, an undercut inhibitor, a copper etching inhibitor, a residue remover and a residual amount of water was prepared. Specific constituent materials and composition ratios are shown in Table 1 below.
구분division 구성물질Constituent material 조성비Composition ratio
실시예 1Example 1 과산화수소/ IDA/ 말레익산/
인산암모늄 및 구연산암모늄/
아미노테트라졸/ 중불화암모늄/ 물Hydrogen peroxide / IDA / maleic acid /
Ammonium phosphate and ammonium citrate /
Aminotetrazole / Ammonium hydroxide / Water 		15.0/1.6/1.5/1.0/0.40/0.05/잔량15.0 / 1.6 / 1.5 / 1.0 / 0.40 / 0.05 / balance
실시예 2Example 2 19.0/2.0/1.0/1.0/0.70/0.05/잔량19.0 / 2.0 / 1.0 / 1.0 / 0.70 / 0.05 / balance
실시예 3Example 3 23.0/1.6/1.5/1.0/0.40/0.05/잔량23.0 / 1.6 / 1.5 / 1.0 / 0.40 / 0.05 / balance
실시예 4Example 4 23.0/1.6/0.5/1.0/0.40/0.05/잔량23.0 / 1.6 / 0.5 / 1.0 / 0.40 / 0.05 / balance
실시예 5Example 5 11.5/2.0/2.0/1.0/0.15/0.05/잔량11.5 / 2.0 / 2.0 / 1.0 / 0.15 / 0.05 / balance
실시예 6Example 6 17.0/2.0/0.8/0.1/0.35/0.05/잔량17.0 / 2.0 / 0.8 / 0.1 / 0.35 / 0.05 / balance
비교예 1Comparative Example 1 과산화수소/ IDA/ 황산칼륨/
인산암모늄/
아미노테트라졸/ 중불화칼륨/ 물Hydrogen peroxide / IDA / potassium sulfate /
Ammonium phosphate /
Aminotetrazole / potassium hydroxide / water 		21.5/3.0/1.0/1.0/0.80/0.05/잔량21.5 / 3.0 / 1.0 / 1.0 / 0.80 / 0.05 / balance
비교예 2Comparative Example 2 과산화수소/ IDA/ 글리콜산/
인산나트륨/
아미노테트라졸/ 중불화암모늄/ 물Hydrogen peroxide / IDA / glycolic acid /
Sodium Phosphate /
Aminotetrazole / Ammonium hydroxide / Water 		23.0/1.3/1.0/1.0/0.80/0.05/잔량23.0 / 1.3 / 1.0 / 1.0 / 0.80 / 0.05 / balance
실시예 7Example 7 과산화수소/ IDA/ 말레익산/
인산암모늄 및 구연산암모늄/
아미노테트라졸/ 중불화암모늄/
에틸렌글리콜/ 물Hydrogen peroxide / IDA / maleic acid /
Ammonium phosphate and ammonium citrate /
Aminotetrazole / ammonium < RTI ID = 0.0 >
Ethylene glycol / water 		19.0/2.1/2.8/0.23/0.3/0.05/5.0/잔량19.0 / 2.1 / 2.8 / 0.23 / 0.3 / 0.05 / 5.0 / balance
실시예 8Example 8 11.5/2.0/2.0/0.23/0.3/0.05/5.0/잔량11.5 / 2.0 / 2.0 / 0.23 / 0.3 / 0.05 / 5.0 / balance
실시예 9Example 9 14.5/2.0/2.1/0.23/0.3/0.05/5.0/잔량14.5 / 2.0 / 2.1 / 0.23 / 0.3 / 0.05 / 5.0 / balance
실시예 10Example 10 17.5/2.1/2.0/0.23/0.3/0.05/5.0/잔량17.5 / 2.1 / 2.0 / 0.23 / 0.3 / 0.05 / 5.0 / balance
실시예 11Example 11 19.0/2.9/1.5/0.23/0.3/0.05/5.0/잔량19.0 / 2.9 / 1.5 / 0.23 / 0.3 / 0.05 / 5.0 / balance
실시예 12Example 12 19.0/1.5/2.9/0.23/0.3/0.05/5.0/잔량19.0 / 1.5 / 2.9 / 0.23 / 0.3 / 0.05 / 5.0 / balance
실시예 13Example 13 19.0/2.3/1.9/0.23/0.3/0.05/5.0/잔량19.0 / 2.3 / 1.9 / 0.23 / 0.3 / 0.05 / 5.0 / balance
실시예 14Example 14 19.0/2.3/2.1/0.23/0.3/0.05/5.0/잔량19.0 / 2.3 / 2.1 / 0.23 / 0.3 / 0.05 / 5.0 / balance
실시예 15Example 15 19.0/2.0/2.5/0.23/0.3/0.05/5.0/잔량19.0 / 2.0 / 2.5 / 0.23 / 0.3 / 0.05 / 5.0 / balance
실시예 16Example 16 19.0/2.0/2.3/0.23/0.3/0.05/5.0/잔량19.0 / 2.0 / 2.3 / 0.23 / 0.3 / 0.05 / 5.0 / balance
실시예 17Example 17 19.0/2.1/2.4/0.23/0.3/0.05/5.0/잔량19.0 / 2.1 / 2.4 / 0.23 / 0.3 / 0.05 / 5.0 / balance
실시예 18Example 18 19.0/2.1/2.8/0.23/0.3/0.05/5.0/잔량19.0 / 2.1 / 2.8 / 0.23 / 0.3 / 0.05 / 5.0 / balance
실시예 7 ~ 18 : 휘발 억제제 추가 첨가
언더컷 방지제 : 무기 인산염(인산암모늄)과 유기산계 암모늄(구연산암모늄)을 1 : 1.3 중량비로 혼합Examples 7 to 18: Additional addition of a volatilization inhibitor
Undercutting agent: An inorganic phosphate (ammonium phosphate) and an organic acid-based ammonium (ammonium citrate) were mixed at a weight ratio of 1: 1.3

식각성능 평가Etching performance evaluation
본 발명에서 제안된 식각용 조성물의 성능을 파악하기 위하여 구리/몰리브덴-티타늄 합금의 이중막 기판을 준비하였다. 몰리브덴과 티타늄 합금은 1 : 1의 중량비로 구성되었으며, 구리 및 몰리브덴-티타늄 합금은 LCD 유리기판 제조과정과 동일하게 스퍼터링 방법을 통해 기판에 증착하였다. 구리막과 몰리브덴-티타늄 합금막은 두가지 두께로 증착하였는데 두께는 각각 구리 2000Å/몰리브덴-티타늄 300Å, 구리 2500Å/몰리브덴-티타늄 100Å 이였다.In order to understand the performance of the etching composition proposed in the present invention, a double-layered substrate of copper / molybdenum-titanium alloy was prepared. Molybdenum and titanium alloys were formed at a weight ratio of 1: 1. Copper and molybdenum-titanium alloys were deposited on a substrate by sputtering in the same manner as LCD glass substrates. Copper films and molybdenum-titanium alloy films were deposited in two thicknesses: copper 2000 Å / molybdenum-titanium 300 Å, copper 2500 Å / molybdenum-titanium 100 Å, respectively.
실시예 1 ~ 18 및 비교예 1 ~ 2 의 조성물을 각각 분사식 습식 식각 방식의 실험장비(KCTECH사 제조, 모델명: ETCHER(TFT))에 넣고 가열하여 온도가 33±0.5℃로 유지될 때 상기 이중막 기판의 식각 공정을 수행하였다. 오버 에치(O/E) 비율은 패드부분의 EPD(End Point Detection)를 기준으로 60% 막별로 적용하여 식각하였다. 식각이 완료되면 초순수로 세정한 후 건조 장치를 이용하여 건조하고, 포토레지스트 박리기(stripper)를 이용하여 포토레지스트를 제거하여 전자주사현미경(SEM, Phillips사 제조, 모델명: NOVA-200)을 이용하여 식각 프로파일을 경사각, 양측 CD(Critical Dimension) 손실, 식각 잔류물 등을 평가하였다. 또한, 식각액의 안정성을 확인하기 위하여 구리 이온의 농도를 증가시켜 식각액이 안정한 상태의 최대 구리 농도를 확인하였다.The compositions of Examples 1 to 18 and Comparative Examples 1 and 2 were placed in an experimental equipment of a spray-type wet etching system (manufactured by KCTECH, model name: ETCHER (TFT)) and heated. When the temperature was maintained at 33 ± 0.5 ° C, The etching process of the film substrate was performed. The over-etch (O / E) ratio was etched by 60% film thickness based on EPD (End Point Detection) of pad part. After the etching was completed, the substrate was cleaned with ultrapure water, dried using a drying device, and then photoresist was removed using a photoresist stripper. The photoresist was removed using a scanning electron microscope (SEM, manufactured by Phillips, model NOVA-200) The etch profile was evaluated for tilt angle, loss of critical dimension (CD) on both sides, and etch residue. Also, to confirm the stability of the etching solution, the maximum copper concentration in the stable state of the etchant was confirmed by increasing the copper ion concentration.
구분division 경사
각도
(˚)slope
Angle
(°) 		양측
CD
손실
(㎛)Both sides
CD
Loss
(탆) 		하부
MoTi
돌출
(㎛)bottom
MoTi
protrusion
(탆) 		O/E
비율
(%)O / E
ratio
(%) 		잔사
여부Residue
Whether 		석출
발생
여부Precipitation
Occur
Whether 		최대
구리
이온
농도
(ppm)maximum
Copper
ion
density
(ppm) 		비고Remarks
실시예1Example 1 65.765.7 1.11.1 0.140.14 6060 ×× 발생Occur 11,98011,980 양호Good
실시예2Example 2 64.564.5 1.01.0 0.130.13 6060 ×× 발생Occur 11,50011,500 양호Good
실시예3Example 3 66.766.7 1.71.7 0.110.11 6060 ×× 발생Occur 10,60010,600 양호Good
실시예4Example 4 69.269.2 1.51.5 0.130.13 6060 ×× 발생Occur 9,8259,825 양호Good
실시예5Example 5 60.260.2 1.41.4 0.130.13 6060 ×× 발생Occur 15,36015,360 양호Good
실시예6Example 6 62.362.3 1.41.4 0.130.13 6060 ×× 발생Occur 11,95011,950 양호Good
비교예1Comparative Example 1 65.265.2 1.41.4 0.150.15 6060 ×× 발생Occur 4,0004,000 보통usually
비교예2Comparative Example 2 64.064.0 1.41.4 0.110.11 6060 ×× 발생Occur 4,0004,000 보통usually

상기 표 2는 본 발명의 기존의 일괄 식각용 조성물과 본 발명에서 제안된 산화제, 식각 조정제, 킬레이트제, 언더컷 방지제, 구리식각 억제제, 잔사 제거제 및 잔량의 물을 포함하는 식각용 조성물의 식각성능을 구리막/몰리브덴-티타늄 합금막의 두께가 각각 2000Å/300Å인 이중막 기판을 기준으로 비교한 것이다. 기존 식각용 조성물의 경우 최대 용해 가능한 구리 이온의 농도가 4,000 ppm 수준이나 본 발명의 경우 동일한 식각 프로파일에 식각 장비의 이물과 석출이 발견되지 않으며 최대 용해 가능 구리 이온의 농도도 6,000 ppm을 상회하여 기존 식각액 대비 식각액의 안정성이 향상되었음을 확인할 수 있다. 또한 기존 식각액 대비하여 CD 손실과 경사각, 하부막 잔사 부분은 동등함을 확인할 수 있다.Table 2 shows the etching performance of the conventional batch etching composition of the present invention and the composition for etching including the oxidizing agent, the etching control agent, the chelating agent, the undercut preventing agent, the copper etching inhibiting agent, the residue removing agent and the residual water proposed in the present invention And a copper / molybdenum-titanium alloy film having a thickness of 2000 Å / 300 Å, respectively. In the case of the conventional etching composition, the maximum soluble copper ion concentration is about 4,000 ppm. However, in the present invention, foreign substances and precipitation of the etching equipment are not found in the same etching profile and the maximum soluble copper ion concentration exceeds 6,000 ppm, It can be confirmed that the stability of the etchant relative to the etchant is improved. In addition, it can be confirmed that the CD loss, inclination angle, and bottom film residue are equivalent to those of the conventional etching solution.
구분division 경사
각도
(˚)slope
Angle
(°) 		양측
CD
손실
(㎛)Both sides
CD
Loss
(탆) 		하부
MoTi
돌출
(㎛)bottom
MoTi
protrusion
(탆) 		O/E
비율
(%)O / E
ratio
(%) 		잔사
여부Residue
Whether 		석출
발생
여부Precipitation
Occur
Whether 		최대
구리
이온
농도
(ppm)maximum
Copper
ion
density
(ppm) 		비고Remarks
실시예7Example 7 50.650.6 1.591.59 0.090.09 6060 ×× ×× 8,5308,530 우수Great
실시예8Example 8 52.052.0 1.061.06 0.060.06 6060 ×× ×× 9,8909,890 우수Great
실시예9Example 9 55.055.0 1.241.24 0.070.07 6060 ×× ×× 10,26010,260 우수Great
실시예10Example 10 57.257.2 1.201.20 0.070.07 6060 ×× ×× 9,2409,240 우수Great
실시예11Example 11 52.952.9 1.151.15 0.230.23 6060 ×× ×× 13,00013,000 우수Great
실시예12Example 12 47.647.6 1.401.40 0.150.15 6060 ×× ×× 9,8259,825 우수Great

상기 표 3는 휘발 억제제를 추가로 포함하는 본 발명의 금속막 식각용 조성물의 식각성능을 구리막/몰리브덴-티타늄 합금막의 두께가 각각 2000Å/300Å인 이중막 기판을 기준으로 나타낸 것으로, 동일한 식각 프로파일에 식각장비의 이물과 석출이 발견되지 않으며 최대 용해 가능 구리 이온의 농도도 6,000 ppm을 상회한다. 또한 표 2 의 비교예 1 ~ 2와 비교시 경사각이 5˚ 이상 낮아 후속 박막 증착 및 패턴 제조에 유리함을 확인할 수 있다.Table 3 shows the etching performance of the composition for etching a metal film of the present invention, which further includes a volatilization inhibitor, on the basis of a bilayer substrate having a thickness of 2000 Å / 300 Å of a copper film / molybdenum-titanium alloy film, No foreign bodies and precipitation of the etching equipment were found, and the maximum soluble copper ion concentration exceeded 6,000 ppm. Compared with Comparative Examples 1 and 2 in Table 2, the inclination angle was 5 ° or lower, which is advantageous for subsequent thin film deposition and pattern fabrication.

구분division Cu/MoTi
막두께
(Å)
Cu / MoTi
Film thickness
(A)
경사
각도
(˚)slope
Angle
(°) 		양측
CD
손실
(㎛)Both sides
CD
Loss
(탆) 		하부
MoTi
돌출
(㎛)bottom
MoTi
protrusion
(탆) 		Etch
Time
(s)Etch
Time
(s) 		잔사
여부Residue
Whether 		비고Remarks
실시예13Example 13 2000/3002000/300 46.246.2 1.451.45 0.220.22 7575 ×× 보통usually
실시예14Example 14 48.248.2 1.401.40 0.300.30 7575 ×× 보통usually
실시예15Example 15 51.651.6 1.611.61 0.180.18 7575 ×× 우수Great
실시예16Example 16 50.350.3 1.721.72 0.200.20 7575 ×× 우수Great
실시예17Example 17 51.751.7 1.441.44 0.250.25 7575 ×× 보통usually
실시예18Example 18 54.154.1 1.601.60 0.160.16 7575 ×× 우수Great
실시예13Example 13 2500/1002500/100 51.151.1 1.321.32 0.080.08 6060 ×× 우수Great
실시예14Example 14 48.248.2 1.411.41 0.080.08 6060 ×× 우수Great
실시예15Example 15 47.547.5 1.271.27 0.080.08 6060 ×× 우수Great
실시예16Example 16 51.251.2 1.361.36 0.080.08 6060 ×× 우수Great
실시예17Example 17 48.448.4 1.351.35 0.080.08 6060 ×× 우수Great
실시예18Example 18 50.650.6 1.591.59 0.090.09 6060 ×× 우수Great

상기 표 4는 구리/몰리브덴-티타늄 합금 이중막에서 하부 합금막의 두께에 따른 식각 프로파일을 나타낸 것이다. 통상적으로 상부 구리막과 하부 합금막의 두께가 변하면 다층막간 전자 이동속도 차이로 인해 식각 조정제의 성능이 떨어져 하부 합금막의 잔사가 문제되나, 본 발명의 식각용 조성물의 경우 하부 합금막의 잔사 및 돌출이 없으며 양호한 식각 프로파일을 얻게 되는 것을 알 수 있다. 따라서, 박막 증착 공정에서 막두께를 변화시켜도 강건한 식각 프로파일을 보임으로써 공정 운용상에 큰 이점으로 작용할 것으로 판단된다.Table 4 shows the etching profile according to the thickness of the lower alloy film in the copper / molybdenum-titanium alloy double film. In general, when the thickness of the upper copper film and the lower alloy film is changed, the performance of the etching regulator is lowered due to the difference in the electron mobility between the multilayer films. However, in the etching composition of the present invention, there is no residue or protrusion of the lower alloy film A good etching profile can be obtained. Therefore, it is expected that it will be a great advantage in the process operation by showing a robust etching profile even when the film thickness is changed in the thin film deposition process.

Claims (11)

  1. 산화제 7 ~ 30 중량%;
    식각 조정제 0.1 ~ 5 중량%;
    킬레이트제 0.1 ~ 5 중량%;
    언더컷 방지제 0.01 ~ 3 중량%;
    구리식각 억제제 0.01 ~ 5 중량%;
    잔사 제거제 0.01 ~ 5 중량%; 및
    전체 조성물 총 중량이 100 중량%가 되도록 하는 잔량의 물;
    을 포함하는 금속막 식각용 조성물.

    7 to 30% by weight of an oxidizing agent;
    0.1 to 5% by weight of an etching regulator;
    0.1 to 5 wt% chelating agent;
    0.01 to 3% by weight of an undercut inhibitor;
    0.01 to 5% by weight of a copper etching inhibitor;
    0.01 to 5% by weight of a residue remover; And
    A balance of water such that the total weight of the total composition is 100% by weight;
    Wherein the metal film is a metal film.

  2. 제 1 항에 있어서, 상기 산화제는 과산화수소인 것을 특징으로 하는 금속막 식각용 조성물.

    The composition for etching a metal film according to claim 1, wherein the oxidizing agent is hydrogen peroxide.

  3. 제 1 항에 있어서, 상기 식각 조정제는 아세트산, 시트르산, 옥살산, 말레익산, 글리콜산, 호박산, 타르타르산, 퓨마릭산, 살리실산, 말릭산 및 피바릭산 중에서 선택한 1종 이상인 것을 특징으로 하는 금속막 식각용 조성물.

    The metal film etching composition according to claim 1, wherein the etching control agent is at least one selected from the group consisting of acetic acid, citric acid, oxalic acid, maleic acid, glycolic acid, succinic acid, tartaric acid, fumaric acid, salicylic acid, malic acid and sebacic acid .

  4. 제 1 항에 있어서, 상기 킬레이트제는 니트릴로트리아세틱 에시드, 이미노디아세틱 에시드, 메틸 이미노디아세틱 에시드, 히드록시에틸 이미노디아세틱 에시드, 디에틸렌트리아민 펜타아세틱 에시드, 에틸렌디아민 테트라아세틱 에시드, N-히드록시에틸 에틸렌디아민 테트라아세틱 에시드, 메틸 에틸렌디아민 테트라아세틱 에시드, 트리에틸렌 테트라아민 헥사아세틱 에시드, 에틸렌 디아민 테트라메틸렌 포스포닉 에시드, 디에틸렌 트리아민 펜타메틸렌 포스포닉 에시드, 히드록시 에틸리덴 디포스포닉 에시드, 아미노 트리메틸렌 포스포닉 에시드, 글리신, 아르기닌, 글루타민산, 알라닌, 시스테인, 글루타민, 글리포스페이트 및 글라이실릭산 중에서 선택한 1종 이상인 것을 특징으로 하는 금속막 식각용 조성물.

    The method of claim 1, wherein the chelating agent is selected from the group consisting of nitrilotriacetic acid, iminodiacetic acid, methyliminodiacetic acid, hydroxyethyliminodiacetic acid, diethylenetriamine pentaacetic acid, ethylenediamine tetra But are not limited to, acetic acid, acetic acid, N-hydroxyethylethylenediamine tetraacetic acid, methylethylenediamine tetraacetic acid, triethylenetetraamine hexaacetic acid, ethylenediamine tetramethylenephosphonic acid, diethylenetriaminepenta methylenephosphonic acid Wherein the composition is at least one selected from the group consisting of hydroxyethylidene diphosphonic acid, aminotrimethylene phosphonic acid, glycine, arginine, glutamic acid, alanine, cysteine, glutamine, glyphosphate and glycylic acid.

  5. 제 1 항에 있어서, 상기 언더컷 방지제는 인산암모늄, 인산수소암모늄, 인산이수소암모늄, 인산나트륨, 인산수소나트륨 및 인산이수소나트륨 중에서 선택한 1종 이상의 무기 인산염, 및 암모늄 아세테이트, 할로겐 유도된 암모늄 아세테이트, 초산암모늄 및 구연산암모늄 중에서 선택한 1종 이상의 유기산계 암모늄염인 것을 특징으로 하는 금속막 식각용 조성물.

    The undercut preventing agent according to claim 1, wherein the undercut inhibitor is at least one inorganic phosphate selected from ammonium phosphate, ammonium hydrogen phosphate, ammonium dihydrogen phosphate, sodium phosphate, sodium hydrogen phosphate and sodium dihydrogen phosphate, and ammonium acetate, , Ammonium acetate, and ammonium citrate, wherein the organic acid ammonium salt is at least one organic acid ammonium salt selected from the group consisting of ammonium nitrate, ammonium nitrate, and ammonium citrate.

  6. 제 5 항에 있어서, 상기 무기 인산염과 상기 유기산계 암모늄염의 중량비는 1 : 0.25 ~ 2 인 것을 특징으로 하는 금속막 식각용 조성물.

    6. The composition for etching a metal film according to claim 5, wherein the weight ratio of the inorganic phosphate to the organic acid based ammonium salt is 1: 0.25-2.

  7. 제 1 항에 있어서, 상기 구리식각 억제제는 아미노테트라졸, 이미다졸, 인돌, 퓨린, 피라졸, 피리딘, 피리미딘, 피롤, 피롤리딘, 피롤린, 벤조트리아졸 또는 이들의 혼합물인 것을 특징으로 하는 금속막 식각용 조성물.

    The method according to claim 1, wherein the copper etching inhibitor is an aminotetrazole, imidazole, indole, purine, pyrazole, pyridine, pyrimidine, pyrrole, pyrrolidine, pyrroline, benzotriazole, Wherein the metal film is a metal film.

  8. 제 1 항에 있어서, 상기 잔사 제거제는 불화암모늄, 불화수소암모늄, 불화나트륨, 불화칼륨, 중불화암모늄, 중불화나트륨 및 중불화칼륨 중에서 선택한 1종 이상인 것을 특징으로 하는 금속막 식각용 조성물.

    The composition for etching a metal film according to claim 1, wherein the residue removing agent is at least one selected from ammonium fluoride, ammonium hydrogen fluoride, sodium fluoride, potassium fluoride, ammonium fluoride, sodium fluoride, and potassium fluoride.

  9. 제 1 항에 있어서, 휘발 억제제 0.1 ~ 7 중량%를 추가로 포함하는 것을 특징으로 하는 금속막 식각용 조성물.

    The composition for etching a metal film according to claim 1, further comprising 0.1 to 7% by weight of a volatilization inhibitor.

  10. 제 9 항에 있어서, 상기 휘발 억제제는 에틸렌 글리콜, 프로필렌 글리콜, 폴리에틸렌글리콜 또는 이들의 혼합물인 것을 특징으로 하는 금속막 식각용 조성물.

    10. The composition for etching a metal film according to claim 9, wherein the volatilization inhibitor is ethylene glycol, propylene glycol, polyethylene glycol or a mixture thereof.

  11. 제 1 항 내지 제 10 항 중에서 선택한 어느 한 항에 있어서, 상기 금속막은 구리, 몰리브덴, 티타늄 및 몰리브텐-티타늄 합금 중에서 선택한 1 종 이상을 포함한, 단일막 또는 다중막인 것을 특징으로 하는 금속막 식각용 조성물.The metal film according to any one of claims 1 to 10, wherein the metal film is a single film or a multilayer film containing at least one selected from copper, molybdenum, titanium, and molybdenum-titanium alloy Composition for etching.
PCT/KR2011/003427 2010-11-12 2011-05-09 Composition for etching metal films WO2012064001A1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
JP2013531466A JP5827336B2 (en) 2010-11-12 2011-05-09 Metal film etching composition
CN201180047122.0A CN103282549B (en) 2010-11-12 2011-05-09 For the composition of etching sheet metal

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR1020100112948A KR101270560B1 (en) 2010-11-12 2010-11-12 Composition for etching metal layer
KR10-2010-0112948 2010-11-12

Publications (1)

Publication Number Publication Date
WO2012064001A1 true WO2012064001A1 (en) 2012-05-18

Family

ID=46051124

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2011/003427 WO2012064001A1 (en) 2010-11-12 2011-05-09 Composition for etching metal films

Country Status (5)

Country Link
JP (1) JP5827336B2 (en)
KR (1) KR101270560B1 (en)
CN (1) CN103282549B (en)
TW (1) TWI503451B (en)
WO (1) WO2012064001A1 (en)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015002284A (en) * 2013-06-17 2015-01-05 株式会社Adeka Etchant composition and etching method
JP2015030809A (en) * 2013-08-05 2015-02-16 三和油化工業株式会社 Etchant composition
CN108319110A (en) * 2017-01-17 2018-07-24 固安鼎材科技有限公司 A kind of colour photoetching compositions and colored filter and preparation method thereof
CN110295368A (en) * 2018-03-23 2019-10-01 东进世美肯株式会社 Not comprising phosphatic tin indium oxide/Ag multilayer film etchant
WO2020159771A1 (en) * 2019-01-31 2020-08-06 Fujifilm Electronic Materials U.S.A., Inc. Etching compositions
CN111621785A (en) * 2019-02-28 2020-09-04 易案爱富科技有限公司 Metal film etching composition and etching method using same
CN113737183A (en) * 2021-08-12 2021-12-03 湖北兴福电子材料有限公司 Selective copper etching solution
CN115725974A (en) * 2022-12-15 2023-03-03 合肥中聚和成电子材料有限公司 Copper etching liquid composition

Families Citing this family (44)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101933529B1 (en) * 2012-12-28 2019-03-15 동우 화인켐 주식회사 Etchant composition for copper-containing metal layer and preparing method of an array substrate for liquid crystal display using same
KR101933528B1 (en) * 2012-12-28 2019-03-15 동우 화인켐 주식회사 Etchant composition for copper-containing metal layer and preparing method of an array substrate for liquid crystal display using same
KR101924384B1 (en) * 2012-12-28 2018-12-03 동우 화인켐 주식회사 Etchant composition for copper-containing metal
KR20140086665A (en) * 2012-12-28 2014-07-08 동우 화인켐 주식회사 Etchant composition for copper-containing metal layer and preparing method of an array substrate for liquid crystal display using same
CN107227463B (en) * 2013-01-14 2020-05-19 易安爱富科技有限公司 Etching solution composition for copper/molybdenum film or copper/molybdenum alloy film
KR101960342B1 (en) * 2013-02-28 2019-03-21 동우 화인켐 주식회사 Echaing composition, method of preparing metal line and method of manufacturing array substrate using the same
TWI510676B (en) * 2013-07-10 2015-12-01 Daxin Materials Corp Metal etchant compositions for etching copper and molybdenum and their use for etching Metal etching method for copper and molybdenum
KR101517013B1 (en) * 2013-10-02 2015-05-04 주식회사 이엔에프테크놀로지 Etching composition for copper and molibdenum containing film
US20150104952A1 (en) * 2013-10-11 2015-04-16 Ekc Technology, Inc. Method and composition for selectively removing metal hardmask and other residues from semiconductor device substrates comprising low-k dielectric material and copper
WO2015054464A1 (en) * 2013-10-11 2015-04-16 E. I. Du Pont De Nemours And Company Removal composition for selectively removing hard mask and methods thereof
TWI495762B (en) * 2013-11-01 2015-08-11 Daxin Materials Corp Etchant composition and etching method
TWI495763B (en) * 2013-11-01 2015-08-11 Daxin Materials Corp Etchant composition and etching method
KR102178949B1 (en) 2013-11-21 2020-11-16 삼성디스플레이 주식회사 Echtant and method for manufacturing display device using the same
KR20150124540A (en) 2014-04-28 2015-11-06 삼성디스플레이 주식회사 Echtant and method for manufacturing display device using the same
KR102218556B1 (en) * 2014-06-26 2021-02-22 동우 화인켐 주식회사 Etching solution composition for metal layer and manufacturing method of an array substrate for Liquid crystal display using the same
KR102209680B1 (en) * 2014-06-27 2021-01-29 동우 화인켐 주식회사 Etching solution composition for metal layer and manufacturing method of an array substrate for Liquid crystal display using the same
KR20160001985A (en) * 2014-06-30 2016-01-07 동우 화인켐 주식회사 Etching solution composition for metal layer and manufacturing method of an array substrate for Liquid crystal display using the same
KR20160010098A (en) * 2014-07-18 2016-01-27 동우 화인켐 주식회사 Etching solution composition for copper layer and titanium layer and method of preparing array substrate for liquid crystal display using the same
KR102255577B1 (en) * 2014-08-25 2021-05-25 엘지디스플레이 주식회사 Etching composition
KR102331036B1 (en) 2014-10-10 2021-11-26 삼영순화(주) Etching solution composition and etching method using the same
JP6494254B2 (en) * 2014-11-18 2019-04-03 関東化學株式会社 Copper / molybdenum metal laminated film etching solution composition, etching method using the composition, and method for extending the life of the composition
JP6531612B2 (en) * 2014-11-27 2019-06-19 三菱瓦斯化学株式会社 Liquid composition and etching method using the same
KR101670421B1 (en) * 2015-02-13 2016-10-28 한국항공대학교산학협력단 Method for etching a multi-layered metal film and etchant
KR102368356B1 (en) * 2015-03-19 2022-03-02 동우 화인켐 주식회사 Etchant composition and manufacturing method of an array for liquid crystal display
KR102281191B1 (en) * 2015-03-19 2021-07-23 동우 화인켐 주식회사 Etchant composition and manufacturing method of an array for liquid crystal display
TWI674335B (en) * 2015-07-24 2019-10-11 南韓商東友精細化工有限公司 Etchant composition, method for manufacturing array substrate for liquid crystal display device and array substrate using the same
CN105386056A (en) * 2015-12-04 2016-03-09 宁波东盛集成电路元件有限公司 Metal etching agent used for etching copper-containing metal layer and preparation method for metal etching agent
KR102455790B1 (en) * 2015-12-22 2022-10-19 주식회사 이엔에프테크놀로지 Copper Etchant Composition
KR102479444B1 (en) * 2015-12-30 2022-12-21 삼영순화(주) Etchant and manufacturing method for semiconductor device using the same
KR102384594B1 (en) * 2016-06-08 2022-04-08 동우 화인켐 주식회사 Manufacturing method of an array substrate for display device
KR102070323B1 (en) * 2016-10-14 2020-01-29 주식회사 이엔에프테크놀로지 Etching Composition
CN106498397B (en) * 2016-11-16 2019-04-09 中国科学院深圳先进技术研究院 A method of based on salt erosion in titanium-based implant surface in-situ construction multi-stage nano topological structure
CN108359987A (en) * 2017-01-26 2018-08-03 易案爱富科技有限公司 Etch combination
CN106917128B (en) * 2017-03-10 2019-10-15 北京工业大学 A kind of tin-molybdenum codope titanium dioxide nanotube array electrode and preparation method
DE102017122483B3 (en) * 2017-09-27 2018-10-25 Excor Korrosionsforschung Gmbh Compositions of vapor-phase corrosion inhibitors and their use and process for their preparation
CN109055937B (en) * 2018-07-03 2020-06-23 杭州电子科技大学 Chemical etching method for obtaining high-transmittance aluminum alloy
CN110923713B (en) * 2019-12-31 2020-12-08 成都中电熊猫显示科技有限公司 Etching liquid for copper-molybdenum and alloy films and preparation method thereof
CN113122267A (en) * 2019-12-31 2021-07-16 安集微电子科技（上海）股份有限公司 Application of accelerator composition in removing titanium nitride in copper damascene process
CN111334299B (en) * 2020-03-26 2021-11-30 成都中电熊猫显示科技有限公司 Etching liquid and preparation method thereof
JP7399314B2 (en) 2020-04-14 2023-12-15 インテグリス・インコーポレーテッド Method and composition for etching molybdenum
KR102421008B1 (en) 2020-04-22 2022-07-15 삼영순화(주) Etchant composition for seed layer containing copper
CN114182259B (en) * 2021-12-10 2024-02-23 Tcl华星光电技术有限公司 Etching liquid
CN114807941B (en) * 2022-02-25 2023-08-15 浙江奥首材料科技有限公司 Copper-molybdenum etching solution with high efficiency and long service life, and preparation method and application thereof
CN115074734B (en) * 2022-08-22 2022-11-08 深圳市板明科技股份有限公司 Copper-reducing additive for aluminum substrate circuit board and preparation method and use method thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20030048606A (en) * 2001-12-12 2003-06-25 엘지.필립스 엘시디 주식회사 1-step Etching Method for Cu/Mo line having inner Mo barrier layer by Mo
KR20040051502A (en) * 2002-12-12 2004-06-18 엘지.필립스 엘시디 주식회사 ETCHING SOLUTIONS AND METHOD TO REMOVE MOLYBDENUM RESIDUE FOR Cu MOLYBDENUM MULTILAYERS
KR100601740B1 (en) * 2005-04-11 2006-07-18 테크노세미켐 주식회사 Etchant for ito & izo thin film
KR20070097922A (en) * 2006-03-30 2007-10-05 동우 화인켐 주식회사 Etching composition for etching copper-based/molybdenum based multilayer film or indium oxide film and method for etching metal layer using the same

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7521366B2 (en) * 2001-12-12 2009-04-21 Lg Display Co., Ltd. Manufacturing method of electro line for liquid crystal display device
JP4696565B2 (en) * 2005-01-19 2011-06-08 三菱化学株式会社 Etching solution and etching method
JP2009076601A (en) * 2007-09-19 2009-04-09 Nagase Chemtex Corp Etching solution
KR101495683B1 (en) * 2008-09-26 2015-02-26 솔브레인 주식회사 Cu or Cu/Mo or Cu/Mo alloy electrode etching liquid in Liquid Crystal Display system
KR101529733B1 (en) * 2009-02-06 2015-06-19 동우 화인켐 주식회사 Manufacturing method of an array substrate for liquid crystal display

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20030048606A (en) * 2001-12-12 2003-06-25 엘지.필립스 엘시디 주식회사 1-step Etching Method for Cu/Mo line having inner Mo barrier layer by Mo
KR20040051502A (en) * 2002-12-12 2004-06-18 엘지.필립스 엘시디 주식회사 ETCHING SOLUTIONS AND METHOD TO REMOVE MOLYBDENUM RESIDUE FOR Cu MOLYBDENUM MULTILAYERS
KR100601740B1 (en) * 2005-04-11 2006-07-18 테크노세미켐 주식회사 Etchant for ito & izo thin film
KR20070097922A (en) * 2006-03-30 2007-10-05 동우 화인켐 주식회사 Etching composition for etching copper-based/molybdenum based multilayer film or indium oxide film and method for etching metal layer using the same

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015002284A (en) * 2013-06-17 2015-01-05 株式会社Adeka Etchant composition and etching method
JP2015030809A (en) * 2013-08-05 2015-02-16 三和油化工業株式会社 Etchant composition
CN108319110A (en) * 2017-01-17 2018-07-24 固安鼎材科技有限公司 A kind of colour photoetching compositions and colored filter and preparation method thereof
CN108319110B (en) * 2017-01-17 2022-08-02 固安鼎材科技有限公司 Color photoresist composition, color filter and preparation method thereof
CN110295368A (en) * 2018-03-23 2019-10-01 东进世美肯株式会社 Not comprising phosphatic tin indium oxide/Ag multilayer film etchant
CN110295368B (en) * 2018-03-23 2024-04-09 东进世美肯株式会社 Indium tin oxide/silver multi-layer film etching liquid composition containing no phosphate
WO2020159771A1 (en) * 2019-01-31 2020-08-06 Fujifilm Electronic Materials U.S.A., Inc. Etching compositions
CN113454267A (en) * 2019-01-31 2021-09-28 富士胶片电子材料美国有限公司 Etching composition
EP3918110A4 (en) * 2019-01-31 2022-11-02 FUJIFILM Electronic Materials U.S.A, Inc. Etching compositions
CN111621785A (en) * 2019-02-28 2020-09-04 易案爱富科技有限公司 Metal film etching composition and etching method using same
CN113737183A (en) * 2021-08-12 2021-12-03 湖北兴福电子材料有限公司 Selective copper etching solution
CN115725974A (en) * 2022-12-15 2023-03-03 合肥中聚和成电子材料有限公司 Copper etching liquid composition

Also Published As

Publication number Publication date
CN103282549A (en) 2013-09-04
JP2013543261A (en) 2013-11-28
TW201219601A (en) 2012-05-16
JP5827336B2 (en) 2015-12-02
KR20120051488A (en) 2012-05-22
TWI503451B (en) 2015-10-11
CN103282549B (en) 2015-09-02
KR101270560B1 (en) 2013-06-03

Similar Documents

Publication Publication Date Title
WO2012064001A1 (en) Composition for etching metal films
KR102058679B1 (en) Etching composition for copper/molybdenum or copper/molybdenum alloy multilayers
KR101400953B1 (en) Etching composition for copper and molibdenum alloy
KR101333551B1 (en) Etching composition for copper and molibdenum alloy
KR101404511B1 (en) Etchant composition, and method for etching a multi-layered metal film
KR20150089887A (en) Etching solution composition for copper layer and titanium layer and method of preparing array substrate for liquid crystal display using the same
KR101561518B1 (en) Etching composition for copper/molybdenum or copper/molybdenum alloy multilayers
KR20110128032A (en) Manufacturing method of an array substrate for liquid crystal display
KR101292449B1 (en) Etching composition for etching copper-based/molybdenum based multilayer film or indium oxide film and method for etching metal layer using the same
KR102091847B1 (en) Manufacturing method of an array substrate for liquid crystal display
KR20160112470A (en) Etchant composition and manufacturing method of an array for liquid crystal display
KR102131394B1 (en) Manufacturing method of an array substrate for liquid crystal display
KR20080024818A (en) Composition of etching solutions for multilayers of cu and molybdenum
KR101539765B1 (en) Manufacturing method of an array substrate for liquid crystal display
KR20170112886A (en) Etching solution composition for copper-based metal layer, manufacturing method of an array substrate for crystal display using the same
KR20140118318A (en) Etchant composition for copper-containing metal layer and preparing method of an array substrate for liquid crystal display using same
KR20160010098A (en) Etching solution composition for copper layer and titanium layer and method of preparing array substrate for liquid crystal display using the same
KR20180088282A (en) ETCHANT composition
KR101934863B1 (en) Etchant composition for etching double layer of metal layer and indium oxide layer and method for etching using the same
KR102142419B1 (en) Manufacturing method of an array substrate for liquid crystal display
KR20150035213A (en) Manufacturing method of an array substrate for liquid crystal display
KR20080024817A (en) Composition of etching solutions for multilayers of cu and molybdenum
KR102169571B1 (en) Manufacturing method of an array substrate for liquid crystal display
KR20220019623A (en) Etchant composition, manufacturing method of wire and array substrate for liquid crystal display
KR20130070517A (en) Manufacturing method of an array substrate for liquid crystal display

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 11839107

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2013531466

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 11839107

Country of ref document: EP

Kind code of ref document: A1