WO2011010877A2 - Etchant composition for the formation of a metal line - Google Patents

Etchant composition for the formation of a metal line Download PDF

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Publication number
WO2011010877A2
WO2011010877A2 PCT/KR2010/004807 KR2010004807W WO2011010877A2 WO 2011010877 A2 WO2011010877 A2 WO 2011010877A2 KR 2010004807 W KR2010004807 W KR 2010004807W WO 2011010877 A2 WO2011010877 A2 WO 2011010877A2
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Prior art keywords
acid
etching
group
weight
compound
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PCT/KR2010/004807
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French (fr)
Korean (ko)
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WO2011010877A3 (en
Inventor
임민기
양승재
이유진
박영철
권오병
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동우 화인켐 주식회사
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Priority claimed from KR1020090066917A external-priority patent/KR101621534B1/en
Priority claimed from KR1020090077210A external-priority patent/KR101733804B1/en
Application filed by 동우 화인켐 주식회사 filed Critical 동우 화인켐 주식회사
Priority to CN201080033845.0A priority Critical patent/CN102471686B/en
Publication of WO2011010877A2 publication Critical patent/WO2011010877A2/en
Publication of WO2011010877A3 publication Critical patent/WO2011010877A3/en

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K13/00—Etching, surface-brightening or pickling compositions
    • C09K13/04—Etching, surface-brightening or pickling compositions containing an inorganic acid
    • C09K13/08—Etching, surface-brightening or pickling compositions containing an inorganic acid containing a fluorine compound
    • 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
    • C23F1/20—Acidic compositions for etching aluminium 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
    • C23F1/44—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 collectively comprises a single layer or a double layer or multiple layers formed of at least one metal selected from the group consisting of titanium, titanium alloys, aluminum and aluminum alloys, which are used for the gate and source / drain electrodes of the flat panel display. It relates to an etchant composition capable of wet etching.
  • the process of forming the metal wiring on the substrate is generally composed of a metal film forming process by sputtering, a photoresist forming process in an optional region by photoresist coating, exposure and development, and an etching process. And washing steps before and after the individual unit steps.
  • 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.
  • Al having a low resistance As the conductive film among the metal films included in the flat panel display, Al having a low resistance is used.
  • the aluminum layer is short-circuited with other conductive layers by a hillock in a subsequent process, and comes into contact with the oxide layer to insulate the insulating layer.
  • Mo, Ti, Cr, and alloys containing these as main components are used as the buffer layer on the upper or lower portion of aluminum. Recently, Ti having corrosion resistance, robustness, and high strength has been spotlighted.
  • Electrode in which the Ti layer is used as a buffer layer has been conventionally etched by using a halogen gas by a dry etching process, but has an anisotropic profile and an excellent etching control ability compared to the wet etching process. There is a problem in that productivity is reduced because equipment is required, difficulty in constructing a large area, and slow etching speed.
  • Korean Patent Application Nos. 10-1999-0005010, 10-1999-0043017, and the like disclose the use of HF as a main component of an etchant composition for wet etching a Ti layer.
  • HF a lot of constraints are placed on the process conditions due to damage to the underlying film and equipment, which causes a decrease in productivity.
  • the present invention is to solve the problems of the prior art as described above,
  • an etching liquid composition of a single film or a double film or more of a multilayer formed of at least one metal selected from the group consisting of titanium, titanium alloys, aluminum and aluminum alloys containing a residual amount of water.
  • the etchant composition of the present invention may further comprise 0.01 to 5% by weight of the cyclic amine compound.
  • the etchant composition of the present invention can wet-etch a single film or a double film or more of a multilayer formed of at least one metal selected from the group consisting of titanium, titanium alloys, aluminum and aluminum alloys, and the etching process because the number of etching treatments is large. Significantly improves productivity. In addition, the etching speed is fast, there is no damage to the lower layer and the equipment, uniform etching between the pattern / non-pattern provides excellent etching characteristics, it does not require expensive equipment configuration and is very economical because it is advantageous for large area Provides the advantage.
  • Example 1 is an electron scanning micrograph showing the result of etching the Ti / Al / Ti triple layer with the etchant composition of Example 3.
  • FIG. 2 is an electron scanning micrograph showing the result of etching a triple layer of Ti / Al / Ti with the etchant composition of Comparative Example 4.
  • FIG. 2 is an electron scanning micrograph showing the result of etching a triple layer of Ti / Al / Ti with the etchant composition of Comparative Example 4.
  • 3 and 4 are electron scanning microscope photographs showing changes in etching characteristics (Side Etch, etc.) according to the number of etching results as a result of etching the Ti / Al / Ti triple layer with the etchant compositions of Examples 10 and 11, respectively.
  • the present invention relates to 5 to 30% by weight of H 2 O 2 , 0.1 to 2% by weight of a fluorine-containing compound, 1 to 10% by weight of a compound having an amino group and a carboxyl group, and 0.1 to 5% by weight of a nitrate compound, based on the total weight of the composition.
  • the etchant composition of the present invention is an etchant for collectively etching a single layer or a double layer or multiple layers formed of one or more metals selected from the group consisting of titanium, titanium alloys, aluminum, and aluminum alloys, wherein the multilayer is referred to as aluminum or
  • the concept includes a double film in which a titanium or titanium alloy film is stacked on or under an aluminum alloy film, and also includes a case of a triple metal film or more in which a titanium or titanium alloy film and an aluminum or aluminum alloy film are alternately stacked.
  • the etchant composition of the present invention can be preferably used in a triple layer of which the upper layer is made of titanium or titanium alloy film, the middle layer is made of aluminum or aluminum alloy film, and the lower layer is made of titanium or titanium alloy film.
  • the titanium or titanium alloy film is a concept including a metal film made of Ti as a main component and an alloy using another metal according to the properties of the Ti film or the film, and the aluminum or aluminum alloy film is Al according to the properties of the Al film or the film.
  • the concept includes a metal film made of an alloy by using a main component and another metal.
  • H 2 O 2 serves to oxidize the surface of the Ti and Al film, it is preferably contained in 5 to 30% by weight, more preferably in 10 to 25% by weight relative to the total weight of the composition.
  • H 2 O 2 is contained in less than 5% by weight, the etching rate of the Ti and Al layers and the etching rate difference between the pattern and the non-pattern increase, causing process problems. Pattern loss due to overetching of the Al film may occur, and the metal wiring may lose its function.
  • the fluorine-containing compound serves to etch the surface of the oxidized Ti and Al film, it is preferably contained in 0.1 to 2% by weight relative to the total weight of the composition. If the content is less than 0.1% by weight, residues may occur due to the low etching rate of the Ti and Al films located on the upper and lower portions, or stains may occur in the substrate due to non-uniform etching. Damage to the membrane may occur and control of the process speed is also difficult.
  • 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, sodium bifluoride, potassium bifluoride, ammonium bifluoride, Hydrogen fluoride etc. can be mentioned, These can be used individually by 1 type or in combination of 2 or more types.
  • the compound having an amino group and a carboxyl group serves as a regulator for providing a tip removal effect and an etching uniformity improving effect on the Ti film.
  • the compound having an amino group and a carboxyl group is preferably contained in 1 to 10% by weight, more preferably 3 to 5% by weight based on the total weight of the composition. If the compound having an amino group and a carboxyl group is contained in less than 1% by weight, a tip of the Ti film may occur, which may cause a problem in a subsequent process, and when it exceeds 10% by weight, overetching of the Ti film may occur. .
  • Examples of the compound having an amino group and a carboxyl group include alanine series, aminobutyric acid series, glutamic acid series, glycine series, iminodiacetic acid series, nitrilotriacetic acid series, and sarcosine series compounds, and these may be used alone or in combination of two or more. This can be used together.
  • alanine aminobutyric acid, glutamic acid, glycine, glycine, iminodiacetic acid, nitrilotriacetic acid, and sarcosine.
  • glutamic acid glutamic acid
  • glycine glycine
  • iminodiacetic acid nitrilotriacetic acid
  • sarcosine sarcosine.
  • the nitrate compound serves to improve the straightness of the wiring consisting of the Ti and Al film during etching, it is preferably contained in 0.1 to 5% by weight relative to the total weight of the composition.
  • the nitrate compound is contained in less than 0.1% by weight, the etching uniformity is reduced, the wiring shape is formed unevenly, and the problem of staining occurs in the substrate.
  • the content exceeds 5% by weight, an overetching phenomenon occurs due to an increase in the etching rate of the Ti and Al films, and a stain occurs due to a decrease in etching uniformity.
  • the nitrate compound means an organic or inorganic compound containing nitrate ions, and examples thereof include ammonium nitrate, sodium nitrate, potassium nitrate, and the like. It may be used alone or two or more kinds together.
  • 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 a cyclic amine compound.
  • Ti and Al metal ions increase in the etchant, and the increase of the metal ions is coupled with the change of the composition in the chemical solution, causing the lowering of the etching rate, thereby lowering the etching characteristics.
  • the cyclic amine compound Since the cyclic amine compound reacts with metal ions to form a stable form, the cyclic amine compound serves to increase the number of processed substrates.
  • the cyclic amine compound is preferably contained in 0.01 to 5% by weight based on the total weight of the composition. When the content of the cyclic compound is less than 0.01% by weight, the metal ion stabilization effect is insignificant, and when the content of the cyclic compound is more than 5% by weight, the solubility of the cyclic compound is low, so that it does not dissolve well when preparing a chemical solution.
  • the cyclic amine compound may include pyrrolidine, pyrroline, pyrrole, indole, pyrazole, imidazole, pyrimidine, purine, pyridine, benzotriazole and derivatives thereof. More than one species may be used together.
  • the etchant composition of the present invention may further add a conventional additive in addition to the components mentioned above, such additives include an etch regulator, a surfactant, a metal ion sequestrant, a corrosion inhibitor, a pH regulator and the like.
  • the etching control agent may be an organic acid.
  • the organic acid means an organic acid except for the compound having an amino group and a carboxyl group.
  • the organic acid serves to improve the etching uniformity with respect to the Ti and Al film, it may be contained in 0.5 to 5% by weight based on the total weight of the composition.
  • When included in the above range it is possible to reduce the occurrence of stains in the substrate due to the etching uniformity decrease, it is possible to reduce the occurrence of over-etching phenomenon for the Ti and Al film.
  • the organic acid is butanoic acid, citric acid, formic acid, formic acid, gluconic acid, glycolic acid, malonic acid, oxalic acid, Pentanoic acid, other water-soluble organic acids, and the like, and these may be used alone or in combination of two or more.
  • a SiNx layer was deposited on the glass, a Ti / Al / Ti triple layer was stacked on the SiNx layer, and a photoresist patterned in a uniform shape was used on the triple layer.
  • Etching liquid prepared in Examples 1 to 9 and Comparative Examples 1 to 5 was put into a spray equipment of the etching method (SEMES, model name: ETCHER (TFT)) and warmed by setting the temperature to 40 °C, the temperature was After reaching 40 ⁇ 0.1 ° C., an etching process was performed. The etching was performed by giving 30% over etching of the total etching time. 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 spray equipment of the etching method
  • TFT ETCHER
  • Comparative Example 1 the NH 4 FHF was contained in an excessive amount, and the lower layer was damaged.
  • Comparative Example 2 the CH 3 COOH was contained in an excessive amount, resulting in uneven etching and residues in the substrate due to a decrease in the etching rate. It was observed, in the case of Comparative Example 3, H 2 O 2 contained in a very small amount, non-uniform etching and residues were observed, and in Comparative Example 4, amino diacetic acid and nitrate were not included in the etchant composition, non-uniform etching And staining and tip generation of upper Ti were also observed. And, in the case of Comparative Example 5, it was confirmed that the etching rate is increased by the excessive inclusion of nitrate, thereby causing stains on the substrate due to the uniformity decrease due to overetching.
  • the number of etching treatments was evaluated by removing the photoresist with the etchant prepared in Examples 10 and 11 in the same manner as the etching characteristic evaluation. At this time, the total etching time was over Etch 30% compared to the EPD to fix the total etching rate of the new liquid, and the number of processing was performed by 100 sheets to 100 sheets in etching.
  • the change in side etch (CD) loss was evaluated using an electron scanning microscope (SEM: manufactured by Hitachi, model name: S-4700), and the results are shown in Table 3 below.
  • the etching solution of Example 11 showed a large change in the side etching decreases according to the number of treatments, and the etching straightness was lowered.
  • the variation of the side etching compared to the BLK is not severe, and even 1000 sheets showed excellent etching characteristics.

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Abstract

The present invention relates to an etchant composition for the formation of a metal line. The etchant composition can wet-etch, in a batch, a single-layer film formed of one or more metals selected from a group consisting of titanium, titanium alloy, aluminum, and an aluminum alloy, or a multilayer film including a double-layer film, thus simplifying the etching process and improving productivity. Further, the etchant composition of the present invention has a high etching rate, prevents damage to a lower film and equipment, enables uniform etching, provides excellent etching characteristics, eliminates the need for expensive equipment, is advantageous when used for large display devices, and provides remarkable economical advantages.

Description

금속 배선 형성을 위한 식각액 조성물Etch solution composition for forming metal wiring
본 발명은 평판디스플레이의 구성 중 게이트 및 소스/드레인 전극에 사용되는, 티타늄, 티타늄 합금, 알루미늄 및 알루미늄 합금으로 이루어진 군으로부터 선택되는 1종 이상의 금속으로 형성되는 단일막 또는 이중막 이상의 다중막을 일괄하여 습식 식각 할 수 있는 식각액 조성물에 관한 것이다.The present invention collectively comprises a single layer or a double layer or multiple layers formed of at least one metal selected from the group consisting of titanium, titanium alloys, aluminum and aluminum alloys, which are used for the gate and source / drain electrodes of the flat panel display. It relates to an etchant composition capable of wet etching.
평판디스플레이 장치에서 기판 위에 금속 배선을 형성하는 과정은 통상적으로 스퍼터링에 의한 금속막 형성공정, 포토레지스트 도포, 노광 및 현상에 의한 선택적인 영역에서의 포토레지스트 형성공정, 및 식각 공정에 의한 단계로 구성되고, 개별적인 단위 공정 전후의 세정 공정 등을 포함한다. 이러한 식각 공정은 포토레지스트 마스크를 사용하여 선택적인 영역에 금속막을 남기는 공정을 의미하며, 통상적으로 플라즈마 등을 이용한 건식 식각 또는 식각 용액을 사용하는 습식 식각이 사용된다.In the flat panel display device, the process of forming the metal wiring on the substrate is generally composed of a metal film forming process by sputtering, a photoresist forming process in an optional region by photoresist coating, exposure and development, and an etching process. And washing steps before and after the individual unit steps. 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.
평판디스플레이에 포함되는 금속막 중 전도막으로는 낮은 저항을 갖는 Al을 사용하게 되는데, 알루미늄 층은 후속 공정에서 힐락(Hillock)에 의하여 다른 전도층과 쇼트현상을 일으키고, 산화물층과 접촉하여 절연층을 형성시키는 문제가 있다. 따라서, 버퍼층으로 알루미늄 상부 또는 하부에 Mo, Ti, Cr 및 이들을 주성분으로 하는 합금 등을 사용하게 되며, 최근에는 내부식성, 견고성, 고강도를 갖는 Ti가 각광 받고 있다. As the conductive film among the metal films included in the flat panel display, Al having a low resistance is used. The aluminum layer is short-circuited with other conductive layers by a hillock in a subsequent process, and comes into contact with the oxide layer to insulate the insulating layer. There is a problem to form. Therefore, Mo, Ti, Cr, and alloys containing these as main components are used as the buffer layer on the upper or lower portion of aluminum. Recently, Ti having corrosion resistance, robustness, and high strength has been spotlighted.
Ti층이 버퍼(Buffer)층으로 사용되는 전극은, 종래에 건식 식각 공정에 의해 할로겐 가스를 사용하여 식각되었으나, 습식 식각 공정에 비하여 이방성 프로파일을 가지며 식각 제어력이 우수하다는 장점에도 불구하고, 고가의 장비가 필요하고, 대면적화의 구성에 어려움이 있으며, 식각 속도가 느리기 때문에 생산성이 저하된다는 문제가 있었다.Electrode in which the Ti layer is used as a buffer layer has been conventionally etched by using a halogen gas by a dry etching process, but has an anisotropic profile and an excellent etching control ability compared to the wet etching process. There is a problem in that productivity is reduced because equipment is required, difficulty in constructing a large area, and slow etching speed.
따라서, 상기와 같은 Ti 버퍼층을 습식으로 식각하는 방법들이 개발되고 있다. 예컨대, 대한민국 특허출원 10-1999-0005010호, 10-1999-0043017호 등은 Ti층을 습식 식각하기 위한 식각액 조성물의 주성분으로 HF를 사용하는 것을 개시하고 있다. 그러나, 습식 식각을 위하여 HF를 사용하는 경우에는, 하부막 및 장비의 손상 때문에 공정상의 조건에 많은 제약이 수반되며, 이런 제약은 생산성을 저하시키는 원인으로 작용한다.Therefore, methods for wet etching the Ti buffer layer as described above have been developed. For example, Korean Patent Application Nos. 10-1999-0005010, 10-1999-0043017, and the like disclose the use of HF as a main component of an etchant composition for wet etching a Ti layer. However, when HF is used for wet etching, a lot of constraints are placed on the process conditions due to damage to the underlying film and equipment, which causes a decrease in productivity.
본 발명은, 상기와 같은 종래 기술의 문제를 해결하기 위한 것으로서, The present invention is to solve the problems of the prior art as described above,
티타늄, 티타늄 합금, 알루미늄 및 알루미늄 합금으로 이루어진 군으로부터 선택되는 1종 이상의 금속으로 형성되는 단일막 또는 이중막 이상의 다중막을 일괄 습식 식각할 수 있고, 식각처리 매수가 많기 때문에 식각 공정의 생산성을 크게 향상시키며; 식각속도가 빠르고, 하부막 및 장비에 대한 손상이 없으며, 패턴/비패턴 간의 균일한 에칭이 가능하므로 우수한 식각 특성을 제공하며; 고가의 장비구성이 필요하지 않고 대면적화에 유리하여 경제적인 식각액 조성물을 제공하는 것을 목적으로 한다.It is possible to carry out a batch wet etching of a single layer or a double layer or more of multiple layers formed of one or more metals selected from the group consisting of titanium, titanium alloys, aluminum and aluminum alloys, and greatly increases the productivity of the etching process due to the large number of etching treatments. And; Fast etching speed, no damage to underlying film and equipment, uniform etching between patterns / non-patterns, thus providing excellent etching characteristics; It is an object of the present invention to provide an economical etchant composition that does not require expensive equipment configuration and is advantageous for large area.
본 발명은, The present invention,
조성물 총중량에 대하여, 5~30 중량%의 H2O2, 0.1~2 중량%의 함불소 화합물, 1~10 중량%의 아미노기와 카르복실기를 동시에 함유하는 화합물, 0.1~5 중량%의 질산염 화합물 및 잔량의 물을 함유하는 티타늄, 티타늄 합금, 알루미늄 및 알루미늄 합금으로 이루어진 군으로부터 선택되는 1종 이상의 금속으로 형성되는 단일막 또는 이중막 이상의 다중막의 식각액 조성물을 제공한다. 5 to 30% by weight of H 2 O 2 , 0.1 to 2% by weight of a fluorine-containing compound, a compound containing 1 to 10% by weight of an amino group and a carboxyl group, 0.1 to 5% by weight of a nitrate compound, based on the total weight of the composition, and Provided is an etching liquid composition of a single film or a double film or more of a multilayer formed of at least one metal selected from the group consisting of titanium, titanium alloys, aluminum and aluminum alloys containing a residual amount of water.
상기 본 발명의 식각액 조성물은 0.01~5 중량%의 고리형 아민 화합물을 더 포함할 수 있다. The etchant composition of the present invention may further comprise 0.01 to 5% by weight of the cyclic amine compound.
본 발명의 식각액 조성물은 티타늄, 티타늄 합금, 알루미늄 및 알루미늄 합금으로 이루어진 군으로부터 선택되는 1종 이상의 금속으로 형성된 단일막 또는 이중막 이상의 다중막을 일괄 습식 식각할 수 있고, 식각처리 매수가 많기 때문에 식각 공정의 생산성을 크게 향상시킨다. 또한, 식각속도가 빠르고, 하부막 및 장비에 대한 손상이 없으며, 패턴/비패턴 간의 균일한 에칭이 가능하여 우수한 식각 특성을 제공하며, 고가의 장비구성이 필요하지 않고 대면적화에 유리하여 매우 경제적인 이점을 제공한다. The etchant composition of the present invention can wet-etch a single film or a double film or more of a multilayer formed of at least one metal selected from the group consisting of titanium, titanium alloys, aluminum and aluminum alloys, and the etching process because the number of etching treatments is large. Significantly improves productivity. In addition, the etching speed is fast, there is no damage to the lower layer and the equipment, uniform etching between the pattern / non-pattern provides excellent etching characteristics, it does not require expensive equipment configuration and is very economical because it is advantageous for large area Provides the advantage.
도 1은 실시예3의 식각액 조성물로 Ti/Al/Ti 삼중막을 식각한 결과를 나타내는 전자주사현미경 사진이다.1 is an electron scanning micrograph showing the result of etching the Ti / Al / Ti triple layer with the etchant composition of Example 3.
도2는 비교예4의 식각액 조성물로 Ti/Al/Ti 삼중막을 식각한 결과를 나타내는 전자주사현미경 사진이다.FIG. 2 is an electron scanning micrograph showing the result of etching a triple layer of Ti / Al / Ti with the etchant composition of Comparative Example 4. FIG.
도 3 및 4는 각각 실시예10 및 실시예11의 식각액 조성물로 Ti/Al/Ti 삼중막을 식각한결과로서, 식각매수에 따른 식각특성(Side Etch등)의 변화를 나타내는 전자주사현미경 사진이다.3 and 4 are electron scanning microscope photographs showing changes in etching characteristics (Side Etch, etc.) according to the number of etching results as a result of etching the Ti / Al / Ti triple layer with the etchant compositions of Examples 10 and 11, respectively.
본 발명은 조성물 총중량에 대하여, 5~30 중량%의 H2O2, 0.1~2 중량%의 함불소 화합물, 1~10 중량%의 아미노기와 카르복실기를 갖는 화합물, 0.1~5 중량%의 질산염 화합물 및 잔량의 물을 함유하는 티타늄, 티타늄 합금, 알루미늄 및 알루미늄 합금으로 이루어진 군으로부터 선택되는 1종 이상의 금속으로 형성되는 단일막 또는 이중막 이상의 다중막의 식각액 조성물에 관한 것이다.The present invention relates to 5 to 30% by weight of H 2 O 2 , 0.1 to 2% by weight of a fluorine-containing compound, 1 to 10% by weight of a compound having an amino group and a carboxyl group, and 0.1 to 5% by weight of a nitrate compound, based on the total weight of the composition. And an etching solution composition of a single film or a double film or more of a multilayer formed of at least one metal selected from the group consisting of titanium, titanium alloys, aluminum and aluminum alloys containing a residual amount of water.
본 발명의 식각액 조성물은 티타늄, 티타늄 합금, 알루미늄 및 알루미늄 합금으로 이루어진 군으로부터 선택되는 1종 이상의 금속으로 형성되는 단일막 또는 이중막 이상의 다중막을 일괄 식각하는 식각액이며, 여기서 다중막이라 함은 알루미늄 또는 알루미늄 합금막의 상부 또는 하부에 티타늄 또는 티타늄 합금막이 적층된 이중막을 포함하며, 또한, 티타늄 또는 티타늄 합금막 및 알루미늄 또는 알루미늄 합금막이 교대로 적층되는 삼중막 이상의 다중 금속막의 경우도 포함하는 개념이다. The etchant composition of the present invention is an etchant for collectively etching a single layer or a double layer or multiple layers formed of one or more metals selected from the group consisting of titanium, titanium alloys, aluminum, and aluminum alloys, wherein the multilayer is referred to as aluminum or The concept includes a double film in which a titanium or titanium alloy film is stacked on or under an aluminum alloy film, and also includes a case of a triple metal film or more in which a titanium or titanium alloy film and an aluminum or aluminum alloy film are alternately stacked.
본 발명의 식각액 조성물은 특히, 상부층이 티타늄 또는 티타늄 합금막, 중간층이 알루미늄 또는 알루미늄 합금막, 하부층이 티타늄 또는 티타늄 합금막으로 이루어진 삼중막에 바람직하게 사용될 수 있다.In particular, the etchant composition of the present invention can be preferably used in a triple layer of which the upper layer is made of titanium or titanium alloy film, the middle layer is made of aluminum or aluminum alloy film, and the lower layer is made of titanium or titanium alloy film.
상기에서 티타늄 또는 티타늄 합금막이란 Ti막 또는 막의 특성에 따라 Ti을 주성분으로 하고 다른 금속을 사용하여 합금으로 된 금속막을 포함하는 개념이며, 알루미늄 또는 알루미늄 합금막이란 Al막 또는 막의 특성에 따라 Al을 주성분으로 하고 다른 금속을 사용하여 합금으로 된 금속막을 포함하는 개념이다. The titanium or titanium alloy film is a concept including a metal film made of Ti as a main component and an alloy using another metal according to the properties of the Ti film or the film, and the aluminum or aluminum alloy film is Al according to the properties of the Al film or the film. The concept includes a metal film made of an alloy by using a main component and another metal.
본 발명에서 H2O2는 Ti 및 Al막의 표면을 산화시키는 역할을 하며, 조성물 총 중량에 대하여 5~30 중량%로 함유되는 것이 바람직하며, 10~25 중량%로 함유되는 것이 더욱 바람직하다. H2O2가 5 중량% 미만으로 함유되는 경우에는 Ti 및 Al층의 에칭 속도 저하와 패턴/비패턴 간의 식각속도 차이가 커져서 공정상의 문제가 야기되며, 30 중량%를 초과하는 경우에는 Ti 및 Al막의 과식각에 의한 패턴 소실이 발생하여 금속 배선이 기능을 상실할 수 있다.In the present invention, H 2 O 2 serves to oxidize the surface of the Ti and Al film, it is preferably contained in 5 to 30% by weight, more preferably in 10 to 25% by weight relative to the total weight of the composition. When H 2 O 2 is contained in less than 5% by weight, the etching rate of the Ti and Al layers and the etching rate difference between the pattern and the non-pattern increase, causing process problems. Pattern loss due to overetching of the Al film may occur, and the metal wiring may lose its function.
본 발명에서 함불소 화합물은 산화된 Ti 및 Al막 표면을 식각하는 역할을 하며, 조성물 총 중량에 대하여 0.1~2 중량%로 함유되는 것이 바람직하다. 0.1 중량% 미만으로 함유되는 경우에는 상하부에 위치하는 Ti 및 Al막의 낮은 식각속도에 의해서 잔사가 발생하거나 불균일 식각으로 인해 기판내에 얼룩이 발생하며, 2 중량%를 초과하는 경우에는 과도한 식각속도에 의해서 하부막에 손상이 발생할 수 있으며, 공정 속도의 제어도 어려운 문제가 있다.In the present invention, the fluorine-containing compound serves to etch the surface of the oxidized Ti and Al film, it is preferably contained in 0.1 to 2% by weight relative to the total weight of the composition. If the content is less than 0.1% by weight, residues may occur due to the low etching rate of the Ti and Al films located on the upper and lower portions, or stains may occur in the substrate due to non-uniform etching. Damage to the membrane may occur and control of the process speed is also difficult.
상기 함불소 화합물은 불소 이온 또는 다원자 불소이온이 해리될 수 있는 화합물을 의미하며, 상기 함불소 화합물의 예로는 불화암모늄, 불화나트륨, 불화칼륨, 중불화나트륨, 중불화칼륨, 중불화암모늄, 불화수소 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, sodium bifluoride, potassium bifluoride, ammonium bifluoride, Hydrogen fluoride etc. can be mentioned, These can be used individually by 1 type or in combination of 2 or more types.
본 발명에서 아미노기와 카르복실기를 갖는 화합물은 Ti막에 대하여 Tip 제거 및 식각균일성 향상 효과를 제공하는 조절제 역할을 한다. In the present invention, the compound having an amino group and a carboxyl group serves as a regulator for providing a tip removal effect and an etching uniformity improving effect on the Ti film.
상기 아미노기와 카르복실기를 갖는 화합물은 조성물 총 중량에 대하여 1~10 중량%로 함유되는 것이 바람직하며, 3~5 중량%로 함유되는 것이 더욱 바람직하다. 아미노기와 카르복실기를 갖는 화합물이 1 중량% 미만으로 함유되는 경우에는 Ti막의 Tip이 발생 하여 후속 공정에 문제를 야기 시킬 수 있으며, 10 중량%를 초과하는 경우에는 Ti막의 과식각 현상이 발생 할 수 있다.The compound having an amino group and a carboxyl group is preferably contained in 1 to 10% by weight, more preferably 3 to 5% by weight based on the total weight of the composition. If the compound having an amino group and a carboxyl group is contained in less than 1% by weight, a tip of the Ti film may occur, which may cause a problem in a subsequent process, and when it exceeds 10% by weight, overetching of the Ti film may occur. .
상기 아미노기와 카르복실기를 갖는 화합물로는 알라닌계열, 아미노부티르산계열, 글루탐산계열, 글리신계열, 이미노디아세트산계열, 니트릴로트리아세트산계열, 사르코신계열 화합물을 들 수 있으며, 이들은 1종 단독으로 또는 2종 이상이 함께 사용될 수 있다.Examples of the compound having an amino group and a carboxyl group include alanine series, aminobutyric acid series, glutamic acid series, glycine series, iminodiacetic acid series, nitrilotriacetic acid series, and sarcosine series compounds, and these may be used alone or in combination of two or more. This can be used together.
구체적인 예로는 알라닌(alanine), 아미노부티르산(aminobutyric acid), 글루탐산(glutamic acid), 글리신(glycine), 이미노디아세트산(iminodiacetic acid), 니트릴로트리아세트산(nitrilotriacetic acid) 및 사르코신(sarcosine) 등을 들 수 있다. Specific examples include alanine, aminobutyric acid, glutamic acid, glycine, glycine, iminodiacetic acid, nitrilotriacetic acid, and sarcosine. Can be.
본 발명에서 질산염 화합물은 식각시에 Ti 및 Al막으로 이루어진 배선의 직진성을 향상시키는 역할을 하며, 조성물 총 중량에 대하여 0.1~5 중량%로 함유되는 것이 바람직하다. 상기 질산염 화합물이 0.1 중량% 미만으로 함유되는 경우에는 식각균일성이 저하되어 배선 모양이 불균일하게 형성되며, 기판내에 얼룩 문제가 발생한다. 또한, 5 중량%를 초과하는 경우에는 Ti 및 Al막의 식각속도 증가로 인한 과식각 현상이 발생하며, 식각균일성 저하로 인한 얼룩이 발생한다.In the present invention, the nitrate compound serves to improve the straightness of the wiring consisting of the Ti and Al film during etching, it is preferably contained in 0.1 to 5% by weight relative to the total weight of the composition. When the nitrate compound is contained in less than 0.1% by weight, the etching uniformity is reduced, the wiring shape is formed unevenly, and the problem of staining occurs in the substrate. In addition, when the content exceeds 5% by weight, an overetching phenomenon occurs due to an increase in the etching rate of the Ti and Al films, and a stain occurs due to a decrease in etching uniformity.
본 발명에서 질산염 화합물은 질산이온을 포함하는 유,무기 화합물을 의미하며, 예컨대, 질산암모늄(ammonium nitrate), 질산나트륨(sodium nitrate), 질산칼륨(potassium nitrate) 등을 들 수 있으며, 이들은 1종 단독으로 또는 2종 이상이 함께 사용될 수 있다.In the present invention, the nitrate compound means an organic or inorganic compound containing nitrate ions, and examples thereof include ammonium nitrate, sodium nitrate, potassium nitrate, and the like. It may be used alone or two or more kinds together.
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 고리형 아민 화합물을 더 포함할 수 있다. The etchant composition of the present invention may further include a cyclic amine compound.
식각액 조성물을 사용하여 식각하는 동안 식각액 내에 Ti 및 Al 금속 이온이 증가 하게 되는데, 이러한 금속이온의 증가는 약액내의 조성변화와 맞물려서 식각속도의 저하를 유발 하여 식각 특성을 저하시킨다. During etching using the etchant composition, Ti and Al metal ions increase in the etchant, and the increase of the metal ions is coupled with the change of the composition in the chemical solution, causing the lowering of the etching rate, thereby lowering the etching characteristics.
상기 고리형 아민 화합물은 금속 이온과 반응하여 안정된 형태를 이루기 때문에 기판의 처리매수를 증가시키는 역할을 한다. 상기 고리형 아민 화합물은 조성물 총 중량에 대하여 0.01~5 중량%로 함유되는 것이 바람직하다. 상기 고리형 화합물이 0.01 중량% 미만으로 함유되면 금속이온 안정화 효과가 미미하며, 5중량%를 초과하는 경우에는 고리형 화합물의 용해도가 낮기 때문에 약액 제조 시에 잘 녹지 않는 문제가 발생한다.Since the cyclic amine compound reacts with metal ions to form a stable form, the cyclic amine compound serves to increase the number of processed substrates. The cyclic amine compound is preferably contained in 0.01 to 5% by weight based on the total weight of the composition. When the content of the cyclic compound is less than 0.01% by weight, the metal ion stabilization effect is insignificant, and when the content of the cyclic compound is more than 5% by weight, the solubility of the cyclic compound is low, so that it does not dissolve well when preparing a chemical solution.
상기 고리형 아민 화합물로는 피롤리딘, 피롤린, 피롤, 인돌, 피라졸, 이미다졸, 피리미딘, 푸린, 피리딘, 벤조트리아졸 및 이들의 유도체를 들 수 있으며, 이들은 1종 단독으로 또는 2종 이상이 함께 사용될 있다.The cyclic amine compound may include pyrrolidine, pyrroline, pyrrole, indole, pyrazole, imidazole, pyrimidine, purine, pyridine, benzotriazole and derivatives thereof. More than one species may be used together.
본 발명의 식각액 조성물은 상기에 언급된 성분들 외에 통상의 첨가제를 더 첨가할 수 있으며, 그러한 첨가제로는 식각조절제, 계면활성제, 금속 이온 봉쇄제, 부식 방지제, pH 조절제 등을 들 수 있다.The etchant composition of the present invention may further add a conventional additive in addition to the components mentioned above, such additives include an etch regulator, a surfactant, a metal ion sequestrant, a corrosion inhibitor, a pH regulator and the like.
특히, 본 발명에서 상기 식각조절제로는 유기산을 사용할 수 있다. 본 발명에서 유기산이란, 상기 아미노기와 카르복실기를 갖는 화합물을 제외한 유기산을 의미한다. 유기산은 Ti 및 Al막에 대하여 식각균일성을 향상시키는 역할을 하며, 조성물 총 중량에 대하여 0.5~5 중량%로 함유될 수 있다. 상기와 같은 범위로 포함되는 경우에 식각균일성 저하로 인한 기판내의 얼룩의 발생을 감소시킬 수 있으며, Ti 및 Al막에 대한 과식각 현상 발생을 감소시킬 수 있다.In particular, in the present invention, the etching control agent may be an organic acid. In the present invention, the organic acid means an organic acid except for the compound having an amino group and a carboxyl group. The organic acid serves to improve the etching uniformity with respect to the Ti and Al film, it may be contained in 0.5 to 5% by weight based on the total weight of the composition. When included in the above range it is possible to reduce the occurrence of stains in the substrate due to the etching uniformity decrease, it is possible to reduce the occurrence of over-etching phenomenon for the Ti and Al film.
상기 유기산으로는 부탄산(butanoic acid), 시트르산(citric acid), 포름산(formic acid), 글루콘산(gluconic acid), 글리콜산(glycolic acid), 말론산(malonic acid), 옥살산(oxalic acid), 펜탄산(pentanoic acid), 그 외 수용성 유기산 등을 들 수 있으며, 이들은 1종 단독으로 또는 2종 이상이 함께 사용될 수 있다.The organic acid is butanoic acid, citric acid, formic acid, formic acid, gluconic acid, glycolic acid, malonic acid, oxalic acid, Pentanoic acid, other water-soluble organic acids, and the like, and these may be used alone or in combination of two or more.
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, 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 can be appropriately modified and changed by those skilled in the art within the scope of the present invention.
실시예 1 내지 11 및 비교예 1내지 5: 식각액 조성물의 제조Examples 1 to 11 and Comparative Examples 1 to 5: Preparation of the etchant composition
하기 표 1에 기재된 성분 및 조성비에 따라 식각액 조성물 180 kg을 제조하였다. 180 kg of an etchant composition was prepared according to the components and the composition ratios shown in Table 1 below.
표 1
H2O2 NH4FHF 이미노디아세트산 질산암모늄 C6H5N3 CH3COOH 물
실시예 1 25 1 3 3 0 0 68
실시예 2 20 1 5 1 0 0 73
실시예 3 15 1 3 0.5 0 1 79.5
실시예 4 15 1.2 4 2 0 0 77.8
실시예 5 10 1 5 3 0 0 81
실시예 6 25 1 3 3 0 3 65
실시예 7 20 1 5 1 0 4 69
실시예 8 15 1.2 4 2 0 2 75.8
실시예 9 10 1 5 3 0 5 76
실시예 10 15 1 55 0.5 0.5 0 78
실시예 11 15 1 5 0.5 0 0 78.5
비교예 1 20 2.5 5 2 0 4 66.5
비교예 2 15 0.8 4 3 0 9 68.2
비교예 3 4 0.3 2 5 0 3 85.7
비교예 4 20 0.5 0 0 0 0 79.5
비교예 5 15 1 3 7 0 1 73.0
Table 1
H 2 O 2 NH 4 FHF Imino diacetic acid Ammonium Nitrate C 6 H 5 N 3 CH 3 COOH water
Example 1 25 One 3 3 0 0 68
Example 2 20 One 5 One 0 0 73
Example 3 15 One 3 0.5 0 One 79.5
Example 4 15 1.2 4 2 0 0 77.8
Example 5 10 One 5 3 0 0 81
Example 6 25 One 3 3 0 3 65
Example 7 20 One 5 One 0 4 69
Example 8 15 1.2 4 2 0 2 75.8
Example 9 10 One 5 3 0 5 76
Example 10 15 One 55 0.5 0.5 0 78
Example 11 15 One 5 0.5 0 0 78.5
Comparative Example 1 20 2.5 5 2 0 4 66.5
Comparative Example 2 15 0.8 4 3 0 9 68.2
Comparative Example 3 4 0.3 2 5 0 3 85.7
Comparative Example 4 20 0.5 0 0 0 0 79.5
Comparative Example 5 15 One 3 7 0 One 73.0
(단위: 중량%)(Unit: weight%)
시험예. Test example.
(1)식각 특성 평가(1) etching characteristic evaluation
본 시험에서 기판으로는 글래스 위에 SiNx층이 증착 되어 있고 SiNx층 위에 Ti/Al/Ti 삼중막이 적층되어 있으며, 삼중막 위에는 일정한 형태의 모양으로 포토레지스트가 패터닝된 것을 사용하였다.In this test, a SiNx layer was deposited on the glass, a Ti / Al / Ti triple layer was stacked on the SiNx layer, and a photoresist patterned in a uniform shape was used on the triple layer.
분사식 식각 방식의 실험장비(SEMES사 제조, 모델명: ETCHER(TFT)) 내에 상기 실시예 1 내지 9 및 비교예 1 내지 5에서 제조된 식각액을 넣고 온도를 40℃로 세팅하여 가온한 후, 온도가 40±0.1℃에 도달한 후, 식각 공정을 수행하였다. 총 에칭 시간을 EPD 대비 30%의 Over Etch를 주어 식각을 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; HITACHI사 제조, 모델명: S-4700)을 이용하여 식각 프로파일의 경사각, 사이드 에치(CD(critical dimension) 손실, 식각 잔류물 및 하부막 손상을 평가하여, 그 결과를 하기 표 2에 나타내었다.Etching liquid prepared in Examples 1 to 9 and Comparative Examples 1 to 5 was put into a spray equipment of the etching method (SEMES, model name: ETCHER (TFT)) and warmed by setting the temperature to 40 ℃, the temperature was After reaching 40 ± 0.1 ° C., an etching process was performed. The etching was performed by giving 30% over etching of the total etching time. 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 the 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 below.
[식각 프로파일의 평가 기준][Evaluation Criteria of Etch Profile]
◎: 매우 우수(CD Skew:≤1㎛, Taper Angle: 40°~ 90°)◎: Excellent (CD Skew: ≤1㎛, Taper Angle: 40 ° ~ 90 °)
○: 우수(CD Skew:≤1.5㎛, Taper Angle: 40°~ 90°)○: Excellent (CD Skew: ≤1.5㎛, Taper Angle: 40 ° ~ 90 °)
△: 양호(CD Skew:≤2㎛, Taper Angle: 40°~ 90°)△: good (CD Skew: ≤2㎛, Taper Angle: 40 ° -90 °)
×: 불량(Pattern 소실 및 잔사 발생)×: defective (pattern loss and residue)
표 2
박막의 종류 식각프로파일 하부막손상 잔사
실시예 1 Ti/Al/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
실시예 9 ◎ 없음 없음
비교예 1 × 있음 없음
비교예 2 × 없음 있음
비교예 3 × 없음 있음
비교예 4 × 없음 없음
비교예 5 × 없음 없음
TABLE 2
Type of thin film Etch Profile Lower membrane damage Residue
Example 1 Ti / Al / 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
Example 9 ◎ none none
Comparative Example 1 × has exist none
Comparative Example 2 × none has exist
Comparative Example 3 × none has exist
Comparative Example 4 × none none
Comparative Example 5 × none none
상기 표 2에 나타낸 바와 같이, 실시예 1~9의 식각액으로 식각하는 경우 식각프로파일이 매우 우수하고, 하부막 손상이 없으며, 잔사 발생이 없는 우수한 식각 특성이 나타남을 확인할 수 있었다(도1 참조). 반면, 비교예 1~5의 식각액으로 식각 할 경우, 전체에서 식각프로파일의 불량이 관찰되었고, 일부에서는 하부막 손상, 잔사발생도 관찰되었다(도2 참조). As shown in Table 2, in the case of etching with the etchant of Examples 1 to 9 it was confirmed that the etching profile is very excellent, there is no damage to the lower film, there is an excellent etching characteristic without the occurrence of residue (see Fig. 1) . On the other hand, when etching with the etchant of Comparative Examples 1 to 5, the defect of the etching profile was observed in the whole, and in some cases the lower film damage, residues were also observed (see Fig. 2).
구체적으로, 비교예 1의 경우 NH4FHF가 과량으로 함유되어 하부막 손상이 발생하였으며, 비교예 2의 경우, CH3COOH가 과량으로 함유됨으로써 식각 속도의 저하로 인한 기판내의 불균일 식각 및 잔사 발생이 관찰되었으며, 비교예 3의 경우, H2O2가 너무 미량으로 포함되어 불균일 식각 및 잔사 발생이 관찰되었으며, 비교예 4의 경우, 아미노디아세트산 및 질산염이 식각액 조성물에 포함되지 않음으로써 불균일 식각과 그로 인한 얼룩의 발생 및 상부 Ti의 Tip 발생도 관찰되었다. 그리고, 비교예 5의 경우, 질산염이 과량으로 포함됨으로써 식각속도가 증가되고, 그에 따라 과식각에 의한 균일성 저하로 기판에 얼룩 발생됨이 확인되었다.Specifically, in Comparative Example 1, the NH 4 FHF was contained in an excessive amount, and the lower layer was damaged. In Comparative Example 2, the CH 3 COOH was contained in an excessive amount, resulting in uneven etching and residues in the substrate due to a decrease in the etching rate. It was observed, in the case of Comparative Example 3, H 2 O 2 contained in a very small amount, non-uniform etching and residues were observed, and in Comparative Example 4, amino diacetic acid and nitrate were not included in the etchant composition, non-uniform etching And staining and tip generation of upper Ti were also observed. And, in the case of Comparative Example 5, it was confirmed that the etching rate is increased by the excessive inclusion of nitrate, thereby causing stains on the substrate due to the uniformity decrease due to overetching.
(2) 식각 처리매수 평가(2) Evaluation of the number of etching treatments
상기 식각 특성 평가와 동일한 방법으로 실시예10 및 실시예11에서 제조된 식각액으로 포토레지스트를 제거하여 식각 처리매수를 평가하였다. 이때, 총 에칭 시간을 EPD 대비 Over Etch 30%로 하여 신액의 총 식각 속도를 고정하고, 처리매수를 100매부터 1000매까지 100매 단위로 하여 식각을 실시하였다. 전자주사현미경(SEM: HITACHI사 제조, 모델명: S-4700)을 이용하여 사이드 에치(CD(critical dimension)) 손실 변화를 평가하여, 그 결과를 하기 표 3에 나타내었다. The number of etching treatments was evaluated by removing the photoresist with the etchant prepared in Examples 10 and 11 in the same manner as the etching characteristic evaluation. At this time, the total etching time was over Etch 30% compared to the EPD to fix the total etching rate of the new liquid, and the number of processing was performed by 100 sheets to 100 sheets in etching. The change in side etch (CD) loss was evaluated using an electron scanning microscope (SEM: manufactured by Hitachi, model name: S-4700), and the results are shown in Table 3 below.
표 3
식각액 Side Etch(㎛) 처리매수
BLK 100매 200매 300매 400매 500매 600매 700매 800매 900매 1000매
실시예10 1.23 1.20 1.03 0.99 0.92 0.92 0.92 0.88 0.80 0.74 0.78
실시예11 0.92 0.88 0.85 0.84 0.84 0.70 0.59 0.50 0.42 0.41 0.39
TABLE 3
Etchant Side Etch (μm) Treatment
BLK 100 sheets 200 sheets 300 sheets 400 sheets 500 sheets 600 sheets 700 sheets 800 sheets 900 sheets 1000 sheets
Example 10 1.23 1.20 1.03 0.99 0.92 0.92 0.92 0.88 0.80 0.74 0.78
Example 11 0.92 0.88 0.85 0.84 0.84 0.70 0.59 0.50 0.42 0.41 0.39
상기 표 2에서 확인되는 바와 같이, 실시예10의 식각액에 비해 실시예11의 식각액의 경우 처리매수에 따라 Side Etch의 감소 변화폭이 크며 식각 직진성이 저하되는 특성을 보였다. 반면, 실시예10의 식각액의 경우는 BLK 대비 Side Etch의 변화폭이 심하지 않으며, 1000매에서도 식각 직진성이 우수한 식각특성을 보였다.As shown in Table 2, compared to the etching solution of Example 10, the etching solution of Example 11 showed a large change in the side etching decreases according to the number of treatments, and the etching straightness was lowered. On the other hand, in the case of the etching solution of Example 10, the variation of the side etching compared to the BLK is not severe, and even 1000 sheets showed excellent etching characteristics.

Claims (7)

  1. 조성물 총중량에 대하여, 5~30 중량%의 H2O2, 0.1~2 중량%의 함불소 화합물, 1~10 중량%의 아미노기와 카르복실기를 갖는 화합물, 0.1~5 중량%의 질산염 및 잔량의 물을 함유하는 티타늄, 티타늄 합금, 알루미늄 및 알루미늄 합금으로 이루어진 군으로부터 선택되는 1종 이상의 금속으로 형성되는 단일막 또는 이중막 이상의 다중막용 식각액 조성물. 5-30% by weight of H 2 O 2 , 0.1-2% by weight of fluorine-containing compound, 1-10% by weight of amino and carboxyl groups, 0.1-5% by weight of nitrate and residual water Etch liquid composition for a single film or a double film or more formed of at least one metal selected from the group consisting of titanium, titanium alloys, aluminum and aluminum alloys containing.
  2. 청구항 1에 있어서, 0.01~5 중량%의 고리형 아민 화합물을 더 포함하는 것을 특징으로 하는 식각액 조성물. The etchant composition according to claim 1, further comprising 0.01 to 5% by weight of a cyclic amine compound.
  3. 청구항 1에 있어서, 상기 함불소 화합물은 불소 이온 또는 다원자 불소이온이 해리될 수 있는 화합물로서, 불화암모늄, 불화나트륨, 불화칼륨, 중불화나트륨, 중불화칼륨, 중불화암모늄 및 불화수소로 이루어진 군으로부터 선택되는 1종 또는 2종 이상의 것임을 특징으로 하는 식각액 조성물.The method of claim 1, wherein the fluorine-containing compound is a compound capable of dissociating fluorine ions or polyatomic fluorine ions, ammonium fluoride, sodium fluoride, potassium fluoride, sodium bifluoride, potassium bifluoride, ammonium bifluoride and hydrogen fluoride Etching liquid composition, characterized in that one or two or more selected from the group.
  4. 청구항 1에 있어서, 상기 아미노기와 카르복실기를 갖는 화합물은 알라닌계열, 아미노부티르산계열, 글루탐산계열, 글리신계열, 이미노디아세트산계열, 니트릴로트리아세트산계열 및 사르코신계열 화합물로 이루어진 군으로부터 선택되는 1종 또는 2종 이상의 것임을 특징으로 하는 식각액 조성물.The compound according to claim 1, wherein the compound having an amino group and a carboxyl group is selected from the group consisting of alanine series, aminobutyric acid series, glutamic acid series, glycine series, imino diacetic acid series, nitrilotriacetic acid series and sarcosine series compounds. Etch liquid composition, characterized in that more than one species.
  5. 청구항 1에 있어서, 상기 질산염 화합물은 질산암모늄(ammonium nitrate), 질산나트륨(sodium nitrate) 및 질산칼륨(potassium nitrate)으로 이루어진 군으로부터 선택되는 1종 또는 2종 이상의 것임을 특징으로 하는 식각액 조성물.The etchant composition according to claim 1, wherein the nitrate compound is one or two or more selected from the group consisting of ammonium nitrate, sodium nitrate, and potassium nitrate.
  6. 청구항 2에 있어서, 상기 고리형 아민 화합물은 피롤리딘, 피롤린, 피롤, 인돌, 피라졸, 이미다졸, 피리미딘, 푸린, 피리딘 및 이들의 유도체로 이루어진 군으로부터 선택되는 1종 또는 2종 이상의 것임을 특징으로 하는 식각액 조성물.The cyclic amine compound according to claim 2, wherein the cyclic amine compound is one or two or more selected from the group consisting of pyrrolidine, pyrroline, pyrrole, indole, pyrazole, imidazole, pyrimidine, purine, pyridine and derivatives thereof Etch liquid composition, characterized in that.
  7. 청구항 1에 있어서, 부탄산(butanoic acid), 시트르산(citric acid), 포름산(formic acid), 글루콘산(gluconic acid), 글리콜산(glycolic acid), 말론산(malonic acid), 옥살산(oxalic acid) 및 펜탄산(pentanoic acid)으로 이루어진 군으로부터 선택되는 1종 또는 2종 이상의 유기산을 더 포함하는 것을 특징으로 하는 식각액 조성물.The method of claim 1, wherein butanoic acid, citric acid, formic acid, gluconic acid, glycolic acid, malonic acid, oxalic acid And pentanic acid (pentanoic acid) etching liquid composition characterized in that it further comprises one or two or more organic acids selected from the group consisting of.
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