WO2011019222A9 - Etchant composition for forming copper interconnects - Google Patents

Etchant composition for forming copper interconnects Download PDF

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Publication number
WO2011019222A9
WO2011019222A9 PCT/KR2010/005310 KR2010005310W WO2011019222A9 WO 2011019222 A9 WO2011019222 A9 WO 2011019222A9 KR 2010005310 W KR2010005310 W KR 2010005310W WO 2011019222 A9 WO2011019222 A9 WO 2011019222A9
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WO
WIPO (PCT)
Prior art keywords
acid
based metal
metal film
etching
copper
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PCT/KR2010/005310
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French (fr)
Korean (ko)
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WO2011019222A3 (en
WO2011019222A2 (en
Inventor
양승재
임민기
권오병
이유진
유인호
박영철
신혜라
이준우
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동우 화인켐 주식회사
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Priority claimed from KR1020090074828A external-priority patent/KR101805185B1/en
Priority claimed from KR1020090084866A external-priority patent/KR101805186B1/en
Priority claimed from KR1020090085436A external-priority patent/KR101745721B1/en
Application filed by 동우 화인켐 주식회사 filed Critical 동우 화인켐 주식회사
Priority to CN2010800362125A priority Critical patent/CN102471688A/en
Publication of WO2011019222A2 publication Critical patent/WO2011019222A2/en
Publication of WO2011019222A9 publication Critical patent/WO2011019222A9/en
Publication of WO2011019222A3 publication Critical patent/WO2011019222A3/en

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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F1/00—Etching metallic material by chemical means
    • C23F1/10—Etching compositions
    • C23F1/14—Aqueous compositions
    • C23F1/16—Acidic compositions
    • C23F1/26—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
    • C23F1/02—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
    • 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
    • C23F1/44—Compositions for etching metallic material from a metallic material substrate of different composition
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31—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

Definitions

  • the present invention relates to a wet etchant composition for a multilayer including a copper-based metal film and a titanium-based metal film.
  • the process of forming metal wiring on a substrate in a semiconductor device and a flat panel display device is performed by a metal film forming process by sputtering, a photoresist forming process and an etching process for a selective region by photoresist coating, exposure and development. It consists of the steps, and the washing process before and after an individual unit process, etc. are included.
  • the etching process refers to a process of leaving a metal film in a selective region using a photoresist mask, and typically, dry etching using plasma or wet etching using an etching solution is used.
  • chromium Cr resistivity: 12.7 ⁇ 10 -8 ⁇ m
  • molybdenum Mo resistivity: 5 ⁇ 10 -8 ⁇ m
  • aluminum Al resistivity: 2.65 ⁇ 10 -8 ⁇ m
  • alloys thereof are difficult to use as gates and data wirings used in large-sized TFT LCDs.
  • a copper film which is one of the new low resistance metal films.
  • the copper film is known to have an advantage that the resistance is significantly lower than that of the aluminum film or the chromium film and that there is no big problem in the environment.
  • the copper film has many disadvantages in the process of applying and patterning the photoresist, and the disadvantages of poor adhesion to the silicon insulating film have been found.
  • a material which is particularly in the limelight is a copper-titanium film.
  • an etchant for such a copper-titanium film an etchant described in Korean Laid-Open Patent Publication No. 2001-11390 is known. That is, the patent document includes a step of sequentially depositing a copper film and a titanium film on a substrate and simultaneously forming a gate electrode by simultaneously etching a copper film as a first gate metal and a titanium film as a second gate metal according to a predetermined pattern.
  • a method of forming a gate electrode of a thin film transistor and a mixed etchant of HF, HNO 3 and CH 3 COOH used in such an etching process are disclosed.
  • the present invention is to solve the above problems of the prior art, to provide an excellent etching profile for a multi-layer including a copper-based metal film and a titanium-based metal film, and to minimize damage and residue generation to the substrate and the lower insulating film It is an object to provide an etching solution composition.
  • the present invention relates to a copper-based metal film comprising 0.1 to 5% by weight of an inorganic salt oxidizing agent, 0.1 to 5% by weight of a chlorine-containing compound, 0.01 to 2% by weight of a fluorine-containing compound and a balance of water.
  • an etching liquid composition of a multilayer including a titanium-based metal film is provided.
  • the etchant composition of the present invention provides an excellent etching profile during the etching of multiple films including a copper-based metal film and a titanium-based metal film, and the subsequent process can be stably performed by minimizing damage and residues on the substrate and the lower insulating film. To be.
  • the etching liquid composition of the present invention as in the case of chromium or the like, it is possible to manufacture a flat panel display in an environmentally friendly manner by making it possible to replace the substances defined as environmentally harmful substances with copper.
  • 1, 3 and 5 are electron scanning micrographs showing the results of etching the Cu / Ti double layer with the etchant composition of Examples 1, 11 and 19, respectively.
  • the present invention comprises a copper-based metal film and a titanium-based metal film containing 0.1 to 5% by weight of an inorganic salt oxidizing agent, 0.1 to 5% by weight of a chlorine-containing compound, 0.01 to 2% by weight of a fluorine-containing compound and a balance of water
  • the present invention relates to an etching liquid composition of a multilayer.
  • the copper-based metal film means a copper film or a copper alloy film
  • the titanium-based metal film means a titanium film or a titanium alloy film.
  • the multilayer film including the copper-based metal film and the titanium-based metal film may include, for example, a "titanium-based metal film / copper-based metal film" and a titanium-based metal film having a copper-based metal film as a lower film and a titanium-based metal film as an upper film.
  • a double film of "copper metal film / titanium metal film” having a lower film and a copper metal film as an upper film, and further comprising a titanium metal film / copper metal film / titanium metal film or a copper metal film / It also includes the case of multiple films of triplet or more in which copper-based metals and titanium-based metal films are alternately laminated, such as titanium-based metal films / copper-based metal films.
  • Such a multilayer may determine the structure of the multilayer in consideration of a combination of materials constituting the membrane disposed on the upper portion of the membrane or the membrane disposed below, or adhesion to the membranes.
  • the copper film and the titanium film are not limited in thickness to each other, and various combinations are possible. For example, the thickness of the copper film may be formed larger than the thickness of the titanium film, or may be formed small.
  • the etchant composition comprising the inorganic salt oxidizing agent, the chlorine-containing compound, the fluorine-containing compound and the water of the present invention can be prepared by a conventionally known method, and preferably has a purity for semiconductor processing.
  • the inorganic salt oxidizing agent is a main component for etching the copper-based metal film, and is contained in an amount of 0.1 to 5% by weight based on the total weight of the composition, and when it is contained below 0.1% by weight, the etching rate of the copper-based metal film is lowered. There is no advantage, and if it exceeds 5% by weight, overetching may occur and wiring may be lost.
  • Examples of the inorganic salt oxidizing agent include CuCl 2 , Cu (NO 3 ) 2 , CuSO 4 , and the like, and these may be used alone or in combination of two or more.
  • the chlorine-containing compound in the present invention means a compound capable of dissociating chlorine ions, and serves as an auxiliary oxidant for etching the copper-based metal film.
  • the chlorine-containing compound is preferably included in 0.1 to 5% by weight, more preferably in 0.1 to 3% by weight based on the total weight of the composition.
  • the chlorine-containing compound is less than 0.1% by weight, the etching rate of the copper-based metal film is lowered, so that the etching profile is poor.
  • overetching may occur and wiring may be lost.
  • chlorine-containing compound examples include HCl, NaCl, KCl, NH 4 Cl, and the like, which may be used alone or in combination of two or more.
  • NaCl and NH 4 Cl may be more preferably used among them.
  • the fluorine-containing compound serves as a main component for etching the titanium-based metal film, it is contained in 0.01 to 2% by weight relative to the total weight of the composition. If the content is less than 0.01% by weight, the etching rate of the titanium-based metal film may be lowered, and residues may occur. If the content exceeds 2% by weight, the substrate (Glass, etc.) and the insulating film (silicon film, etc.) may be damaged. .
  • the fluorine-containing compound means a compound capable of dissociating fluorine ions or polyatomic fluorine ions.
  • Examples of the fluorine-containing compound include ammonium fluoride, sodium fluoride, potassium fluoride, ammonium bifluoride, sodium bifluoride, potassium bifluoride, and the like. These may be used alone or in combination of two or more.
  • Water used in the present invention means deionized water and is used for the semiconductor process, preferably water of 18 dl / cm or more.
  • the etchant composition of the present invention may further include one or more etching control agents selected from the group consisting of organic and inorganic acids in addition to the above-mentioned components.
  • the etching control agent may be included in 0.1 to 10% by weight based on the total weight of the composition.
  • the organic acid in the etching control agent serves to control the etching rate between the copper and the other metal in the film containing copper by inhibiting the etching of copper.
  • an organic acid is used as an etching control agent, it is preferably included in 0.1 to 10% by weight based on the total weight of the etching liquid composition. If the organic acid is included in less than 0.1% by weight, the etching rate of copper and titanium may be too fast to increase side etching, and a bad profile may be generated, and if it exceeds 10% by weight, the etching rate of copper and titanium may be too high. It can be suppressed and residues can be generated.
  • the organic acid may include citric acid, glycolic acid, glycolic acid, acetic acid, sulfonic acid, oxalic acid, water-soluble compounds having an amino group and a carboxyl group, and the like.
  • the water-soluble compound having an amino group and a carboxyl group not only serves as the above-mentioned etch control agent, but also prevents resorption by chelating copper ions dissociated at the time of etching, thereby increasing the number of processed sheets of the substrate. More preferably.
  • water-soluble compound having an amino group and a carboxyl group examples include alanine, aminobutyric acid, glutamic acid, glycine, glycine, iminodiacetic acid, nitrilotriacetic acid and sarco And sarcosine, and these may be used alone or in combination of two or more.
  • the inorganic acid plays a role opposite to that of the organic acid. That is, the inorganic acid oxidizes and etches the copper-based metal film and serves to oxidize the titanium-based metal film.
  • the inorganic acid is used as an etching control agent, it is preferably contained in 0.1 to 10% by weight based on the total weight of the etching liquid composition.
  • the inorganic acid is contained in less than 0.1% by weight, the etching rate of the copper-based metal film and the titanium-based metal film may be lowered, resulting in poor etching profiles and residues.
  • the inorganic acid exceeds 10% by weight, overetching and photoresist cracks ( This can cause a short circuit due to chemical infiltration.
  • inorganic acid examples include nitric acid, sulfuric acid, phosphoric acid, perchloric acid, and the like. These may be used alone or in combination of two or more.
  • the etchant composition of the present invention may further comprise at least one of a surfactant, a metal ion sequestrant, a corrosion inhibitor and a pH adjusting agent in addition to the above-mentioned components.
  • It provides a method for producing a thin film transistor comprising the step of forming a pattern of metal wiring using the etchant composition.
  • Example 1 CuCl 2 NaCl NH 4 FHF C 6 H 8 O 7 water
  • Example 2 0.3 1.0 0.2 0.5 98.0
  • Example 3 0.3 0.5 0.2 1.0 98.0
  • Example 4 0.5 0.5 0.2 2.0 96.8
  • Example 5 0.5 1.0 0.2 0.5 97.8
  • Example 6 1.0 1.0 0.3 1.0 96.7
  • Example 7 1.0 0.2 0.3 2.0 96.5
  • Test Example 1 Evaluation of etching characteristics of the etching solution composition of Examples 1 to 8 and Comparative Examples 1 to 3
  • a copper / titanium bilayer was deposited on a silicon layer on a glass substrate, and a substrate on which a photoresist was patterned in a uniform form was used as a specimen.
  • Etching liquid prepared in Examples 1 to 8 and Comparative Examples 1 to 3 were put into a spraying etching apparatus (SEMES, model name: ETCHER (TFT)), and the temperature was set to 25 ° C., followed by heating. After reaching 25 ⁇ 0.1 ° C., an etching process was performed. Total etch time was given at 30% 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.
  • SEMES spraying etching apparatus
  • PR photoresist stripper
  • the etchant composition of Examples 1 to 8 had excellent etching profiles, no damage to the glass substrate and the silicon layer, and showed excellent etching characteristics without residue.
  • Comparative Examples 1 to The etchant composition of 3 was found to be unsuitable for use because of poor etching profiles, unetch of copper and titanium films, and loss of copper patterns were observed (see FIGS. 1 and 2).
  • the etchant composition was prepared to be 180 kg.
  • Example 9 0.3 0.2 0.2 One 98.3 Example 10 0.4 0.3 0.1 0.5 98.7 Example 11 0.5 0.3 0.2 One 98 Example 12 0.5 0.5 0.1 0.5 98.4 Example 13 0.7 0.3 0.2 One 97.8 Example 14 0.7 0.5 0.3 One 97.5 Example 15 One 0.5 0.2 One 97.3 Example 16 2 One 0.3 One 95.7 Example 17 3 One 0.3 One 94.7 Example 18 3 1.2 0.3 One 94.5 Comparative Example 4 0.05 0.01 0.2 One 98.74 Comparative Example 5 One 0.5 0.02 0.5 97.98 Comparative Example 6 7 One 0.2 2 89.8 Comparative Example 7 0.5 0.3 2.5 One 95.7 Comparative Example 8 0.7 0.3 0.2 12 86.8
  • Test Example 3 Evaluation of the etching properties of the etching solution composition of Examples 9 to 18 and Comparative Examples 4 to 8
  • the etchant composition of Examples 9 to 18 showed excellent etching profiles, no damage to the glass substrate and the silicon layer, and showed excellent etching characteristics without residue.
  • Comparative Examples 4 to The etchant composition of 8 was found to be unsuitable for use because of poor etching profiles, unetch of copper and titanium films and loss of copper patterns were observed (see FIGS. 3 and 4).
  • Example 19 0.3 0.1 0.2 0.5 98.9
  • Example 20 0.3 0.5 0.2 0.5 98.5
  • Example 21 0.5 0.2 0.2 1.0 98.1
  • Example 22 0.5 0.5 0.2 0.7 98.1
  • Example 23 1.0 0.3 0.2 0.5 98.0
  • Example 24 1.0 0.5 0.3 1.0 97.2
  • Example 25 3.0 0.2 0.3 2.0 94.5
  • Example 26 3.0 1.0 0.3 2.0 93.7
  • the etchant composition of Examples 19 to 26 exhibited excellent etching characteristics, no damage to the glass substrate and the silicon layer, and excellent etching characteristics without residue.
  • Comparative Examples 9 to The etchant composition of 11 was found to be unsuitable for use because of poor etching profiles, unetch of copper and titanium films and loss of copper patterns were observed (see FIGS. 5 and 6).

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Abstract

The present invention relates to a wet etchant composition to a multilayer film comprising a copper-based metal layer and a titanium-based metal layer. The etchant composition of the present invention provides an excellent etching profile in case of etching said multilayer film, and minimizes the damage of a glass substrate and a lower insulating layer and the generation of residue, thereby enabling the stable performance of a subsequent process.

Description

구리 배선의 형성을 위한 식각액 조성물Etch solution composition for formation of copper wiring
본 발명은 구리계 금속막과 티타늄계 금속막을 포함하는 다중막에 대한 습식 식각액 조성물에 관한 것이다.The present invention relates to a wet etchant composition for a multilayer including a copper-based metal film and a titanium-based metal film.
일반적으로 반도체 장치 및 평판표시장치에서 기판 상에 금속배선을 형성하는 과정은 스퍼터링에 의한 금속막 형성공정, 포토레지스트 도포, 노광 및 현상에 의한 선택적인 영역에 대한 포토레지스트 형성공정 및 식각공정에 의한 단계로 구성되고, 개별적인 단위 공정 전후의 세정공정 등을 포함한다.In general, the process of forming metal wiring on a substrate in a semiconductor device and a flat panel display device is performed by a metal film forming process by sputtering, a photoresist forming process and an etching process for a selective region by photoresist coating, exposure and development. It consists of the steps, and the washing process before and after an individual unit process, etc. are included.
상기 식각공정은 포토레지스트 마스크를 사용하여 선택적인 영역에 금속막을 남기는 공정을 의미하며, 통상적으로 플라즈마 등을 이용한 건식 식각 또는 식각액을 사용하는 습식 식각이 사용된다.The etching process refers to a process of leaving a metal film in a selective region using a photoresist mask, and typically, dry etching using plasma or wet etching using an etching solution is used.
근래들어, 반도체장치나 평판표시장치에서 금속배선의 저항이 주요한 관심사로 떠오르고 있다. 저항은 RC 신호지연을 유발하는 주요한 인자이므로, 평판표시장치에서 패널크기를 증가시키고 고해상도를 실현하는데 있어서 매우 중요하다.In recent years, the resistance of metal wiring has emerged as a major concern in semiconductor devices and flat panel display devices. Since resistance is a major factor causing RC signal delay, it is very important for increasing panel size and high resolution in flat panel displays.
평판표시장치에서 필수적으로 요구되는 RC 신호지연의 감소를 실현하기 위해서는 저저항의 물질개발이 필수적이며, 종래에 주로 사용되었던 크롬(Cr 비저항: 12.7×10-8Ωm), 몰리브덴(Mo 비저항:5×10-8Ωm), 알루미늄(Al 비저항: 2.65×10-8Ωm) 및 이들의 합금은 대형 TFT LCD 에 사용되는 게이트 및 데이터 배선 등으로 이용하기 어려운 실정이다.In order to realize a reduction in the RC delay signal which is essentially required in the flat panel display device, and the essential material development of low resistance, mainly used was chromium (Cr resistivity: 12.7 × 10 -8 Ωm) in the art, molybdenum (Mo resistivity: 5 × 10 -8 Ωm), aluminum (Al resistivity: 2.65 × 10 -8 Ωm) and alloys thereof are difficult to use as gates and data wirings used in large-sized TFT LCDs.
이와 같은 배경하에서, 새로운 저저항 금속막 중 하나인 구리막에 대한 관심이 높다. 구리막은 알루미늄막이나 크롬막보다 저항이 현저하게 낮고 환경적으로도 큰 문제가 없는 장점이 있는 것으로 알려지고 있기 때문이다. 그러나, 구리 막은 포토레지스트를 도포하고 패터닝하는 공정상 어려운 점들이 많으며, 실리콘 절연막과의 접착력이 나쁜 단점이 발견되었다.Under such a background, there is a high interest in a copper film, which is one of the new low resistance metal films. This is because the copper film is known to have an advantage that the resistance is significantly lower than that of the aluminum film or the chromium film and that there is no big problem in the environment. However, the copper film has many disadvantages in the process of applying and patterning the photoresist, and the disadvantages of poor adhesion to the silicon insulating film have been found.
이에 따라, 저저항 구리 단일막의 단점을 보완하는 다중 금속막에 대한 연구가 진행되고 있으며, 그 중에서도, 특히 각광 받는 물질이 구리-티타늄 막이다. 이러한 구리-티타늄 막에 대한 식각액으로 종래에 알려진 것으로는 대한민국 공개특허공보 제 2001-11390호에 기재된 식각액을 들 수 있다. 즉, 상기 특허문헌은 기판상에 구리막과 티타늄막을 차례로 증착하는 단계와 소정의 패턴에 따라 제 1 게이트금속인 구리막과 제 2 게이트금속인 티타늄막을 동시에 식각하여 게이트전극을 형성하는 단계를 포함하는 박막트랜지스터의 게이트전극 형성방법과 이러한 식각공정에 사용되는 HF, HNO3 및 CH3COOH의 혼합 식각액을 개시하고 있다.Accordingly, researches on multiple metal films that compensate for the shortcomings of the low-resistance copper single layer have been in progress, and among them, a material which is particularly in the limelight is a copper-titanium film. As an etchant for such a copper-titanium film, an etchant described in Korean Laid-Open Patent Publication No. 2001-11390 is known. That is, the patent document includes a step of sequentially depositing a copper film and a titanium film on a substrate and simultaneously forming a gate electrode by simultaneously etching a copper film as a first gate metal and a titanium film as a second gate metal according to a predetermined pattern. A method of forming a gate electrode of a thin film transistor and a mixed etchant of HF, HNO 3 and CH 3 COOH used in such an etching process are disclosed.
그러나, 구리-티타늄 막의 식각에 상기의 혼합 식각액과 같이 구리막에 대한 식각용액과 티타늄막의 식각용액을 단순히 혼합한 식각액을 사용하는 경우는 식각 프로파일이 불량하고, 후속공정에도 어려움이 따르며, 특히 티타늄 막의 식각에 쓰이는 플루오린 이온(F-)이 글래스 기판과 실리콘층에 손상을 일으키기 때문에 실제로 공정에 사용하기에 적합하지 않다.However, in the case of using an etching solution in which the etching solution for the copper film and the etching solution for the titanium film are simply mixed with the etching solution of the copper-titanium film as described above, the etching profile is poor, and the subsequent process is difficult, especially titanium. Fluorine ions (F − ), which are used to etch the film, cause damage to the glass substrate and the silicon layer and are therefore not suitable for use in the process.
또한 기존의 구리 에칭액인 과산화수소는 에칭 프로파일, 식각 매수 및 경시면에서는 뛰어나지만, 과산화수소 자체의 불안정성에 기인하는 위험성 문제는 아직 해결 되지 않아 식각액으로서 부족함이 있다.In addition, although hydrogen peroxide, which is a conventional copper etching solution, is excellent in etching profile, number of etching, and time-lapse, a risk problem due to instability of hydrogen peroxide itself is not yet solved, and thus there is a shortage as an etching solution.
본 발명은 종래기술의 상기와 같은 문제를 해결하기 위한 것으로서, 구리계 금속막과 티타늄계 금속막을 포함하는 다중막에 대하여 우수한 식각 프로파일을 제공하며, 기판 및 하부 절연막에 대한 손상 및 잔사 발생이 최소화되는 식각액 조성물을 제공하는 것을 목적으로 한다.The present invention is to solve the above problems of the prior art, to provide an excellent etching profile for a multi-layer including a copper-based metal film and a titanium-based metal film, and to minimize damage and residue generation to the substrate and the lower insulating film It is an object to provide an etching solution composition.
본 발명은, 조성물 총 중량에 대하여 0.1~5 중량%의 무기염 산화제, 0.1~5 중량%의 함염소화합물, 0.01~2 중량%의 함불소화합물 및 잔량의 물을 포함하는 구리계 금속막과 티타늄계 금속막을 포함하는 다중막의 식각액 조성물을 제공한다.The present invention relates to a copper-based metal film comprising 0.1 to 5% by weight of an inorganic salt oxidizing agent, 0.1 to 5% by weight of a chlorine-containing compound, 0.01 to 2% by weight of a fluorine-containing compound and a balance of water. Provided is an etching liquid composition of a multilayer including a titanium-based metal film.
본 발명의 식각액 조성물은 구리계 금속막과 티타늄계 금속막을 포함하는 다중막의 식각시에 우수한 식각 프로파일을 제공하며, 기판 및 하부 절연막에 대한 손상 및 잔사 발생을 최소함으로써 후속 공정이 안정적으로 수행될 수 있게 한다. The etchant composition of the present invention provides an excellent etching profile during the etching of multiple films including a copper-based metal film and a titanium-based metal film, and the subsequent process can be stably performed by minimizing damage and residues on the substrate and the lower insulating film. To be.
또한, 본 발명의 식각액 조성물은 크롬 등의 경우처럼 환경유해 물질로 규정된 물질을 구리로 대체하는 것을 가능하게 함으로써 환경친화적으로 평판표시 장치를 제작하는 것을 가능하게 한다.In addition, the etching liquid composition of the present invention, as in the case of chromium or the like, it is possible to manufacture a flat panel display in an environmentally friendly manner by making it possible to replace the substances defined as environmentally harmful substances with copper.
도 1, 3 및 5는 각각 실시예1, 실시예11 및 실시예 19의 식각액 조성물로 Cu/Ti 이중막을 식각한 결과를 나타낸 전자주사현미경 사진이다.1, 3 and 5 are electron scanning micrographs showing the results of etching the Cu / Ti double layer with the etchant composition of Examples 1, 11 and 19, respectively.
도 2, 4 및 6은 각각 비교예1, 비교예6 및 비교예9의 식각액 조성물로 Cu/Ti 이중막을 식각한 결과를 나타내는 전자주사현미경 사진이다.2, 4 and 6 are electron scanning micrographs showing the results of etching the Cu / Ti double layer with the etchant composition of Comparative Example 1, Comparative Example 6 and Comparative Example 9, respectively.
본 발명은 0.1~5 중량%의 무기염 산화제, 0.1~5 중량%의 함염소화합물, 0.01~2 중량%의 함불소화합물 및 잔량의 물을 포함하는 구리계 금속막과 티타늄계 금속막을 포함하는 다중막의 식각액 조성물에 관한 것이다.The present invention comprises a copper-based metal film and a titanium-based metal film containing 0.1 to 5% by weight of an inorganic salt oxidizing agent, 0.1 to 5% by weight of a chlorine-containing compound, 0.01 to 2% by weight of a fluorine-containing compound and a balance of water The present invention relates to an etching liquid composition of a multilayer.
본 발명에서 구리계 금속막은 구리막 또는 구리 합금막을 의미하며, 상기 티타늄계 금속막은 티타늄막 또는 티타늄 합금막을 의미한다. 또한, 상기 구리계 금속막과 티타늄계 금속막을 포함하는 다중막은 예컨대, 구리계 금속막을 하부막으로 하고 티타늄계 금속막을 상부막으로 하는 "티타늄계 금속막/구리막계 금속막", 티타늄계 금속막을 하부막으로 하고 구리계 금속막을 상부막으로 하는 "구리계 금속막/티타늄계 금속막" 의 이중막을 포함하며, 또한 티타늄계 금속막/구리계 금속막/티타늄계 금속막 또는 구리계 금속막/티타늄계 금속막/구리계 금속막처럼 구리계 금속과 티타늄계 금속막이 교대로 적층된 3 중막 이상의 다중막의 경우도 포함한다. 이러한 다중막은 막의 상부에 배치되는 막이나 하부에 배치되는 막을 구성하는 물질 또는 상기 막들과의 접합성(adhesion) 등을 복합적으로 고려하여 다중막의 구조를 결정할 수 있다. 또한, 구리막과 티타늄막은 각각 서로의 두께가 한정되지 않고, 다양한 조합이 가능하다. 예를 들어, 구리막의 두께가 티타늄막의 두께보다 크게 형성될 수도 있고, 작게 형성될 수도 있다. In the present invention, the copper-based metal film means a copper film or a copper alloy film, and the titanium-based metal film means a titanium film or a titanium alloy film. Further, the multilayer film including the copper-based metal film and the titanium-based metal film may include, for example, a "titanium-based metal film / copper-based metal film" and a titanium-based metal film having a copper-based metal film as a lower film and a titanium-based metal film as an upper film. And a double film of "copper metal film / titanium metal film" having a lower film and a copper metal film as an upper film, and further comprising a titanium metal film / copper metal film / titanium metal film or a copper metal film / It also includes the case of multiple films of triplet or more in which copper-based metals and titanium-based metal films are alternately laminated, such as titanium-based metal films / copper-based metal films. Such a multilayer may determine the structure of the multilayer in consideration of a combination of materials constituting the membrane disposed on the upper portion of the membrane or the membrane disposed below, or adhesion to the membranes. In addition, the copper film and the titanium film are not limited in thickness to each other, and various combinations are possible. For example, the thickness of the copper film may be formed larger than the thickness of the titanium film, or may be formed small.
본 발명의 무기염 산화제, 함염소화합물, 함불소화합물 및 물을 포함하는 식각액 조성물은 통상적으로 공지된 방법에 의해서 제조가 가능하며, 반도체 공정용의 순도를 가지는 것이 바람직하다. The etchant composition comprising the inorganic salt oxidizing agent, the chlorine-containing compound, the fluorine-containing compound and the water of the present invention can be prepared by a conventionally known method, and preferably has a purity for semiconductor processing.
본 발명에서 무기염 산화제는 구리계 금속막을 식각하는 주성분으로서, 조성물 총 중량에 대하여 0.1~5 중량%로 함유되며, 0.1중량% 미만으로 함유 되는 경우에는 구리계 금속막의 식각속도가 저하되어 공정상에서 이점이 없으며, 5 중량%를 초과하게 되면 과식각이 발생하여 배선이 소실 될 수 있다.In the present invention, the inorganic salt oxidizing agent is a main component for etching the copper-based metal film, and is contained in an amount of 0.1 to 5% by weight based on the total weight of the composition, and when it is contained below 0.1% by weight, the etching rate of the copper-based metal film is lowered. There is no advantage, and if it exceeds 5% by weight, overetching may occur and wiring may be lost.
상기 무기염 산화제로는 예컨대, CuCl2, Cu(NO3)2, CuSO4 등을 들 수 있으며, 이들은 1종 단독으로 또는 2종 이상이 함께 사용될 수 있다.Examples of the inorganic salt oxidizing agent include CuCl 2 , Cu (NO 3 ) 2 , CuSO 4 , and the like, and these may be used alone or in combination of two or more.
본 발명에서 함염소화합물은, 염소 이온이 해리될 수 있는 화합물을 의미하며, 구리계 금속막을 식각하는 보조 산화제 역할을 한다. 상기 함염소화합물은 조성물 총 중량에 대하여 0.1~5 중량%로 포함되는 것이 바람직하며, 0.1~3중량%로 포함되는 것이 더욱 바람직하다. 상기 함염소화합물이 0.1중량% 미만으로 함유 되는 경우에는 구리계 금속막의 식각속도가 저하되어 식각 프로파일이 불량하게 되며, 5 중량%를 초과하게 되면 과식각이 발생하여 배선이 소실 될 수 있다. The chlorine-containing compound in the present invention means a compound capable of dissociating chlorine ions, and serves as an auxiliary oxidant for etching the copper-based metal film. The chlorine-containing compound is preferably included in 0.1 to 5% by weight, more preferably in 0.1 to 3% by weight based on the total weight of the composition. When the chlorine-containing compound is less than 0.1% by weight, the etching rate of the copper-based metal film is lowered, so that the etching profile is poor. When the content of the chlorine compound exceeds 5% by weight, overetching may occur and wiring may be lost.
상기 함염소화합물로는 예컨대 HCl, NaCl, KCl, NH4Cl 등을 들 수 있으며, 이들은 1종 단독으로 또는 2종 이상이 함께 사용될 수 있다. 특히, 이들 중에서 NaCl 및 NH4Cl이 더욱 바람직하게 사용될 수 있다. Examples of the chlorine-containing compound include HCl, NaCl, KCl, NH 4 Cl, and the like, which may be used alone or in combination of two or more. In particular, NaCl and NH 4 Cl may be more preferably used among them.
본 발명에서 함불소화합물은 티타늄계 금속막을 식각하는 주성분으로 작용하며, 조성물 총 중량에 대하여 0.01~2 중량%로 함유된다. 0.01중량% 미만으로 함유 되는 경우에는 티타늄계 금속막의 식각속도가 저하되어 잔사가 발생 할 수 있으며, 2중량%를 초과하게 되면 기판(Glass 등)과 절연막(실리콘막 등)에 손상을 일으킬 수 있다. In the present invention, the fluorine-containing compound serves as a main component for etching the titanium-based metal film, it is contained in 0.01 to 2% by weight relative to the total weight of the composition. If the content is less than 0.01% by weight, the etching rate of the titanium-based metal film may be lowered, and residues may occur. If the content exceeds 2% by weight, the substrate (Glass, etc.) and the insulating film (silicon film, etc.) may be damaged. .
상기 함불소화합물은 불소 이온 또는 다원자 불소이온이 해리될 수 있는 화합물을 의미하며, 상기 함불소화합물로는 불화암모늄, 불화나트륨, 불화칼륨, 중불화암모늄, 중불화나트륨, 중불화칼륨 등을 들 수 있으며, 이들은 1종 단독으로 또는 2종 이상이 함께 사용될 있다.The fluorine-containing compound means a compound capable of dissociating fluorine ions or polyatomic fluorine ions. Examples of the fluorine-containing compound include ammonium fluoride, sodium fluoride, potassium fluoride, ammonium bifluoride, sodium bifluoride, potassium bifluoride, and the like. These may be used alone or in combination of two or more.
본 발명에서 사용되는 물은 탈이온수를 의미하며 반도체 공정용을 사용하며, 바람직하게는 18㏁/㎝ 이상의 물을 사용한다. Water used in the present invention means deionized water and is used for the semiconductor process, preferably water of 18 dl / cm or more.
본 발명의 식각액 조성물은 상기에 언급된 성분들 외에 유기산 및 무기산으로 이루어진 군으로부터 선택되는 1종 이상의 식각조절제를 더 포함할 수 있다. 상기 식각조절제는 조성물 총 중량에 대하여 0.1~10 중량%로 포함될 수 있다.The etchant composition of the present invention may further include one or more etching control agents selected from the group consisting of organic and inorganic acids in addition to the above-mentioned components. The etching control agent may be included in 0.1 to 10% by weight based on the total weight of the composition.
상기 식각조절제 중 유기산은 구리의 식각을 억제하여 구리를 포함하는 막에서 구리와 다른 금속 사이의 식각 속도를 조절해 주는 역할을 한다. 식각조절제로서 유기산이 사용되는 경우, 식각액 조성물 총 중량에 대하여 0.1~10 중량%로 포함되는 것이 바람직하다. 유기산이 0.1 중량% 미만으로 포함되는 경우에는, 구리 및 티타늄의 식각 속도가 너무 빨라져서 사이드 에칭이 커질 수 있으며, 불량 프로파일이 생성될 수 있고, 10 중량%를 초과하면 구리 및 티타늄의 식각속도가 너무 억제되어 잔사가 발생될 수 있다.The organic acid in the etching control agent serves to control the etching rate between the copper and the other metal in the film containing copper by inhibiting the etching of copper. When an organic acid is used as an etching control agent, it is preferably included in 0.1 to 10% by weight based on the total weight of the etching liquid composition. If the organic acid is included in less than 0.1% by weight, the etching rate of copper and titanium may be too fast to increase side etching, and a bad profile may be generated, and if it exceeds 10% by weight, the etching rate of copper and titanium may be too high. It can be suppressed and residues can be generated.
상기 유기산으로는 구연산(Citric acid), 글리콜산(Glycolic acid), 초산(acetic acid), 설폰산(sulfonic acid), 옥살산(oxalic acid), 아미노기와 카르복실기를 갖는 수용성 화합물 등을 들 수 있으며, 이들은 1종 단독으로 또는 2종 이상이 함께 사용될 수 있다. 특히, 상기 아미노기와 카르복실기를 갖는 수용성 화합물은 상기에서 언급한 식각조절제로서의 역할뿐만 아니라, 식각시에 해리된 구리이온을 킬레이팅 하여 재흡착을 방지하고, 이러한 역할에 의해 기판의 처리매수도 증가시키므로 더욱 바람직하게 사용될 수 있다. 상기 아미노기와 카르복실기를 갖는 수용성 화합물로는 알라닌(alanine), 아미노부티르산(aminobutyric acid), 글루탐산(glutamic acid), 글리신(glycine), 이미노디아세트산(iminodiacetic acid), 니트릴로트리아세트산(nitrilotriacetic acid) 및 사르코신(sarcosine) 등을 들 수 있으며, 이들은 1종 단독으로 또는 2종 이상이 함께 사용될 수 있다.The organic acid may include citric acid, glycolic acid, glycolic acid, acetic acid, sulfonic acid, oxalic acid, water-soluble compounds having an amino group and a carboxyl group, and the like. One kind alone or two or more kinds may be used together. In particular, the water-soluble compound having an amino group and a carboxyl group not only serves as the above-mentioned etch control agent, but also prevents resorption by chelating copper ions dissociated at the time of etching, thereby increasing the number of processed sheets of the substrate. More preferably. Examples of the water-soluble compound having an amino group and a carboxyl group include alanine, aminobutyric acid, glutamic acid, glycine, glycine, iminodiacetic acid, nitrilotriacetic acid and sarco And sarcosine, and these may be used alone or in combination of two or more.
상기 식각조절제 중에서 무기산은 유기산과는 반대의 역할을 한다. 즉, 무기산은 구리계 금속막을 산화 및 식각하며, 티타늄계 금속막을 산화시키는 역할을 한다. 식각조절제로서 상기 무기산이 사용되는 경우, 식각액 조성물 총 중량에 대하여 0.1~10 중량%로 함유되는 것이 바람직하다. 상기 무기산이 0.1 중량% 미만으로 함유 되는 경우 구리계 금속막 및 티타늄계 금속막의 식각속도가 저하되어 식각 프로파일 불량 및 잔사가 발생 할 수 있으며, 10 중량%를 초과하게 되면 과식각 및 포토레지스트 크랙(Crack)이 발생하여 약액 침투에 의하여 배선이 단락 될 수 있다.In the etching control agent, the inorganic acid plays a role opposite to that of the organic acid. That is, the inorganic acid oxidizes and etches the copper-based metal film and serves to oxidize the titanium-based metal film. When the inorganic acid is used as an etching control agent, it is preferably contained in 0.1 to 10% by weight based on the total weight of the etching liquid composition. When the inorganic acid is contained in less than 0.1% by weight, the etching rate of the copper-based metal film and the titanium-based metal film may be lowered, resulting in poor etching profiles and residues. When the inorganic acid exceeds 10% by weight, overetching and photoresist cracks ( This can cause a short circuit due to chemical infiltration.
상기 무기산으로는 예컨대, 질산, 황산, 인산, 과염소산 등을 들 수 있으며, 이들은 1종 단독으로 또는 2종 이상이 함께 사용될 수 있다.Examples of the inorganic acid include nitric acid, sulfuric acid, phosphoric acid, perchloric acid, and the like. These may be used alone or in combination of two or more.
본 발명의 식각액 조성물은 상기에 언급된 성분들 외에 계면활성제, 금속 이온 봉쇄제, 부식 방지제 및 pH 조절제 중 하나 이상을 더 포함할 수 있다.The etchant composition of the present invention may further comprise at least one of a surfactant, a metal ion sequestrant, a corrosion inhibitor and a pH adjusting agent in addition to the above-mentioned components.
또한, 본 발명은In addition, the present invention
상기 식각액 조성물을 사용하여 금속배선의 패턴을 형성하는 공정을 포함하는 것을 특징으로 하는 박막트랜지스터의 제조방법을 제공한다.It provides a method for producing a thin film transistor comprising the step of forming a pattern of metal wiring using the etchant composition.
상기 제조방법에 의하면, 박막트랜지스터 상에 우수한 상태의 금속배선을 형성하는 것이 가능하므로 뛰어난 품질의 박막트랜지스터를 제조할 수 있다. According to the above manufacturing method, it is possible to form a metal wiring in an excellent state on the thin film transistor, it is possible to manufacture a thin film transistor of excellent quality.
이하에서, 실시예를 통하여 본 발명을 보다 상세히 설명한다. 그러나, 하기의 실시예는 본 발명을 더욱 구체적으로 설명하기 위한 것으로서, 본 발명의 범위가 하기의 실시예에 의하여 한정되는 것은 아니다. 하기의 실시예는 본 발명의 범위 내에서 당업자에 의해 적절히 수정 또는 변경될 수 있다. Hereinafter, the present invention will be described in more detail with reference to Examples. However, the following examples are intended to illustrate the present invention more specifically, but the scope of the present invention is not limited by the following examples. The following examples may be appropriately modified or changed by those skilled in the art within the scope of the present invention.
실시예1 내지 8 및 비교예1 내지 3: 식각액 조성물의 제조Examples 1 to 8 and Comparative Examples 1 to 3: Preparation of the etchant composition
하기 표 1에 기재된 성분 및 조성비에 따라 식각액 조성물이 180 kg이 되도록 제조하였다.  To the etchant composition according to the components and composition ratios shown in Table 1 to 180 kg was prepared.
표 1
CuCl2 NaCl NH4FHF C6H8O7 물
실시예 1 0.3 1.0 0.2 0.5 98.0
실시예 2 0.3 0.5 0.2 0.5 98.5
실시예 3 0.3 0.5 0.2 1.0 98.0
실시예 4 0.5 0.5 0.2 2.0 96.8
실시예 5 0.5 1.0 0.2 0.5 97.8
실시예 6 1.0 1.0 0.3 1.0 96.7
실시예 7 1.0 0.2 0.3 2.0 96.5
실시예 8 0.3 1.0 0.3 1.0 97.4
비교예 1 7 2 0.2 0.5 90.3
비교예 2 0.3 0.1 - 1.0 98.6
비교예 3 0.5 0.2 0.2 13 86.1
Table 1
CuCl 2 NaCl NH 4 FHF C 6 H 8 O 7 water
Example 1 0.3 1.0 0.2 0.5 98.0
Example 2 0.3 0.5 0.2 0.5 98.5
Example 3 0.3 0.5 0.2 1.0 98.0
Example 4 0.5 0.5 0.2 2.0 96.8
Example 5 0.5 1.0 0.2 0.5 97.8
Example 6 1.0 1.0 0.3 1.0 96.7
Example 7 1.0 0.2 0.3 2.0 96.5
Example 8 0.3 1.0 0.3 1.0 97.4
Comparative Example 1 7 2 0.2 0.5 90.3
Comparative Example 2 0.3 0.1 - 1.0 98.6
Comparative Example 3 0.5 0.2 0.2 13 86.1
주) C6H8O7: 구연산Note) C 6 H 8 O 7 : citric acid
시험예1: 실시예1 내지 8 및 비교예1 내지 3의 식각액 조성물의 식각 특성 평가Test Example 1: Evaluation of etching characteristics of the etching solution composition of Examples 1 to 8 and Comparative Examples 1 to 3
Glass 기판상의 실리콘 층 위에 구리/티타늄 이중막이 증착 되어 있고, 그 위에 일정한 형태로 포토레지스트가 패터닝된 기판을 시편으로 사용하였다.A copper / titanium bilayer was deposited on a silicon layer on a glass substrate, and a substrate on which a photoresist was patterned in a uniform form was used as a specimen.
분사식 식각 방식의 실험장비(SEMES사 제조, 모델명: ETCHER(TFT)) 내에 상기 실시예1 내지 8 및 비교예1 내지 3에서 제조된 식각액을 각각 넣고 온도를 25℃로 세팅하여 가온한 후, 온도가 25±0.1℃에 도달한 후, 식각 공정을 수행하였다. 총 에칭 시간을 EPD를 기준으로 하여 30%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 포토레지스트를 제거하였다. 세정 및 건조 후 전자주사현미경(SEM: HITACHI사 제조, 모델명: S-4700)을 이용하여 식각 프로파일의 경사각, 사이드 에치(CD(critical dimension)) 손실, 식각 잔류물 및 하부막 손상을 평가하여, 그 결과를 표 2 에 나타내었다.Etching liquid prepared in Examples 1 to 8 and Comparative Examples 1 to 3 were put into a spraying etching apparatus (SEMES, model name: ETCHER (TFT)), and the temperature was set to 25 ° C., followed by heating. After reaching 25 ± 0.1 ° C., an etching process was performed. Total etch time was given at 30% 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 cleaning and drying, an electron scanning microscope (SEM: manufactured by Hitachi, model name: S-4700) was used to evaluate the inclination angle of the etching profile, the loss of side etch (CD), the etching residue and the underlying film damage. The results are shown in Table 2.
[식각 프로파일의 평가 기준][Evaluation Criteria of Etch Profile]
◎: 매우 우수(CD Skew:≤1㎛, Taper Angle: 30°~ 60°) ◎: Very good (CD Skew: ≤1㎛, Taper Angle: 30 ° ~ 60 °)
○: 우수(CD Skew:≤1.5㎛, Taper Angle: 30°~ 60°) ○: Excellent (CD Skew: ≤1.5㎛, Taper Angle: 30 ° ~ 60 °)
△: 양호(CD Skew:≤2㎛, Taper Angle: 30°~ 60°) △: Good (CD Skew: ≤2㎛, Taper Angle: 30 ° to 60 °)
×: 불량(금속막 소실 및 잔사 발생) X: Poor (metal film loss and residue)
표 2
박막의 종류 식각프로파일 Glass 및 실리콘막 손상 잔사
실시예 1 Cu/Ti ◎ 없음 없음
실시예 2 ◎ 없음 없음
실시예 3 ◎ 없음 없음
실시예 4 ◎ 없음 없음
실시예 5 ◎ 없음 없음
실시예 6 ◎ 없음 없음
실시예 7 ◎ 없음 없음
실시예 8 ◎ 없음 없음
비교예 1 × Cu Pattern 소실
비교예 2 × Ti Unetch
비교예 3 × Cu Unetch
TABLE 2
Type of thin film Etch Profile Glass and silicon film damage Residue
Example 1 Cu / Ti ◎ none none
Example 2 ◎ none none
Example 3 ◎ none none
Example 4 ◎ none none
Example 5 ◎ none none
Example 6 ◎ none none
Example 7 ◎ none none
Example 8 ◎ none none
Comparative Example 1 × Cu Pattern Loss
Comparative Example 2 × Ti Unetch
Comparative Example 3 × Cu unetch
상기 표2에서 확인되는 바와 같이, 실시예1 내지 8의 식각액 조성물은 식각 프로파일이 우수하며, Glass기판 및 실리콘층에 손상이 없으며, 잔사도 없는 우수한 식각 특성을 나타냈다. 반면, 및 비교예1 내지 3의 식각액 조성물은 불량한 식각 프로파일, 구리 및 티타늄막의 언에치(Unetch) 및 구리 패턴의 소실이 관찰되어 사용하기에 부적합한 것으로 확인되었다(도1 및 도2 참조). As confirmed in Table 2, the etchant composition of Examples 1 to 8 had excellent etching profiles, no damage to the glass substrate and the silicon layer, and showed excellent etching characteristics without residue. On the other hand, and Comparative Examples 1 to The etchant composition of 3 was found to be unsuitable for use because of poor etching profiles, unetch of copper and titanium films, and loss of copper patterns were observed (see FIGS. 1 and 2).
실시예9 내지 18 및 비교예4 내지 8: 식각액 조성물의 제조Examples 9-18 and Comparative Examples 4-8 8: Preparation of Etch Liquid Composition
하기 표 3에 기재된 성분 및 조성비에 따라 식각액 조성물이 180 kg이 되도록 제조하였다.According to the components and the composition ratios described in Table 3 below, the etchant composition was prepared to be 180 kg.
표 3
CuCl2 NaCl NH4FHF HNO3 물
실시예 9 0.3 0.2 0.2 1 98.3
실시예 10 0.4 0.3 0.1 0.5 98.7
실시예 11 0.5 0.3 0.2 1 98
실시예 12 0.5 0.5 0.1 0.5 98.4
실시예 13 0.7 0.3 0.2 1 97.8
실시예 14 0.7 0.5 0.3 1 97.5
실시예 15 1 0.5 0.2 1 97.3
실시예 16 2 1 0.3 1 95.7
실시예 17 3 1 0.3 1 94.7
실시예 18 3 1.2 0.3 1 94.5
비교예 4 0.05 0.01 0.2 1 98.74
비교예 5 1 0.5 0.02 0.5 97.98
비교예 6 7 1 0.2 2 89.8
비교예 7 0.5 0.3 2.5 1 95.7
비교예 8 0.7 0.3 0.2 12 86.8
TABLE 3
CuCl 2 NaCl NH 4 FHF HNO 3 water
Example 9 0.3 0.2 0.2 One 98.3
Example 10 0.4 0.3 0.1 0.5 98.7
Example 11 0.5 0.3 0.2 One 98
Example 12 0.5 0.5 0.1 0.5 98.4
Example 13 0.7 0.3 0.2 One 97.8
Example 14 0.7 0.5 0.3 One 97.5
Example 15 One 0.5 0.2 One 97.3
Example 16 2 One 0.3 One 95.7
Example 17 3 One 0.3 One 94.7
Example 18 3 1.2 0.3 One 94.5
Comparative Example 4 0.05 0.01 0.2 One 98.74
Comparative Example 5 One 0.5 0.02 0.5 97.98
Comparative Example 6 7 One 0.2 2 89.8
Comparative Example 7 0.5 0.3 2.5 One 95.7
Comparative Example 8 0.7 0.3 0.2 12 86.8
시험예3: 실시예9 내지 18 및 비교예4 내지 8의 식각액 조성물의 식각 특성 평가Test Example 3: Evaluation of the etching properties of the etching solution composition of Examples 9 to 18 and Comparative Examples 4 to 8
실시예1 내지 8 및 비교예1 내지 3의 식각액 조성물 대신 실시예9 내지 18 및 비교예4 내지 8의 식각액 조성물을 사용하여 상기 시험예1과 동일한 방법으로 식각특성을 평가하고, 그 결과를 하기 표 4에 나타내었다. Examples 1-8 and Comparative Examples 1-8 Using the etching solution composition of Examples 9 to 18 and Comparative Examples 4 to 8 instead of the etching solution composition of 3 to evaluate the etching characteristics in the same manner as in Test Example 1, the results are shown in Table 4 below.
표 4
박막의 종류 식각프로파일 Glass 및 실리콘막 손상 잔사
실시예 9 Cu/Ti ◎ 없음 없음
실시예 10 ◎ 없음 없음
실시예 11 ◎ 없음 없음
실시예 12 ◎ 없음 없음
실시예 13 ◎ 없음 없음
실시예 14 ◎ 없음 없음
실시예 15 ◎ 없음 없음
실시예 16 ◎ 없음 없음
실시예 17 ◎ 없음 없음
실시예 18 ◎ 없음 없음
비교예 4 × Cu Unetch
비교예 5 × Ti Unetch
비교예 6 × Cu 패턴 소실
비교예 7 × 있음 없음
비교예 8 × Cu 패턴 소실
Table 4
Type of thin film Etch Profile Glass and silicon film damage Residue
Example 9 Cu / Ti ◎ none none
Example 10 ◎ none none
Example 11 ◎ none none
Example 12 ◎ none none
Example 13 ◎ none none
Example 14 ◎ none none
Example 15 ◎ none none
Example 16 ◎ none none
Example 17 ◎ none none
Example 18 ◎ none none
Comparative Example 4 × Cu unetch
Comparative Example 5 × Ti Unetch
Comparative Example 6 × Cu pattern disappeared
Comparative Example 7 × has exist none
Comparative Example 8 × Cu pattern disappeared
상기 표4에서 확인되는 바와 같이, 실시예9 내지 18의 식각액 조성물은 식각 프로파일이 우수하며, Glass기판 및 실리콘층에 손상이 없으며, 잔사도 없는 우수한 식각 특성을 나타냈다. 반면, 비교예4 내지 8의 식각액 조성물은 불량한 식각 프로파일, 구리 및 티타늄막의 언에치(Unetch) 및 구리 패턴의 소실이 관찰되어 사용하기에 부적합한 것으로 확인되었다(도3 및 도4 참조). As confirmed in Table 4, the etchant composition of Examples 9 to 18 showed excellent etching profiles, no damage to the glass substrate and the silicon layer, and showed excellent etching characteristics without residue. On the other hand, Comparative Examples 4 to The etchant composition of 8 was found to be unsuitable for use because of poor etching profiles, unetch of copper and titanium films and loss of copper patterns were observed (see FIGS. 3 and 4).
실시예19 내지 26 및 비교예 9 내지 11: 식각액 조성물의 제조Examples 19 to 26 and Comparative Examples 9 to 11: Preparation of the etchant composition
하기 표 5에 기재된 성분 및 조성비에 따라 식각액 조성물이 180 kg이 되도록 제조하였다.According to the component and the composition ratio shown in Table 5 was prepared so that the etching solution composition is 180 kg.
표 5
CuCl2 NaCl NH4FHF C2H5NO2 물
실시예 19 0.3 0.1 0.2 0.5 98.9
실시예 20 0.3 0.5 0.2 0.5 98.5
실시예 21 0.5 0.2 0.2 1.0 98.1
실시예 22 0.5 0.5 0.2 0.7 98.1
실시예 23 1.0 0.3 0.2 0.5 98.0
실시예 24 1.0 0.5 0.3 1.0 97.2
실시예 25 3.0 0.2 0.3 2.0 94.5
실시예 26 3.0 1.0 0.3 2.0 93.7
비교예 9 9 2 0.2 0.2 88.6
비교예 10 0.5 0.05 0.01 0.8 98.64
비교예 11 0.3 0.1 0.3 15.0 84.3
Table 5
CuCl 2 NaCl NH 4 FHF C 2 H 5 NO 2 water
Example 19 0.3 0.1 0.2 0.5 98.9
Example 20 0.3 0.5 0.2 0.5 98.5
Example 21 0.5 0.2 0.2 1.0 98.1
Example 22 0.5 0.5 0.2 0.7 98.1
Example 23 1.0 0.3 0.2 0.5 98.0
Example 24 1.0 0.5 0.3 1.0 97.2
Example 25 3.0 0.2 0.3 2.0 94.5
Example 26 3.0 1.0 0.3 2.0 93.7
Comparative Example 9 9 2 0.2 0.2 88.6
Comparative Example 10 0.5 0.05 0.01 0.8 98.64
Comparative Example 11 0.3 0.1 0.3 15.0 84.3
주) C2H5NO2: 글리신Note) C 2 H 5 NO 2 : glycine
시험예2: 실시예19 내지 26 및 비교예9 내지 11의 식각액 조성물의 식각 특성 평가Experimental Example 2: Evaluation of the etching properties of the etching liquid composition of Examples 19 to 26 and Comparative Examples 9 to 11
실시예1 내지 8 및 비교예1 내지 3의 식각액 조성물 대신 실시예19 내지 26 및 비교예9 내지 11의 식각액 조성물을 사용하여 상기 시험예1과 동일한 방법으로 식각특성을 평가하고, 그 결과를 하기 표 6에 나타내었다.Examples 1-8 and Comparative Examples 1-8 Using the etching solution composition of Examples 19 to 26 and Comparative Examples 9 to 11 instead of the etching solution composition of 3 to evaluate the etching characteristics in the same manner as in Test Example 1, the results are shown in Table 6 below.
표 6
박막의 종류 식각프로파일 Glass 및 실리콘막 손상 잔사
실시예 19 Cu/Ti ◎ 없음 없음
실시예 20 ◎ 없음 없음
실시예 21 ◎ 없음 없음
실시예 22 ◎ 없음 없음
실시예 23 ◎ 없음 없음
실시예 24 ◎ 없음 없음
실시예 25 ◎ 없음 없음
실시예 26 ◎ 없음 없음
비교예 9 × Cu Pattern 소실
비교예 10 × Ti Unetch
비교예 11 × Cu Unetch
Table 6
Type of thin film Etch Profile Glass and silicon film damage Residue
Example 19 Cu / Ti ◎ none none
Example 20 ◎ none none
Example 21 ◎ none none
Example 22 ◎ none none
Example 23 ◎ none none
Example 24 ◎ none none
Example 25 ◎ none none
Example 26 ◎ none none
Comparative Example 9 × Cu Pattern Loss
Comparative Example 10 × Ti Unetch
Comparative Example 11 × Cu unetch
상기 표6에서 확인되는 바와 같이, 실시예19 내지 26의 식각액 조성물은 식각 프로파일이 우수하며, Glass기판 및 실리콘층에 손상이 없으며, 잔사도 없는 우수한 식각 특성을 나타냈다. 반면, 및 비교예9 내지 11의 식각액 조성물은 불량한 식각 프로파일, 구리 및 티타늄막의 언에치(Unetch) 및 구리 패턴의 소실이 관찰되어 사용하기에 부적합한 것으로 확인되었다(도5 및 도6 참조). As confirmed in Table 6, the etchant composition of Examples 19 to 26 exhibited excellent etching characteristics, no damage to the glass substrate and the silicon layer, and excellent etching characteristics without residue. On the other hand, and Comparative Examples 9 to The etchant composition of 11 was found to be unsuitable for use because of poor etching profiles, unetch of copper and titanium films and loss of copper patterns were observed (see FIGS. 5 and 6).

Claims (11)

  1. 조성물 총 중량에 대하여, 0.1~5 중량%의 무기염 산화제, 0.1~5 중량%의 함염소화합물, 0.01~2 중량%의 함불소화합물 및 잔량의 물을 포함하는 구리계 금속막과 티타늄계 금속막을 포함하는 다중막의 식각액 조성물.Based on the total weight of the composition, a copper-based metal film and titanium-based metal containing 0.1 to 5% by weight of an inorganic salt oxidizing agent, 0.1 to 5% by weight of a chlorine-containing compound, 0.01 to 2% by weight of a fluorine-containing compound and a balance of water Etch liquid composition of a multi-membrane comprising a membrane.
  2. 청구항 1에 있어서, 상기 무기염 산화제는 CuCl2, Cu(NO3)2 및 CuSO4로 이루어진 군으로부터 선택되는 1종 또는 2종 이상의 것임을 특징으로 하는 구리계 금속막과 티타늄계 금속막을 포함하는 다중막의 식각액 조성물.The method according to claim 1, wherein the inorganic salt oxidizing agent comprising a copper-based metal film and a titanium-based metal film, characterized in that one or two or more selected from the group consisting of CuCl 2 , Cu (NO 3 ) 2 and CuSO 4 . Etch solution composition of the membrane.
  3. 청구항 1에 있어서, 상기 함염소화합물은 HCl, NaCl, KCl 및 NH4Cl로 이루어진 군으로부터 선택되는 1종 또는 2종 이상의 것임을 특징으로 하는 구리계 금속막과 티타늄계 금속막을 포함하는 다중막의 식각액 조성물.The etchant composition of claim 1, wherein the chlorine-containing compound is one or two or more selected from the group consisting of HCl, NaCl, KCl, and NH 4 Cl. .
  4. 청구항 1에 있어서, 상기 함불소화합물은 불화암모늄, 불화나트륨, 불화칼륨, 중불화암모늄, 중불화나트륨 및 중불화칼륨으로 이루어진 군으로부터 선택되는 1종 또는 2종 이상의 것임을 특징으로 하는 구리계 금속막과 티타늄계 금속막을 포함하는 다중막의 식각액 조성물. The copper-based metal film of claim 1, wherein the fluorine-containing compound is one or two or more selected from the group consisting of ammonium fluoride, sodium fluoride, potassium fluoride, ammonium bifluoride, sodium bifluoride and potassium bifluoride. And a titanium-based metal film etching liquid composition.
  5. 청구항 1에 있어서, 상기 식각액 조성물 총 중량에 대하여, 0.1~10 중량%의 유기산 및 무기산으로 이루어진 군으로부터 선택되는 1종 이상의 식각조절제를 더 포함하는 것을 특징으로 하는 구리계 금속막과 티타늄계 금속막을 포함하는 다중막의 식각액 조성물. The copper-based metal film and the titanium-based metal film of claim 1, further comprising at least one etching regulator selected from the group consisting of 0.1 to 10% by weight of an organic acid and an inorganic acid, based on the total weight of the etchant composition. Etching liquid composition of the multilayer.
  6. 청구항 1에 있어서, 상기 유기산 및 무기산으로 이루어진 군으로부터 선택되는 1종 이상은 구연산(Citric acid), 글리콜 산(Glycolic acid), 초산(acetic acid), 설폰산(sulfonic acid), 옥살산(oxalic acid), 아미노기와 카르복실기를 갖는 수용성 화합물, 질산, 황산, 인산 및 과염소산으로 이루어진 군으로부터 선택되는 것임을 특징으로 하는 구리계 금속막과 티타늄계 금속막을 포함하는 다중막의 식각액 조성물.The method according to claim 1, wherein at least one selected from the group consisting of organic and inorganic acids is citric acid (Citric acid), glycolic acid (Glycolic acid), acetic acid (acetic acid), sulfonic acid (sulfonic acid), oxalic acid (oxalic acid) And a water-soluble compound having an amino group and a carboxyl group, nitric acid, sulfuric acid, phosphoric acid, and perchloric acid, wherein the copper-based metal film and the titanium-based metal film etching solution composition comprising a titanium-based metal film.
  7. 청구항 6에 있어서, 상기 아미노기와 카르복실기를 갖는 수용성 화합물이 알라닌(alanine), 아미노부티르산(aminobutyric acid), 글루탐산(glutamic acid), 글리신(glycine), 이미노디아세트산(iminodiacetic acid), 니트릴로트리아세트산(nitrilotriacetic acid) 및 사르코신(sarcosine)으로 이루어진 군으로부터 선택되는 것임을 특징으로 하는 구리계 금속막과 티타늄계 금속막을 포함하는 다중막의 식각액 조성물.The method of claim 6, wherein the water-soluble compound having an amino group and a carboxyl group is alanine, aminobutyric acid, glutamic acid, glycine, glycino, iminodiacetic acid, nitrilotriacetic acid) and sarcosine (sarcosine) is an etching liquid composition of a multilayer comprising a copper-based metal film and a titanium-based metal film, characterized in that it is selected from the group consisting of.
  8. 청구항 5에 있어서, 상기 식각조절제가 유기산으로 이루어지는 것임을 특징으로 하는 구리계 금속막과 티타늄계 금속막을 포함하는 다중막의 식각액 조성물.The etching liquid composition according to claim 5, wherein the etching control agent is made of an organic acid.
  9. 청구항 5에 있어서, 상기 식각조절제가 무기산으로 이루어지는 것임을 특징으로 하는 구리계 금속막과 티타늄계 금속막을 포함하는 다중막의 식각액 조성물.The etching liquid composition of claim 5, wherein the etching control agent is made of an inorganic acid. 7.
  10. 청구항 5에 있어서, 상기 식각조절제가 유기산인 아미노기와 카르복실기를 갖는 수용성 화합물로 이루어지는 것임을 특징으로 하는 구리계 금속막과 티타늄계 금속막을 포함하는 다중막의 식각액 조성물.The etching liquid composition according to claim 5, wherein the etching control agent is made of a water-soluble compound having an amino group and a carboxyl group as an organic acid.
  11. 청구항 1의 식각액 조성물을 사용하여 금속배선의 패턴을 형성하는 공정을 포함하는 것을 특징으로 하는 박막트랜지스터의 제조방법.A method of manufacturing a thin film transistor comprising the step of forming a pattern of a metal wiring using the etchant composition of claim 1.
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