WO2011136594A2 - Copper and titanium composition for metal layer etching solution - Google Patents

Copper and titanium composition for metal layer etching solution Download PDF

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Publication number
WO2011136594A2
WO2011136594A2 PCT/KR2011/003172 KR2011003172W WO2011136594A2 WO 2011136594 A2 WO2011136594 A2 WO 2011136594A2 KR 2011003172 W KR2011003172 W KR 2011003172W WO 2011136594 A2 WO2011136594 A2 WO 2011136594A2
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Prior art keywords
etching
composition
titanium
metal film
acid
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PCT/KR2011/003172
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French (fr)
Korean (ko)
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WO2011136594A3 (en
Inventor
임민기
권오병
이유진
유인호
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동우 화인켐 주식회사
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Priority to CN201180016453.8A priority Critical patent/CN102822391B/en
Publication of WO2011136594A2 publication Critical patent/WO2011136594A2/en
Publication of WO2011136594A3 publication Critical patent/WO2011136594A3/en

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    • 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
    • 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
    • C23F1/02—Local etching
    • 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
    • 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
    • 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
    • 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
    • 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
    • C23F1/30—Acidic compositions for etching other metallic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
    • H01L21/283—Deposition of conductive or insulating materials for electrodes conducting electric current
    • H01L21/285—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation
    • H01L21/28506—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers
    • H01L21/28512—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers on semiconductor bodies comprising elements of Group IV of the Periodic System
    • H01L21/2855—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers on semiconductor bodies comprising elements of Group IV of the Periodic System by physical means, e.g. sputtering, evaporation
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
    • H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching

Definitions

  • the present invention relates to a semiconductor device and a flat panel display device, particularly an etching liquid composition for a metal film containing copper and titanium used as a gate, source / drain wiring, and electrode of a TFT.
  • a process of forming a metal wiring on a substrate is typically performed by a metal film forming process by sputtering, a photoresist forming process in a selective region by photoresist coating, exposure and development, and an etching process. It consists of steps. Moreover, the washing
  • the etching process refers to a process of leaving a metal film in a selective region using a photoresist as a mask, and typically, dry etching using plasma or wet etching using an etching solution is used.
  • low-resistance aluminum is used for the gate and source / drain array wiring of the TFT.
  • the aluminum layer is short-circuited with other conductive layers due to hillock and oxides in a subsequent process.
  • the peroxide-based or oxone-based etchant composition in order to etch a double layer containing copper and titanium, there is a problem in that a different etchant composition must be used for each layer.
  • the peroxide-based etchant composition in the case of the etching liquid composition for etching the metal film containing copper, the peroxide-based or oxone-based etchant composition is mainly used, the peroxide-based etchant composition has the disadvantage that the etchant composition is decomposed or unstable due to aging, jade In the case of a hand-based etching solution composition, the etching rate is slow and unstable by time.
  • An object of the present invention is to provide an etchant composition that can implement a fast etching rate and uniform etching.
  • the present invention is based on the total weight of the composition, 5-20% by weight persulfate; 0.01 to 2 wt% fluorine-containing compound; 1-10% by weight of one or more selected from inorganic acids, inorganic acid salts and mixtures thereof; 0.3-5 weight% of a cyclic amine compound; 0.1 to 5% by weight of chlorine-containing compound; 0.1-5% by weight of p-toluene sulfonic acid; And it provides a metal film etching liquid composition comprising copper and titanium, characterized in that it comprises a residual amount of water.
  • the present invention provides a method for manufacturing a semiconductor device or a flat panel display device comprising the step of etching the metal film containing copper and titanium using the etchant composition.
  • the present invention provides a semiconductor device or a flat panel display device manufactured using the etchant composition.
  • the etchant composition of the present invention can wet-etch a metal film containing copper and titanium, and more specifically, a double film of a Cu / Ti structure, thereby providing an effect of simplifying the etching process and improving productivity.
  • using the etchant composition of the present invention can implement a fast etching rate, it is possible to provide a uniform etching can be provided excellent etching characteristics.
  • the etchant composition of the present invention does not damage the equipment, does not require expensive equipment configuration even during etching and can provide a very economical advantage in favor of large area.
  • the etching liquid composition of the present invention may etch IZO or a-ITO used as the pixel electrode in addition to the metal film containing copper and titanium.
  • the source / drain electrode and the pixel electrode may be collectively etched.
  • the etchant composition of the present invention can implement a fast etching rate for copper without including hydrogen peroxide and / or OXONE.
  • the etching liquid composition for metal film containing copper and titanium of the present invention is at least one selected from persulfates, fluorine-containing compounds, inorganic acids, inorganic acid salts and mixtures thereof, cyclic amine compounds, chlorine-containing compounds, p-toluene sulfonic acid and Contains water.
  • Persulfate contained in the etchant composition of the present invention is a main oxidizing agent for etching a film containing copper, it is preferably contained in 5 to 20% by weight, and contained in 7 to 18% by weight relative to the total weight of the composition.
  • the film containing copper is etched in an appropriate amount, and the etching profile is also excellent.
  • the etching rate may be reduced, so that sufficient etching may not be achieved.
  • the persulfate is more than 20% by weight, it is difficult to control the etching degree because the etching rate is too fast.
  • the film and the copper film may be overetched.
  • the persulfate is preferably one or two or more selected from the group consisting of ammonium persulfate (APS), sodium persulfate (SPS) and potassium persulfate (PPS).
  • APS ammonium persulfate
  • SPS sodium persulfate
  • PPS potassium persulfate
  • the fluorine-containing compound included in the etchant composition of the present invention is a main component for etching a film containing titanium, ITO or a-ITO, and is contained in an amount of 0.01 to 2% by weight and 0.05 to 1% by weight based on the total weight of the composition. It is preferred to be included. If the above range is satisfied, the film containing titanium is etched in an appropriate amount, and the etching profile is also excellent. When included below the above range, the etching rate of the film containing titanium is lowered, and residues may occur. If the above range is exceeded, the substrate such as glass and the insulating film containing silicon may be damaged.
  • the fluorine-containing compound refers to a compound that can be dissociated into fluorine ions or polyatomic fluorine ions, and selected from the group consisting of ammonium fluoride, sodium fluoride, potassium fluoride, ammonium bifluoride, sodium bifluoride and potassium bifluoride. Or 2 or more types are preferable.
  • At least one selected from inorganic acids, inorganic acid salts, and mixtures thereof included in the etchant composition of the present invention oxidizes and etches films comprising copper and oxidizes films comprising titanium.
  • At least one selected from the inorganic acids, inorganic acid salts and mixtures thereof is preferably included in an amount of 1 to 10% by weight, and 2 to 7% by weight, based on the total weight of the composition.
  • the film containing copper and the film containing titanium are etched in an appropriate amount, and the etching profile is also excellent.
  • the etching rate may be lowered, and a defect may occur in the etching profile, and residues may occur. If the above-mentioned range is exceeded, overetching may occur, cracks may occur in the photoresist, and the etching solution may penetrate into the cracks, thereby causing a short circuit.
  • the inorganic acid is preferably selected from the group consisting of nitric acid, sulfuric acid, phosphoric acid and perchloric acid.
  • the inorganic acid salt is preferably selected from the group consisting of potassium salts, sodium and ammonium salts of nitric acid, sulfuric acid, phosphoric acid and perchloric acid.
  • the cyclic amine compound included in the etchant composition of the present invention forms a profile upon etching of a film containing copper. Based on the total weight of the composition, the cyclic amine compound is contained in 0.3 to 5% by weight, preferably contained in 0.5 to 3% by weight. When included in the above-described range, there is an effect of forming an appropriate copper etching rate and taper angle, and adjusting the side etching amount.
  • the etching rate of the copper film is increased to increase the risk of overetching.
  • the etching rate of copper may be lowered to prevent the desired degree of etching. .
  • the cyclic amine compound is preferably one or two or more selected from the group consisting of 5-aminotetrazole, tolytriazole, benzotriazole and methyltriazole.
  • the chlorine-containing compound included in the etchant composition of the present invention is an auxiliary oxidant for etching a film containing copper, and is preferably included in an amount of 0.1 to 5% by weight and 0.5 to 3% by weight based on the total weight of the composition. When included in the above-described range, there is an effect of forming the taper angle more effectively.
  • the tapered angle is formed too low, the tapered inclined surface is long, which may cause problems in the subsequent process, if it exceeds 5% by weight, the tapered angle is too high Which may result in poor step coverage in subsequent processes.
  • the chlorine-containing compound means a compound capable of dissociating into chlorine ions, and preferably one or two or more selected from the group consisting of hydrochloric acid, sodium chloride, potassium chloride and ammonium chloride (NH 4 Cl).
  • the p-toluene sulfonic acid included in the etchant composition of the present invention prevents a change in composition by changing its composition over time after preparation of the etchant, and prevents the etching solution from being stored for a long time.
  • the p-toluene sulfonic acid is included in 0.1 to 5% by weight, and preferably in 0.5 to 3% by weight based on the total weight of the composition. If it is included below the above-mentioned range, it is difficult to prevent the change of the chemical solution due to its own over time, and if it exceeds the above-mentioned range, it is possible to prevent the self-timed, but the over-etching phenomenon occurs, the profile is not excellent.
  • Water included in the etchant composition of the present invention means deionized water, and is used for the semiconductor process, preferably water of 18 Pa ⁇ cm or more. With respect to the total weight of the composition, the amount of water is included so that the total weight of the etchant composition of the present invention is 100% by weight.
  • the etchant composition of the present invention may contain one or two or more selected from the group consisting of an etch regulator, a surfactant, a metal ion sequestrant and a corrosion inhibitor in addition to the above-mentioned components.
  • the etchant composition of the present invention is particularly effective for metal films containing copper and titanium, especially for double films of Cu / Ti structures. It is also effective for etching IZO or a-ITO.
  • Example 1 and Comparative Example 1 Preparation of the etchant composition
  • Example 1 10 0.5 3 One One 2 Remaining amount Comparative Example 1 10 0.5 3 One One 0 Remaining amount
  • ATZ 5-amino tetrazole
  • a substrate was manufactured by depositing a SiNx layer on glass, stacking a copper film on the SiNx layer, a titanium film on the copper film, and forming a photoresist pattern on the titanium film in a predetermined shape.
  • the substrate was cut into 550 ⁇ 650 mm using a diamond knife to prepare a specimen.
  • Example 1 and Comparative Example 1 were placed in an experimental equipment of a spray etching method (manufacturer: SEMES, model name: ETCHER (TFT)), and the temperature was set to 25 ° C. and heated. Then, after the temperature reached 30 ⁇ 0.1 °C, the etching process was performed. Total etch time was given at 40% based on EPD. Insert the specimen, start spraying, and when the etching is complete, taken out, washed with deionized water, dried using a hot air drying apparatus, and removed the photoresist using a photoresist stripper (PR) stripper. After washing and drying, the etching characteristics were evaluated using an electron scanning microscope (SEM; manufacturer: HITACHI, model name: S-4700), and the results are shown in Table 2.
  • SEM electron scanning microscope
  • Etching liquid composition of Example 1 and Comparative Example 1 was prepared in a sufficient amount to proceed the reference etching (reference etch) and the remaining conditions of the stored solution at 25 °C after the planned date (here 5 days) after the same conditions, The etching test was performed again, and the experiment was performed by comparing with the reference test result.

Abstract

The present invention relates to a copper and titanium composition for a metal layer etching solution comprising the following, based on the total weight of the composition: 5 to 20 wt % of persulfate; 0.01 to 2 wt % of a fluorine compound; 1-10 wt % of an additive containing one or more acids selected from inorganic acids, salts of inorganic acids, and a mixture thereof; 0.3 to 5 wt % of a cyclic amine compound; 0.1 to 5 wt % of a chlorine compound; 0.1 to 5 wt % of a p-toluene sulfonic acid; and with the remainder being water.

Description

구리와 티타늄을 포함하는 금속막용 식각액 조성물Etching composition for metal film containing copper and titanium
본 발명은 반도체 장치 및 평판표시장치, 특히 TFT의 게이트, 소스/드레인 배선 및 전극으로 사용되는 구리와 티타늄을 포함하는 금속막용 식각액 조성물에 관한 것이다.BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a semiconductor device and a flat panel display device, particularly an etching liquid composition for a metal film containing copper and titanium used as a gate, source / drain wiring, and electrode of a TFT.
반도체 장치 및 평판표시장치에서 기판 위에 금속 배선을 형성하는 과정은 통상적으로 스퍼터링에 의한 금속막 형성공정, 포토레지스트 도포, 노광 및 현상에 의한 선택적인 영역에서의 포토레지스트 형성공정, 및 식각공정에 의한 단계로 구성된다. 또한, 개별적인 단위 공정 전후의 세정공정 등을 포함한다. 이러한 식각공정은 포토레지스트를 마스크로 사용하여 선택적인 영역에 금속막을 남기는 공정을 의미하며, 통상적으로 플라즈마 등을 이용한 건식 식각 또는 식각액을 사용하는 습식 식각이 사용된다.In the semiconductor device and the flat panel display device, a process of forming a metal wiring on a substrate is typically performed by a metal film forming process by sputtering, a photoresist forming process in a selective region by photoresist coating, exposure and development, and an etching process. It consists of steps. Moreover, the washing | cleaning process, etc. before and after an individual unit process are included. The etching process refers to a process of leaving a metal film in a selective region using a photoresist as a mask, and typically, dry etching using plasma or wet etching using an etching solution is used.
반도체 장치 및 평판표시장치의 구성 중, TFT의 게이트, 소스/드레인 어레이 배선으로는 저항이 낮은 알루미늄을 사용하게 되는데 알루미늄 층은 후속 공정에서 힐락(Hillock)에 의한 다른 전도층과의 쇼트현상 및 산화물층과의 접촉에 의한 절연층을 형성시키는 문제가 있다. 이에 TFT의 게이트, 소스/드레인 어레이 배선 및 전극으로 구리와 티타늄을 포함하는 이중막이 소개되고 있다. During the construction of semiconductor devices and flat panel displays, low-resistance aluminum is used for the gate and source / drain array wiring of the TFT. The aluminum layer is short-circuited with other conductive layers due to hillock and oxides in a subsequent process. There is a problem of forming an insulating layer by contact with the layer. Accordingly, a double film including copper and titanium is introduced as a gate, source / drain array wiring, and electrode of a TFT.
하지만, 구리와 티타늄을 포함하는 이중막을 식각하기 위해서는 각 층마다 다른 식각액 조성물을 이용해야 하는 문제점이 있다. 특히 구리를 포함하는 금속막을 식각하기 위한 식각액 조성물의 경우, 과수계 또는 옥손계 식각액 조성물이 주로 이용되는데, 과수계 식각액 조성물의 경우 식각액 조성물이 분해되거나 경시(aging)에 의해 불안정한 단점이 있고, 옥손계 식각액 조성물의 경우 식각 속도가 느리고 경시에 의해 불안정한 단점이 있다.However, in order to etch a double layer containing copper and titanium, there is a problem in that a different etchant composition must be used for each layer. In particular, in the case of the etching liquid composition for etching the metal film containing copper, the peroxide-based or oxone-based etchant composition is mainly used, the peroxide-based etchant composition has the disadvantage that the etchant composition is decomposed or unstable due to aging, jade In the case of a hand-based etching solution composition, the etching rate is slow and unstable by time.
본 발명의 목적은 구리와 티타늄을 포함하는 금속막, 보다 상세하게는 Cu/Ti 구조의 이중막을 일괄 습식 식각할 수 있는 식각액 조성물을 제공하는 것이다.It is an object of the present invention to provide an etching liquid composition capable of performing a batch wet etching of a metal film containing copper and titanium, and more particularly, a double film of a Cu / Ti structure.
본 발명의 목적은 과산화수소 및/또는 옥손(oxone)을 포함하지 않고도 구리에 대하여 빠른 식각속도를 구현할 수 있는 식각액 조성물을 제공하는 것이다.It is an object of the present invention to provide an etchant composition capable of realizing a fast etching rate for copper without including hydrogen peroxide and / or oxone.
본 발명의 목적은 식각 공정의 간소화 및 생산성 향상 효과를 제공할 수 있는 식각액 조성물을 제공하는 것이다.It is an object of the present invention to provide an etching liquid composition that can provide an effect of simplifying the etching process and improving productivity.
본 발명의 목적은 빠른 식각속도 및 균일한 에칭을 구현할 수 있는 식각액 조성물을 제공하는 것이다.An object of the present invention is to provide an etchant composition that can implement a fast etching rate and uniform etching.
본 발명의 목적은 장비를 손상시키지 않으며, 식각 시에도 고가의 장비구성이 필요하지 않는 식각액 조성물을 제공하는 것이다.It is an object of the present invention to provide an etchant composition which does not damage equipment and does not require expensive equipment configuration during etching.
본 발명의 목적은 대면적화에 유리하여 경제적인 이점을 제공할 수 있는 식각액 조성물을 제공하는 것이다. It is an object of the present invention to provide an etchant composition which is advantageous for large area and which can provide economic advantages.
본 발명의 목적은 구리와 티타늄을 포함하는 금속막 이외에도, 화소전극으로 사용되는 IZO 또는 a-ITO를 식각할 수 있는 식각액 조성물을 제공하는 것이다.It is an object of the present invention to provide an etching liquid composition capable of etching IZO or a-ITO used as a pixel electrode in addition to a metal film containing copper and titanium.
본 발명은 조성물 총 중량에 대하여, 과황산염 5~20 중량%; 함불소화합물 0.01~2 중량%; 무기산, 무기산염 및 이들의 혼합물 중에서 선택되는 1종 이상 1~10 중량%; 고리형 아민화합물 0.3~5 중량%; 함염소화합물 0.1~5 중량%; p-톨루엔 술폰산(p-toluene sulfonic acid) 0.1~5 중량%; 및 물 잔량을 포함하는 것을 특징으로 하는 구리와 티타늄을 포함하는 금속막용 식각액 조성물을 제공한다. The present invention is based on the total weight of the composition, 5-20% by weight persulfate; 0.01 to 2 wt% fluorine-containing compound; 1-10% by weight of one or more selected from inorganic acids, inorganic acid salts and mixtures thereof; 0.3-5 weight% of a cyclic amine compound; 0.1 to 5% by weight of chlorine-containing compound; 0.1-5% by weight of p-toluene sulfonic acid; And it provides a metal film etching liquid composition comprising copper and titanium, characterized in that it comprises a residual amount of water.
또한, 본 발명은 상기 식각액 조성물을 사용하여 구리와 티타늄을 포함하는 금속막을 식각하는 공정을 포함하는 것을 특징으로 하는 반도체 소자 또는 평판표시소자의 제조방법을 제공한다.In addition, the present invention provides a method for manufacturing a semiconductor device or a flat panel display device comprising the step of etching the metal film containing copper and titanium using the etchant composition.
또한, 본 발명은 상기 식각액 조성물을 사용하여 제조되는 반도체 소자 또는 평판표시소자를 제공한다.In addition, the present invention provides a semiconductor device or a flat panel display device manufactured using the etchant composition.
본 발명의 식각액 조성물은 구리와 티타늄을 포함하는 금속막, 보다 상세하게는 Cu/Ti 구조의 이중막을 일괄 습식 식각할 수 있어서, 식각 공정의 간소화 및 생산성 향상 효과를 제공할 수 있다. 또한, 본 발명의 식각액 조성물을 이용하면 빠른 식각속도를 구현할 수 있고, 균일한 에칭이 가능하여 우수한 식각 특성을 제공할 수 있다. 또한 본 발명의 식각액 조성물은 장비를 손상시키지 않으며, 식각 시에도 고가의 장비구성이 필요하지 않고 대면적화에 유리하여 매우 경제적인 이점을 제공할 수 있다. 또한 본 발명의 식각액 조성물은 구리와 티타늄을 포함하는 금속막 이외에도, 화소전극으로 사용되는 IZO 또는 a-ITO를 식각할 수 있다. 또한 본 발명의 식각액 조성물은 구리와 티타늄을 포함하는 금속막이 소스/드레인 전극으로 사용되고, 화소전극으로 IZO 또는 a-ITO가 사용될 경우, 소스/드레인 전극과 화소전극을 일괄적으로 식각할 수 있다. 또한, 본 발명의 식각액 조성물은 과산화수소 및/또는 옥손(OXONE)을 포함하지 않고도 구리에 대하여 빠른 식각 속도를 구현할 수 있다.The etchant composition of the present invention can wet-etch a metal film containing copper and titanium, and more specifically, a double film of a Cu / Ti structure, thereby providing an effect of simplifying the etching process and improving productivity. In addition, using the etchant composition of the present invention can implement a fast etching rate, it is possible to provide a uniform etching can be provided excellent etching characteristics. In addition, the etchant composition of the present invention does not damage the equipment, does not require expensive equipment configuration even during etching and can provide a very economical advantage in favor of large area. In addition, the etching liquid composition of the present invention may etch IZO or a-ITO used as the pixel electrode in addition to the metal film containing copper and titanium. In addition, in the etching solution composition of the present invention, when a metal film including copper and titanium is used as the source / drain electrode, and IZO or a-ITO is used as the pixel electrode, the source / drain electrode and the pixel electrode may be collectively etched. In addition, the etchant composition of the present invention can implement a fast etching rate for copper without including hydrogen peroxide and / or OXONE.
이하, 본 발명에 대해 상세히 설명한다.Hereinafter, the present invention will be described in detail.
본 발명의 구리와 티타늄을 포함하는 금속막용 식각액 조성물은 과황산염, 함불소화합물, 무기산, 무기산염 및 이들의 혼합물 중에서 선택되는 1종 이상, 고리형 아민화합물, 함염소화합물, p-톨루엔 술폰산 및 물을 포함한다. The etching liquid composition for metal film containing copper and titanium of the present invention is at least one selected from persulfates, fluorine-containing compounds, inorganic acids, inorganic acid salts and mixtures thereof, cyclic amine compounds, chlorine-containing compounds, p-toluene sulfonic acid and Contains water.
본 발명의 식각액 조성물에 포함되는 과황산염은 구리를 포함하는 막을 식각하는 주산화제로서, 조성물 총 중량에 대하여, 5~20 중량%로 포함되고, 7~18 중량%로 포함되는 것이 바람직하다. Persulfate contained in the etchant composition of the present invention is a main oxidizing agent for etching a film containing copper, it is preferably contained in 5 to 20% by weight, and contained in 7 to 18% by weight relative to the total weight of the composition.
상술한 범위로 포함되면, 구리를 포함하는 막이 적정량으로 식각되고, 식각 프로파일도 우수해진다.When included in the above-mentioned range, the film containing copper is etched in an appropriate amount, and the etching profile is also excellent.
상기 과황산염이 5 중량% 미만으로 포함되면 식각율이 감소하여 충분한 식각이 이루어지지 않을 수 있고, 20 중량%를 초과하는 경우는 식각속도가 지나치게 빠르기 때문에 식각 정도를 제어하기 힘들며, 이에 따라 상기 티타늄막과 상기 구리막이 과식각 될 수 있다.When the persulfate is included in less than 5% by weight, the etching rate may be reduced, so that sufficient etching may not be achieved. When the persulfate is more than 20% by weight, it is difficult to control the etching degree because the etching rate is too fast. The film and the copper film may be overetched.
상기 과황산염은 과황산암모늄(APS), 과황산소다(SPS) 및 과황산칼륨(PPS)으로 이루어진 군에서 선택되는 1종 또는 2종 이상의 것이 바람직하다.The persulfate is preferably one or two or more selected from the group consisting of ammonium persulfate (APS), sodium persulfate (SPS) and potassium persulfate (PPS).
본 발명의 식각액 조성물에 포함되는 함불소화합물은 티타늄을 포함하는 막, ITO 또는 a-ITO를 식각하는 주성분로서, 조성물 총 중량에 대하여, 0.01~2 중량%로 포함되고, 0.05~1 중량%로 포함되는 것이 바람직하다. 상술한 범위를 만족하면, 티타늄을 포함하는 막이 적정량으로 식각되고, 식각 프로파일도 우수해진다. 상술한 범위 미만으로 포함되면, 티타늄을 포함하는 막의 식각속도가 저하되어 잔사가 발생할 수 있다. 상술한 범위를 초과하면 유리 등의 기판과 실리콘을 포함하는 절연막에 손상을 입힐 수 있다.The fluorine-containing compound included in the etchant composition of the present invention is a main component for etching a film containing titanium, ITO or a-ITO, and is contained in an amount of 0.01 to 2% by weight and 0.05 to 1% by weight based on the total weight of the composition. It is preferred to be included. If the above range is satisfied, the film containing titanium is etched in an appropriate amount, and the etching profile is also excellent. When included below the above range, the etching rate of the film containing titanium is lowered, and residues may occur. If the above range is exceeded, the substrate such as glass and the insulating film containing silicon may be damaged.
상기 함불소화합물은 불소 이온 또는 다원자 불소이온으로 해리될 수 있는 화합물을 의미하며, 불화암모늄, 불화나트륨, 불화칼륨, 중불화암모늄, 중불화나트륨 및 중불화칼륨으로 이루어진 군에서 선택되는 1종 또는 2종 이상의 것이 바람직하다.The fluorine-containing compound refers to a compound that can be dissociated into fluorine ions or polyatomic fluorine ions, and selected from the group consisting of ammonium fluoride, sodium fluoride, potassium fluoride, ammonium bifluoride, sodium bifluoride and potassium bifluoride. Or 2 or more types are preferable.
본 발명의 식각액 조성물에 포함되는 무기산, 무기산염 및 이들의 혼합물 중에서 선택되는 1종 이상은 구리를 포함하는 막을 산화 및 식각하고, 티타늄을 포함하는 막을 산화시킨다. 상기 무기산, 무기산염 및 이들의 혼합물 중에서 선택되는 1종 이상은 조성물 총 중량에 대하여, 1~10 중량%로 포함되고, 2~7 중량%로 포함되는 것이 바람직하다. 상술한 범위를 만족하면, 구리를 포함하는 막과 티타늄을 포함하는 막이 적정량으로 식각되고, 식각 프로파일도 우수해진다. 상술한 범위 미만으로 포함되면, 식각속도가 저하되어 식각 프로파일에 불량이 발생할 수 있으며, 잔사가 발생할 수 있다. 상술한 범위를 초과하면, 과식각이 발생할 수 있고, 포토레지스트에 크랙이 발생하여, 크랙으로 식각액이 침투되어 배선이 단락될 수 있다.At least one selected from inorganic acids, inorganic acid salts, and mixtures thereof included in the etchant composition of the present invention oxidizes and etches films comprising copper and oxidizes films comprising titanium. At least one selected from the inorganic acids, inorganic acid salts and mixtures thereof is preferably included in an amount of 1 to 10% by weight, and 2 to 7% by weight, based on the total weight of the composition. When the above range is satisfied, the film containing copper and the film containing titanium are etched in an appropriate amount, and the etching profile is also excellent. When included in the above-described range, the etching rate may be lowered, and a defect may occur in the etching profile, and residues may occur. If the above-mentioned range is exceeded, overetching may occur, cracks may occur in the photoresist, and the etching solution may penetrate into the cracks, thereby causing a short circuit.
상기 무기산은 질산, 황산, 인산 및 과염소산으로 이루어진 군에서 선택되는 것이 바람직하다.The inorganic acid is preferably selected from the group consisting of nitric acid, sulfuric acid, phosphoric acid and perchloric acid.
상기 무기산염은 질산, 황산, 인산 및 과염소산의 칼륨염, 나트륨 및 암모늄염으로 이루어진 군에서 선택되는 것이 바람직하다.The inorganic acid salt is preferably selected from the group consisting of potassium salts, sodium and ammonium salts of nitric acid, sulfuric acid, phosphoric acid and perchloric acid.
본 발명의 식각액 조성물에 포함되는 고리형 아민 화합물은 구리를 포함하는 막의 식각시, 프로파일을 형성한다. 조성물 총 중량에 대하여, 상기 고리형 아민 화합물은 0.3~5 중량%로 포함되고, 0.5~3 중량%로 포함되는 것이 바람직하다. 상술한 범위로 포함되면, 적당한 구리 식각율과 테이퍼 앵글을 형성하고, 사이드 에칭량을 조절하는 효과가 있다.The cyclic amine compound included in the etchant composition of the present invention forms a profile upon etching of a film containing copper. Based on the total weight of the composition, the cyclic amine compound is contained in 0.3 to 5% by weight, preferably contained in 0.5 to 3% by weight. When included in the above-described range, there is an effect of forming an appropriate copper etching rate and taper angle, and adjusting the side etching amount.
상기 고리형 아민 화합물이 0.3 중량% 미만으로 포함되면 구리막의 식각율이 높아져 과식각의 위험이 있으며, 5 중량%를 초과하는 경우는 구리의 식각율이 낮아져 원하는 정도의 식각을 이루지 못하게 될 수 있다.If the cyclic amine compound is included in less than 0.3% by weight, the etching rate of the copper film is increased to increase the risk of overetching. When the cyclic amine compound is included in an amount of more than 5% by weight, the etching rate of copper may be lowered to prevent the desired degree of etching. .
상기 고리형 아민 화합물은 5-아미노테트라졸, 톨리트리아졸, 벤조트리아졸 및 메틸트리아졸으로 이루어진 군에서 선택되는 1종 또는 2종 이상의 것이 바람직하다.The cyclic amine compound is preferably one or two or more selected from the group consisting of 5-aminotetrazole, tolytriazole, benzotriazole and methyltriazole.
본 발명의 식각액 조성물에 포함되는 함염소화합물은 구리를 포함하는 막을 식각하는 보조 산화제로서, 조성물 총 중량에 대하여, 0.1~5 중량%로 포함되고, 0.5~3 중량%로 포함되는 것이 바람직하다. 상술한 범위로 포함되면, 테이퍼 앵글을 보다 효과적으로 형성하는 효과가 있다.The chlorine-containing compound included in the etchant composition of the present invention is an auxiliary oxidant for etching a film containing copper, and is preferably included in an amount of 0.1 to 5% by weight and 0.5 to 3% by weight based on the total weight of the composition. When included in the above-described range, there is an effect of forming the taper angle more effectively.
상기 함염소화합물이 0.1 중량% 미만으로 포함되면 테이퍼 앵글이 너무 낮게 형성되어 테이퍼 경사면이 길어지고, 이로 인해 후속공정에서 문제를 야기시킬 수도 있고, 5 중량%를 초과하는 경우는 테이퍼 앵글이 너무 높게 형성되고 이로 인해 후속공정에서 스텝 커버리지 불량이 발생할 수 있다.When the chlorine-containing compound is included in less than 0.1% by weight, the tapered angle is formed too low, the tapered inclined surface is long, which may cause problems in the subsequent process, if it exceeds 5% by weight, the tapered angle is too high Which may result in poor step coverage in subsequent processes.
상기 함염소화합물은 염소 이온으로 해리될 수 있는 화합물을 의미하며, 염산, 염화나트륨, 염화칼륨 및 염화암모늄(NH4Cl)으로 이루어진 군에서 선택되는 1종 또는 2종 이상의 것이 바람직하다.The chlorine-containing compound means a compound capable of dissociating into chlorine ions, and preferably one or two or more selected from the group consisting of hydrochloric acid, sodium chloride, potassium chloride and ammonium chloride (NH 4 Cl).
본 발명의 식각액 조성물에 포함되는 p-톨루엔 술폰산(p-toluene sulfonic acid)은 식각액 제조 후, 자체 경시에 의해 조성이 변하여 식각 특성이 달라지는 것을 방지하고, 식각액을 장기간 동안 보관할 수 있게 한다. 상기 p-톨루엔 술폰산은 조성물 총 중량에 대하여 0.1~5 중량%로 포함되고, 0.5~3 중량%로 포함되는 것이 바람직하다. 상술한 범위 미만으로 포함되면 자체 경시에 따른 약액의 변화를 막기 힘들고, 상술한 범위를 초과하여 포함되면 자체경시를 방지할 수 있으나, 과에칭 현상이 발생하여 프로파일이 우수하지 못하다.The p-toluene sulfonic acid included in the etchant composition of the present invention prevents a change in composition by changing its composition over time after preparation of the etchant, and prevents the etching solution from being stored for a long time. The p-toluene sulfonic acid is included in 0.1 to 5% by weight, and preferably in 0.5 to 3% by weight based on the total weight of the composition. If it is included below the above-mentioned range, it is difficult to prevent the change of the chemical solution due to its own over time, and if it exceeds the above-mentioned range, it is possible to prevent the self-timed, but the over-etching phenomenon occurs, the profile is not excellent.
본 발명의 식각액 조성물에 포함되는 물은 탈이온수를 의미하며 반도체 공정용을 사용하며, 바람직하게는 18㏁·㎝ 이상의 물을 사용한다. 조성물 총 중량에 대하여, 상기 물은 본 발명의 식각액 조성물의 총 중량이 100 중량%가 되도록 잔량 포함된다. Water included in the etchant composition of the present invention means deionized water, and is used for the semiconductor process, preferably water of 18 Pa · cm or more. With respect to the total weight of the composition, the amount of water is included so that the total weight of the etchant composition of the present invention is 100% by weight.
본 발명의 식각액 조성물은 상기에 언급된 성분들 외에 식각조절제, 계면활성제, 금속 이온 봉쇄제 및 부식 방지제로 이루어진 군으로부터 선택되는 1종 또는 2종 이상을 함유할 수 있다.The etchant composition of the present invention may contain one or two or more selected from the group consisting of an etch regulator, a surfactant, a metal ion sequestrant and a corrosion inhibitor in addition to the above-mentioned components.
본 발명의 식각액 조성물은 구리와 티타늄을 포함하는 금속막, 특히 Cu/Ti 구조의 이중막에 특히 효과적이다. 또한 IZO 또는 a-ITO의 식각에도 효과적이다.The etchant composition of the present invention is particularly effective for metal films containing copper and titanium, especially for double films of Cu / Ti structures. It is also effective for etching IZO or a-ITO.
이하에서, 실시예 및 시험예를 통하여 본 발명을 더욱 상세하게 설명한다. 그러나, 본 발명의 범위가 하기의 실시예 및 시험예에 의하여 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail with reference to Examples and Test Examples. However, the scope of the present invention is not limited by the following examples and test examples.
실시예1 및 비교예1: 식각액 조성물의 제조Example 1 and Comparative Example 1: Preparation of the etchant composition
하기 표 1에 기재된 성분 및 조성비에 따라 식각액 조성물이 180kg이 되도록 제조하였다. To the etchant composition according to the component and composition ratio shown in Table 1 to 180kg was prepared.
표 1
APS(중량%) ABF(중량%) HNO3(중량%) ATZ(중량%) NaCl(중량%) PTA(중량%) 물(중량%)
실시예1 10 0.5 3 1 1 2 잔량
비교예1 10 0.5 3 1 1 0 잔량
Table 1
APS (% by weight) ABF (% by weight) HNO 3 (% by weight) ATZ (% by weight) NaCl (% by weight) PTA (% by weight) Water (% by weight)
Example 1 10 0.5 3 One One 2 Remaining amount
Comparative Example 1 10 0.5 3 One One 0 Remaining amount
*APS: 과황산암모늄* APS: Ammonium Persulfate
ABF: 중불화암모늄ABF: Ammonium Bifluoride
ATZ: 5-아미노 테트라졸ATZ: 5-amino tetrazole
PTA: p-톨루엔 술폰산PTA: p-toluene sulfonic acid
시험예: 식각액 조성물의 특성 평가Test Example: Evaluation of Properties of Etch Liquid Composition
글래스 위에 SiNx층을 증착하고, 상기 SiNx층 위에 구리막을 적층하고, 상기 구리막 상에 티타늄막을 적층하고, 상기 티타늄막 상에 일정한 형태의 모양으로 포토레지스트 패턴을 형성하여 기판을 제조하였다. 상기 기판을 다이아몬드 칼을 이용하여 550×650㎜로 잘라 시편을 제조하였다.A substrate was manufactured by depositing a SiNx layer on glass, stacking a copper film on the SiNx layer, a titanium film on the copper film, and forming a photoresist pattern on the titanium film in a predetermined shape. The substrate was cut into 550 × 650 mm using a diamond knife to prepare a specimen.
<식각특성 평가방법><Etch Characteristic Evaluation Method>
분사식 식각 방식의 실험장비(제조사: SEMES사, 모델명: ETCHER(TFT)) 내에 실시예1 및 비교예1의 식각액 조성물을 넣고 온도를 25℃로 세팅하여 가온하였다. 그 후, 온도가 30±0.1℃에 도달한 후, 식각 공정을 수행하였다. 총 식각 시간을 EPD를 기준으로 하여 40%를 주어 실시하였다. 시편을 넣고 분사를 시작하여 식각이 다 되면 꺼내어 탈이온수로 세정한 후, 열풍(熱風) 건조장치를 이용하여 건조하고, 포토레지스트(PR) 박리기(stripper)를 이용하여 포토 레지스트를 제거하였다. 세정 및 건조 후 전자주사현미경(SEM; 제조사: HITACHI사, 모델명: S-4700)을 이용하여 식각 특성을 평가하여, 그 결과를 표 2에 나타내었다.The etching liquid compositions of Example 1 and Comparative Example 1 were placed in an experimental equipment of a spray etching method (manufacturer: SEMES, model name: ETCHER (TFT)), and the temperature was set to 25 ° C. and heated. Then, after the temperature reached 30 ± 0.1 ℃, the etching process was performed. Total etch time was given at 40% based on EPD. Insert the specimen, start spraying, and when the etching is complete, taken out, washed with deionized water, dried using a hot air drying apparatus, and removed the photoresist using a photoresist stripper (PR) stripper. After washing and drying, the etching characteristics were evaluated using an electron scanning microscope (SEM; manufacturer: HITACHI, model name: S-4700), and the results are shown in Table 2.
<보관특성 평가방법><Evaluation of Storage Characteristics>
실시예1 및 비교예1의 식각액 조성물을 충분히 많은 양으로 제조하여 레퍼런스 식각(reference etch)을 진행하고 남은 약액을 25℃ 에서 보관하면서 계획된 날짜(여기서는 5일을 기준)가 경과한 후, 동일한 조건으로 다시 식각 테스트를 진행하여 레퍼런스 테스트 결과와 비교하여 실험을 진행하였다.Etching liquid composition of Example 1 and Comparative Example 1 was prepared in a sufficient amount to proceed the reference etching (reference etch) and the remaining conditions of the stored solution at 25 ℃ after the planned date (here 5 days) after the same conditions, The etching test was performed again, and the experiment was performed by comparing with the reference test result.
표 2
식각특성 보관특성
실시예1 ◎ ◎
비교예1 ◎ X
TABLE 2
Etching characteristics Storage characteristics
Example 1 ◎ ◎
Comparative Example 1 ◎ X
<식각특성>Etch Characteristics
◎: 매우 우수(CD Skew: ≤1㎛, 테이퍼각: 40°~ 60°), ◎: very good (CD Skew: ≤1 μm, taper angle: 40 ° to 60 °),
○: 우수(CD Skew: ≤1.5㎛, 테이퍼각: 30°~ 60°)○: Excellent (CD Skew: ≤1.5 μm, taper angle: 30 ° to 60 °)
△: 양호(CD Skew: ≤2㎛, 테이퍼각: 30°~ 60°)(Triangle | delta): Good (CD skew: ≤2 micrometer, taper angle: 30 degrees-60 degrees)
×: 불량(금속막 소실 및 잔사 발생),X: defective (metal film loss and residue),
<보관특성><Storage Characteristics>
◎: 매우 우수 (매수경시 진행시, 5일 경과 후 식각프로파일 우수)◎: Very good (Excellent etching profile after 5 days)
×: 불량 (매수경시 진행시, 5일 경과 후 식각프로파일 양호 이하 수준)×: Poor (at the time of purchase, the etch profile after 5 days or less)
표 2를 참조하면, 본 발명을 따른 실시예1의 조성물을 이용하면 식각특성 및 보관특성이 모두 우수한 것을 알 수 있다. 반면에, p-톨루엔 술폰산을 포함하지 않는 비교예1의 조성물의 경우 보관특성이 불량인 것을 알 수 있다.Referring to Table 2, it can be seen that using the composition of Example 1 according to the present invention, both the etching characteristics and the storage characteristics are excellent. On the other hand, the composition of Comparative Example 1 that does not include p-toluene sulfonic acid can be seen that the storage characteristics are poor.

Claims (10)

  1. 조성물 총 중량에 대하여,Regarding the total weight of the composition,
    과황산염 5~20 중량%;Persulfate 5-20 wt%;
    함불소화합물 0.01~2 중량%;0.01 to 2 wt% fluorine-containing compound;
    무기산, 무기산염 및 이들의 혼합물 중에서 선택되는 1종 이상 1~10 중량%;1-10% by weight of one or more selected from inorganic acids, inorganic acid salts and mixtures thereof;
    고리형 아민화합물 0.3~5 중량%;0.3-5 weight% of a cyclic amine compound;
    함염소화합물 0.1~5 중량%; 0.1 to 5% by weight of chlorine-containing compound;
    p-톨루엔 술폰산(p-toluene sulfonic acid) 0.1~5 중량%; 및0.1-5% by weight of p-toluene sulfonic acid; And
    물 잔량을 포함하는 것을 특징으로 하는 구리와 티타늄을 포함하는 금속막용 식각액 조성물. Etching liquid composition for a metal film comprising copper and titanium, characterized in that it comprises a residual amount of water.
  2. 청구항 1에 있어서, The method according to claim 1,
    상기 과황산염은 과황산암모늄, 과황산소다 및 과황산칼륨으로 이루어진 군에서 선택되는 1종 이상의 것임을 특징으로 하는 구리와 티타늄을 포함하는 금속막용 식각액 조성물.The persulfate is an etching solution composition for a metal film containing copper and titanium, characterized in that at least one selected from the group consisting of ammonium persulfate, sodium persulfate and potassium persulfate.
  3. 청구항 1에 있어서, The method according to claim 1,
    상기 함불소화합물은 불화암모늄, 불화나트륨, 불화칼륨, 중불화암모늄, 중불화나트륨 및 중불화칼륨으로 이루어진 군에서 선택되는 1종 이상의 것임을 특징으로 하는 구리와 티타늄을 포함하는 금속막용 식각액 조성물.The fluorine-containing compound is an etching solution composition for a metal film containing copper and titanium, characterized in that at least one selected from the group consisting of ammonium fluoride, sodium fluoride, potassium fluoride, ammonium bifluoride, sodium bifluoride and potassium bifluoride.
  4. 청구항 1에 있어서, The method according to claim 1,
    상기 무기산은 질산, 황산, 인산 및 과염소산으로 이루어진 군에서 선택되고, 상기 무기산염은 질산, 황산, 인산 및 과염소산의 칼륨염, 나트륨 및 암모늄염으로 이루어진 군에서 선택되는 것을 특징으로 하는 구리와 티타늄을 포함하는 금속막용 식각액 조성물.The inorganic acid is selected from the group consisting of nitric acid, sulfuric acid, phosphoric acid and perchloric acid, and the inorganic acid salt is selected from the group consisting of potassium, sodium and ammonium salts of nitric acid, sulfuric acid, phosphoric acid and perchloric acid. Etching liquid composition for a metal film.
  5. 청구항 1에 있어서, The method according to claim 1,
    상기 고리형 아민화합물은 5-아미노 테트라졸, 톨리트리아졸, 벤조트리아졸, 및 메틸벤조트리아졸로 이루어진 군에서 선택되는 1종 이상의 것임을 특징으로 하는 구리와 티타늄을 포함하는 금속막용 식각액 조성물.The cyclic amine compound is an etching solution composition for a metal film containing copper and titanium, characterized in that at least one selected from the group consisting of 5-amino tetrazole, tolytriazole, benzotriazole, and methyl benzotriazole.
  6. 청구항 1에 있어서, The method according to claim 1,
    상기 함염소화합물은 염산, 염화나트륨, 염화칼륨 및 염화암모늄으로 이루어진 군에서 선택되는 1종 이상의 것임을 특징으로 하는 구리와 티타늄을 포함하는 금속막용 식각액 조성물.The chlorine-containing compound is an etching solution composition for a metal film containing copper and titanium, characterized in that at least one selected from the group consisting of hydrochloric acid, sodium chloride, potassium chloride and ammonium chloride.
  7. 청구항 1 내지 청구항 6 중의 어느 한 항의 식각액 조성물을 사용하여 구리와 티타늄을 포함하는 금속막을 식각하는 공정을 포함하는 것을 특징으로 하는 반도체 소자의 제조방법. A method of manufacturing a semiconductor device, comprising the step of etching a metal film containing copper and titanium using the etchant composition according to any one of claims 1 to 6.
  8. 청구항 1 내지 청구항 6 중의 어느 한 항의 식각액 조성물을 사용하여 구리와 티타늄을 포함하는 금속막을 식각하는 공정을 포함하는 것을 특징으로 하는 평판표시소자의 제조방법. A method of manufacturing a flat panel display device comprising the step of etching a metal film containing copper and titanium using the etchant composition according to any one of claims 1 to 6.
  9. 청구항 1 내지 청구항 6 중의 어느 한 항의 식각액 조성물을 사용하여 제조되는 반도체 소자. The semiconductor device manufactured using the etching liquid composition of any one of Claims 1-6.
  10. 청구항 1 내지 청구항 6 중의 어느 한 항의 시각액 조성물을 사용하여 제조되는 평판표시소자.The flat panel display device manufactured using the visual fluid composition of any one of Claims 1-6.
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KR20110121121A (en) 2011-11-07
CN102822391A (en) 2012-12-12

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