KR100448868B1 - Etchant composition for amorphous ito - Google Patents
Etchant composition for amorphous ito Download PDFInfo
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- KR100448868B1 KR100448868B1 KR10-2002-0040029A KR20020040029A KR100448868B1 KR 100448868 B1 KR100448868 B1 KR 100448868B1 KR 20020040029 A KR20020040029 A KR 20020040029A KR 100448868 B1 KR100448868 B1 KR 100448868B1
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- 239000000203 mixture Substances 0.000 title claims abstract description 34
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 72
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 24
- 150000007522 mineralic acids Chemical class 0.000 claims abstract description 23
- 230000001590 oxidative effect Effects 0.000 claims abstract description 18
- 239000004094 surface-active agent Substances 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims description 15
- 239000002253 acid Substances 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 239000012425 OXONE® Substances 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- 239000013543 active substance Substances 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- 150000001450 anions Chemical class 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 125000003709 fluoroalkyl group Chemical group 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 229910052755 nonmetal Inorganic materials 0.000 claims description 2
- HJKYXKSLRZKNSI-UHFFFAOYSA-I pentapotassium;hydrogen sulfate;oxido sulfate;sulfuric acid Chemical compound [K+].[K+].[K+].[K+].[K+].OS([O-])(=O)=O.[O-]S([O-])(=O)=O.OS(=O)(=O)O[O-].OS(=O)(=O)O[O-] HJKYXKSLRZKNSI-UHFFFAOYSA-I 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 239000011593 sulfur Substances 0.000 claims description 2
- 238000005530 etching Methods 0.000 abstract description 52
- 239000012528 membrane Substances 0.000 abstract description 20
- 238000001704 evaporation Methods 0.000 abstract description 11
- 230000008020 evaporation Effects 0.000 abstract description 11
- 239000000654 additive Substances 0.000 abstract description 6
- 230000000996 additive effect Effects 0.000 abstract description 5
- 229910052751 metal Inorganic materials 0.000 abstract description 5
- 239000002184 metal Substances 0.000 abstract description 5
- 239000007800 oxidant agent Substances 0.000 abstract 1
- 239000010408 film Substances 0.000 description 15
- 239000000243 solution Substances 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- 239000007788 liquid Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 229920002120 photoresistant polymer Polymers 0.000 description 5
- 238000001878 scanning electron micrograph Methods 0.000 description 5
- 239000004973 liquid crystal related substance Substances 0.000 description 4
- 238000011109 contamination Methods 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- -1 oxidizing aid Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 238000001039 wet etching Methods 0.000 description 2
- 238000000137 annealing Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 150000004683 dihydrates Chemical group 0.000 description 1
- 239000007884 disintegrant Substances 0.000 description 1
- 238000001312 dry etching Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000003574 free electron Substances 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229910001432 tin ion Inorganic materials 0.000 description 1
- 238000004148 unit process Methods 0.000 description 1
Classifications
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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
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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Weting (AREA)
Abstract
본 발명은 화소전극을 구성하는 ITO 막을 식각하는 식각액에 첨가제를 넣어서 성질을 개선시키는 것에 관한 조성물로서, 이 조성물의 총중량에 대하여 0.5 ~ 8 중량% 의 옥살산; 0.1 ~ 5 중량% 의 무기산; 0.1 ~ 5 중량% 의 산화보조제; 1 ~ 1000 ppm 의 계면활성제 및 상기 조성물 총중량이 100 중량% 가 되도록 물을 첨가시켜 이루어진 비결정질 ITO 막 식각액 조성물을 제공하는 것이다. 본 발명에 의하면, ITO 막 식각액에 의하여 하부금속 막의 손상을 방지함과 아울러 식각속도는 온도변화로서 뿐만 아니라 무기산의 농도를 통해서도 조절이 가능하게 되어 작업공정시간을 자유로이 조정할 수 있고, 식각액의 온도를 비교적 낮게 유지하여 식각액의 증발량을 감소시킴으로써 식각액의 소비량을 줄이고, 또한 ITO 막 식각 중에 빈번하게 발생되는 패턴(pattern) 주변의 잔사 문제는 보조 산화제를 첨가시킴으로써 해결된다.The present invention relates to a composition for improving properties by adding an additive to an etching solution for etching an ITO film constituting a pixel electrode, the composition comprising: 0.5 to 8% by weight of oxalic acid based on the total weight of the composition; 0.1-5% by weight of inorganic acid; 0.1 to 5% by weight of an oxidizing aid; It is to provide an amorphous ITO membrane etchant composition formed by adding 1 to 1000 ppm of surfactant and water so that the total weight of the composition is 100% by weight. According to the present invention, the ITO membrane etchant prevents damage to the underlying metal membrane and the etching rate can be controlled not only as a temperature change but also through the concentration of the inorganic acid, so that the working time can be freely adjusted and the temperature of the etchant can be adjusted. Remaining relatively low reduces the evaporation of the etchant, thereby reducing the consumption of the etchant, and also the problem of residues around the pattern frequently generated during ITO film etching is solved by adding auxiliary oxidants.
Description
본 발명은 반도체 장치에서 금속막의 습식 식각용으로 사용되는 새로운 식각액 조성물에 관한 것으로, 보다 구체적으로 액정표시장치의 화소전극을 구성하는 비결정질 ITO 막 (amorphous Indium-Tin-Oxide) 을 식각하는 식각액 조성물에 관한 것이다.The present invention relates to a novel etchant composition used for wet etching a metal film in a semiconductor device, and more particularly to an etchant composition for etching an amorphous indium-tin-oxide (ITO) film constituting a pixel electrode of a liquid crystal display device. It is about.
액정 표시장치의 화소전극을 구성하는 ITO 막은 우수한 도전성을 가지며 화학적 열적 안정성이 좋고 패턴 가공성이 좋아 널리 이용된다. ITO 는 가시영역에서 전기절연성을 띠지만 산소 부족에 기인한 화학양론 조성에서 어긋나거나 불순물의 도입 (주석이온) 등에 의해 결정될 경우에 자유전자가 생성되어 가시영역에서 투명하면서도 도전성을 갖고있다. 일반적으로 300 ~ 500 ℃ 열처리를 받으면 ITO 의 저항치 (1.7 ~ 2.0 X 10-4 Ωcm)는 2.5 ~ 3 배 상승한다. 다만, 열안정성은 약간 열약하지만 막 두께가 두꺼워질수록 저항의 열처리후의 상승률은 작아지는 경향이 있다. 증착막은 산에 의한 식각속도가 빠르고, ITO 막 중에서는 미세한 패턴 가공이 비교적 쉽다는 장점을 갖는다.The ITO film constituting the pixel electrode of the liquid crystal display device is widely used because it has excellent conductivity, good chemical thermal stability, and good pattern processability. ITO is electrically insulating in the visible region, but free electrons are generated in the visible region when it is shifted from the stoichiometric composition due to lack of oxygen or determined by the introduction of impurities (tin ions). In general, after 300 ~ 500 ℃ heat treatment, the resistance of ITO (1.7 ~ 2.0 X 10-4 Ωcm) is increased 2.5 ~ 3 times. However, the thermal stability is slightly inferior, but as the film thickness increases, the rate of increase after the heat treatment of the resistance tends to decrease. Evaporation film has the advantage that the etching rate by the acid is fast, the fine pattern processing is relatively easy in the ITO film.
반도체 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.The process of forming the metal wiring on the substrate in the semiconductor device is generally composed of a metal film forming process by sputtering, a photoresist forming process in a selective region by photoresist coating, exposure and development, and an etching process. And washing processes before and after individual unit processes. The etching process refers to a process of leaving a metal film in a selective region using a photoresist mask, and typically, a dry etching using a plasma or the like, or a wet etching using an etching solution is used.
이러한 반도체 장치에서, TFT-LCD (thin film transistor-liquid crystal display) 의 액정표시장치의 화소전극을 구성하는 ITO 막은 어닐링의 순서에 따라서 결정질과 비결정질 ITO 막으로 나누어 볼 수 있다. 어닐링을 먼저하여 결정질이 된 ITO 막의 경우 염화제2철, 왕수 등의 식각액을 사용하였다. 염화제2철, 왕수의 식각액은 높은 온도에서 사용하므로 식각액의 증발량이 많기 때문에 식각액에 포함된 유해물질이 작업환경을 오염시키는 단점을 갖고 있었다. 이러한 단점을개선 및 식각 공정을 개선시킨 한국특허 제2000-65954호에는 ITO 막을 어닐링 하지 않은 상태인 비결정질 상태로 증착한 후, 그 상태에서 옥살산의 식각액으로 ITO 막의 패턴을 형성한다. 식각 후에 그 ITO 막을 어닐링하여 결정화단계를 거친다. 또한, 한국 특허공개번호 제2000-17470호에는 옥살산에 염류를 첨가제로 첨가하여서 식각액의 안정성과 식각액의 증발을 극소화시키는 등 식각액의 성능을 향상시킨 것이 개시되어 있다.In such a semiconductor device, an ITO film constituting a pixel electrode of a liquid crystal display device of a thin film transistor-liquid crystal display (TFT-LCD) can be divided into crystalline and amorphous ITO films in the order of annealing. In the case of the crystalline ITO membrane which was annealed first, an etchant such as ferric chloride or aqua regia was used. Since ferric chloride and aqua regia are used at high temperatures, the amount of evaporation of the etchant is high, and thus harmful substances contained in the etchant contaminate the working environment. Korean Patent No. 2000-65954, which improves these disadvantages and improves the etching process, deposits an ITO film in an amorphous state in which it is not annealed, and then forms a pattern of the ITO film with an oxalic acid etchant. After etching, the ITO film is annealed to undergo a crystallization step. In addition, Korean Patent Publication No. 2000-17470 discloses the addition of a salt to oxalic acid as an additive to improve the performance of the etchant, such as minimizing the stability of the etchant and the evaporation of the etchant.
옥살산의 식각액은 Cr, Al, Mo 등의 하부막에 손상을 입히지 않을 뿐만 아니라 식각액의 온도를 80 ℃ 정도로 가열시키지 않아도 80 ℃ 정도에서 식각한 경우보다 2 배정도 빠른 식각속도를 유지 할 수 있으므로 식각액의 증발에 의한 유해물질이 작업환경을 오염시키는 것을 감소시킬 수 있었다.Oxalic acid etchant does not damage the lower layer of Cr, Al, Mo, etc., and it can maintain the etching speed about twice as fast as that of 80 ℃ even without heating the temperature of the etchant. Hazardous substances from evaporation could reduce the contamination of the work environment.
그러나, 온도에 의해서만 식각속도가 결정되는 반면에, 옥살산만으로 제조된 식각액을 ITO 식각에 사용하면 패턴 주위에 잔사가 발생하기 쉬운 단점이 있다.However, while the etching rate is determined only by the temperature, when an etchant prepared only with oxalic acid is used for ITO etching, residues tend to occur around the pattern.
이에 본 발명자들은 이러한 문제점을 해결하고자 예의 검토한 결과, 종래의 옥살산 식각액에 소량의 무기산과 산화보조제를 첨가하는 형태의 식각액을 개발하였다. 무기산은 기존의 결정질 ITO 식각액에 첨가하여 사용되고 있지만, 장비 부식성과 식각액의 증발에 의한 유해물질이 작업환경을 오염시키기 때문에 옥살산만으로 제조된 식각액을 사용하고 있었다. 그러나 무기산계의 장점인 안정적인 식각속도를 얻기 위하여 소량을 첨가하였고, 산화보조제는 식각액의 산화력을 높여 옥살산만을 이용한 식각에서 발생하기 쉬운 잔사 문제를 해결하기 위해 첨가시켰다.Accordingly, the present inventors have intensively studied to solve such problems, and have developed an etching solution in which a small amount of an inorganic acid and an oxidizing aid are added to the conventional oxalic acid etching solution. Inorganic acid is used in addition to the existing crystalline ITO etchant, but because the harmful substances due to equipment corrosion and evaporation of the etchant contaminates the working environment, an etchant prepared only with oxalic acid was used. However, a small amount was added in order to obtain a stable etching rate, which is an advantage of the inorganic acid system, and an oxidizing aid was added to solve the problem of residue that is likely to occur in etching using only oxalic acid by increasing the oxidation power of the etching solution.
개발한 비결정질 ITO 막 식각액은 기존의 식각액에 비하여 식각속도가 온도뿐만 아니라 무기산의 양으로도 조절 가능하게 되었고, 낮은 온도에서 사용하므로 식각액의 증발량이 적다. 따라서, 식각액 증발에 의한 유해물질이 작업환경을 오염시키는 것을 감소시킨다. 또한 옥살산을 주성분으로 하는 식각액에서 발생하기 쉬운 패턴부 잔사 문제도 해결이 가능하다.The developed amorphous ITO membrane etchant can be controlled not only by the etching rate but also by the amount of inorganic acid, compared to the conventional etching solution. Therefore, the harmful substances by the etching liquid evaporation reduce the contamination of the working environment. In addition, it is possible to solve the problem of the pattern portion residues that are likely to occur in the etching liquid containing oxalic acid as a main component.
도 1 는 (a) 식각되지 않은 표면의 주사전자현미경 사진, (b) 식각된 표면의 주사전자현미경 사진을 나타낸 것이다.Figure 1 shows (a) a scanning electron micrograph of the unetched surface, (b) a scanning electron micrograph of the etched surface.
도 2 는 (a) 비교예 1 에 의해 제조된 식각액에 의한 식각공정 후의 표면의 주사전자현미경 사진, (b) 실시예 1 에 의해 제조된 식각액에 의한 식각공정 후의 표면의 주사전자현미경 사진을 나타낸 것이다.Figure 2 shows a scanning electron micrograph of the surface after the etching process by the etching solution prepared in (a), Comparative Example 1, (b) shows a scanning electron micrograph of the surface after the etching process by the etchant prepared in Example 1 will be.
도 3 은 (a) 비교예 1 의 패턴부 잔사의 주사전자현미경 사진, (b) 실시예 1 의 패턴부 잔사의 주사전자현미경 사진을 나타낸 것이다.FIG. 3 shows a scanning electron micrograph of the pattern part residue of (a) Comparative Example 1, and (b) the scanning electron microscope picture of the pattern part residue of Example 1;
본 발명을 실현하기 위한 수단으로서, 옥살산, 무기산, 산화보조제, 계면활성제 및 물을 함유하는 비결정질 ITO 막 식각액 조성물을 제공한다.As a means for realizing the present invention, there is provided an amorphous ITO membrane etchant composition containing oxalic acid, an inorganic acid, an oxidizing aid, a surfactant, and water.
보다 구체적으로, 전체 조성물의 총중량에 대하여 0.5 ~ 8 중량% 의 옥살산; 0.1 ~ 5 중량% 의 무기산; 0.1 ~ 5 중량% 의 산화보조제; 1 ~ 1000 ppm 계면활성제 및 조성물 총중량이 100 중량% 가 되도록 하는 물을 함유시켜 이루어진 비결정질 ITO 막 식각액 조성물을 제공한다.More specifically, 0.5 to 8% by weight of oxalic acid relative to the total weight of the total composition; 0.1-5% by weight of inorganic acid; 0.1 to 5% by weight of an oxidizing aid; An amorphous ITO membrane etchant composition is provided comprising 1 to 1000 ppm of surfactant and water such that the total weight of the composition is 100% by weight.
이하에서 본 발명을 보다 상세히 설명한다.Hereinafter, the present invention will be described in more detail.
본 발명에 의한 식각액 조성물은 비결정질 ITO 막을 식각하기 위한 식각액이다.The etchant composition according to the present invention is an etchant for etching an amorphous ITO membrane.
본 발명의 비결정질 ITO 막 식각액 조성물에 사용되는 옥살산은 99.5 % 이상의 순도를 가진 2 수화물 형태의 것을 이용한다.Oxalic acid used in the amorphous ITO membrane etchant composition of the present invention utilizes a dihydrate form having a purity of at least 99.5%.
본 발명의 비결정질 ITO 막 식각액 조성물에 사용되는 무기산은 염소, 황, 질소 또는 인등의 비금속을 함유하는 산기(酸基)가 수소와 결합하여 생긴 산으로염산, 황산, 질산 또는 인산 등이 있다.The inorganic acid used in the amorphous ITO membrane etching liquid composition of the present invention is an acid produced by the combination of an acid group containing a nonmetal such as chlorine, sulfur, nitrogen, or phosphorus with hydrogen, such as hydrochloric acid, sulfuric acid, nitric acid or phosphoric acid.
본 발명의 비결정질 ITO 막 식각액 조성물에 사용되는 산화보조제는 활성산소를 포함하는 각종 염들로 옥손(칼륨 모노퍼술페이트), K2S2O8, Na2S2O8, (NH4)2S2O8및 H2O2등이 있다.Oxidation aids used in the amorphous ITO membrane etchant composition of the present invention are various salts containing active oxygen, such as oxone (potassium monopersulfate), K 2 S 2 O 8 , Na 2 S 2 O 8 , (NH 4 ) 2 S 2 O 8 and H 2 O 2 .
본 발명의 비결정질 ITO 막 식각액 조성물에 사용되는 계면활성제는 수용액에서 이온화하여 활성제의 주체가 음이온으로서 암모늄 플루오로알킬 설포네이트 등이 있다.Surfactants used in the amorphous ITO membrane etching liquid composition of the present invention are ionized in an aqueous solution, and the main agent of the active agent is ammonium fluoroalkyl sulfonate as an anion.
본 발명의 비결정질 ITO 막 식각액 조성물은 이 조성물의 총 중량이 100 중량% 가 되도록 물로 희석한다.The amorphous ITO membrane etchant composition of the present invention is diluted with water so that the total weight of this composition is 100% by weight.
본 발명의 비결정질 ITO 막 식각액 조성물은 대부분 물로 구성되며, 상기 옥살산, 무기산, 산화보조제 및 계면활성제는 필수적으로 함유하며, 필요에 따라 금속 이온 붕쇄제, 부식 방지제 및 pH 조절제 등의 첨가제를 추가로 함유할 수 있다.Most of the amorphous ITO membrane etchant composition of the present invention is composed of water, and the oxalic acid, inorganic acid, oxidizing aid, and surfactant are essentially contained, and additionally, additives such as metal ion disintegrants, corrosion inhibitors, and pH adjusting agents are necessary. can do.
본 발명의 비결정질 ITO 막 식각액 조성물은 옥살산, 무기산, 산화보조제, 계면활성제 및 물을 함유하고, 또는 물을 제외한 옥살산/무기산/산화보조제/계면활성제의 조성비는 0.5 ~ 8 중량%/0.1 ~ 5 중량%/0.1 ~ 5 중량%/1 ~ 1000 ppm 이 될 때, 비결정질 ITO 막이 일정한 온도에서 함량의 변화로 식각속도의 조절이 가능하고(표 1), 낮은 온도에서 사용하기 때문에 식각액의 증발량이 감소된다. 따라서, 식각액 증발에 의한 유해물질이 작업환경을 오염시키는 것을 방지할 수 있다. 또한 기존 옥살산 식각액이나 옥살산/무기산 식각액에서 나타나던 패턴부 잔사가 산화보조제의 첨가로 인해 나타나지 않았다.The amorphous ITO membrane etchant composition of the present invention contains oxalic acid, inorganic acid, oxidizing aid, surfactant, and water, or the composition ratio of oxalic acid / inorganic acid / oxidizing aid / surfactant except water is 0.5 to 8 wt% / 0.1 to 5 wt% When% / 0.1 to 5% by weight / 1 to 1000 ppm, the etching rate of the amorphous ITO membrane can be controlled by changing the content at a constant temperature (Table 1), and the evaporation amount of the etchant is reduced because it is used at a lower temperature. . Therefore, it is possible to prevent the harmful substances due to the evaporation of the etchant contaminate the working environment. In addition, the pattern part residue that appeared in the existing oxalic acid etchant or oxalic acid / inorganic acid etchant did not appear due to the addition of the oxidizing aid.
본 발명의 실시예의 표 1 에 있어서, 비교예 1 은 전술한 한국특허 제2000-65954호에 개시된 바와 같이 옥살산만을 이용하여 ITO 막을 식각한 경우이다. 실시예 1 ~ 6 은 옥살산에 무기산과 산화보조제를 첨가하여서 실험한 결과이다. 표 1 에서와 같이 첨가제의 양에 따라서 다양한 식각속도를 나타내었다. 무기산의 양이 증가함에 따라서 비결정질 ITO 막 식각속도가 증가되지만, 무기산이 5 중량% 를 초과하면 식각속도의 증가보다 장치부식현상을 고려해 보아야 하는 문제가 생긴다. 산화보조제가 첨가되는 것은 패턴 (pattern) 주변의 잔사를 효과적으로 해결하기 위함이다. 그러나, 산화보조제를 5 중량% 초과하여 사용하면, 잔사가 제거될 뿐만 아니라 미세패턴의 식각을 일으켜 데이터라인에 단락을 발생시킨다.In Table 1 of Examples of the present invention, Comparative Example 1 is a case where the ITO membrane is etched using only oxalic acid as disclosed in the above-described Korean Patent No. 2000-65954. Examples 1 to 6 show the results of experiment by adding an inorganic acid and an oxidizing aid to oxalic acid. As shown in Table 1, various etching rates were shown depending on the amount of the additive. As the amount of inorganic acid increases, the etching rate of amorphous ITO film increases. However, when the inorganic acid exceeds 5% by weight, the device corrosion phenomenon should be considered rather than the increase of the etching rate. The addition of the oxidizing aid is to effectively solve the residue around the pattern. However, when the oxidizing aid is used in excess of 5% by weight, not only the residue is removed but also the etching of the micropattern causes a short circuit in the data line.
이하, 실시예를 들어 본 발명을 상세히 설명하지만, 본 발명은 하기 실시예로만 한정되는 것은 아니다.Hereinafter, although an Example is given and this invention is demonstrated in detail, this invention is not limited only to a following example.
[실시예]EXAMPLE
비교예 1Comparative Example 1
비결정질 ITO 막 기판을 다이아몬드 칼을 이용하여 100 mm X 100 mm 로 자른 시험편을 제작하였다. 조성물의 총중량에 대하여 3.4 중량% 의 옥살산[(COOH)2ㆍ2H2O)]에 물을 첨가하는 식각액을 10 kg 이 되도록 제조하였다. 분사식 식각 방식의 실험장비 (KDNS사 제조, 모델명: ETCHER(TFT)) 내에 제조된 식각액을 넣고 온도를 37 ℃ 로 가온한 후, 온도가 37 ±0.5 ℃ 에 도달하면 식각 공정을 수행하였다. 시험편을 넣고 분사시켜 상기 식각 공정을 수행하고, 이어서 탈이온수로 세정한 후, 열풍건조장치로 건조시켜, 포토 레지스트 박리기 (stripper) 를 이용하여 포토 레지스트를 제거하였다. 세정 및 건조 후 주사전자현미경 (SEM ; 히다찌사 제조, 모델명: S-4700) 을 이용하여 식각의 형성도와, CD (critical dimension) 손실, 식각 잔류물 등으로 평가하였다. 그 결과를 표 1, 도 2 및 도 3 에 나타내었다.A test piece was prepared in which an amorphous ITO membrane substrate was cut to 100 mm × 100 mm using a diamond knife. An etching solution in which water was added to 3.4 wt% of oxalic acid [(COOH) 2 .2H 2 O)] based on the total weight of the composition was prepared to be 10 kg. After the etching solution prepared in the spray etching method (KDNS, model name: ETCHER (TFT)) was added to warm the temperature to 37 ℃, the etching process was performed when the temperature reaches 37 ± 0.5 ℃. After the test piece was inserted and sprayed to carry out the above etching process, and then washed with deionized water, dried with a hot air dryer, the photoresist was removed using a photoresist stripper. After washing and drying, the result was evaluated by using a scanning electron microscope (SEM; manufactured by Hitachi, model: S-4700) for the degree of formation of etching, loss of critical dimension (CD), and etching residue. The results are shown in Table 1, FIG. 2 and FIG.
실시예 1 내지 6Examples 1-6
옥살산, 무기산, 산화보조제, 계면활성제 및 나머지 물을 모두 함유하고, 표 1 에 기재된 조성비로 배합된 식각액을 제조하는 것 이외에는 비교예 1 과 동일한 방법으로 실시한다. 그 결과를 표 1 에 나타낸다. 각 성분의 함량이 본 발명에 의한 비결정질 ITO 막 식각액 조성물의 조성범위에 해당하므로, 식각속도가 빠르고, 잔사가 발생하지 않았다.Oxalic acid, an inorganic acid, an oxidizing aid, a surfactant, and the remaining water are all contained, and the same procedure as in Comparative Example 1 is carried out except that an etchant prepared in the composition ratios shown in Table 1 is prepared. The results are shown in Table 1. Since the content of each component corresponds to the composition range of the amorphous ITO film etching liquid composition according to the present invention, the etching speed is fast and no residue was generated.
비교예 2 및 3Comparative Examples 2 and 3
표 1 에 기재된 조성비로 배합된 식각액을 제조하는 것 이외에는 비교예 1 과 동일한 방법으로 실시한다. 그 결과를 표 1 에 나타낸다. 무기산 또는 산화보조제가 첨가되지 않은 비교예 2 또는 비교예 3 에서 제조된 식각액의 경우에는, 실시예 1 ~ 6 에서 제조된 비결정질 ITO 막 식각액 보다 효과가 저하되는 것으로 나타났다.The same procedure as in Comparative Example 1 was carried out except that the etching solution formulated at the composition ratios shown in Table 1 was prepared. The results are shown in Table 1. In the case of the etching solution prepared in Comparative Example 2 or Comparative Example 3, in which the inorganic acid or the oxidizing aid was not added, the effect was lowered than the amorphous ITO membrane etching solution prepared in Examples 1 to 6.
본 발명은 의하면, 비결정질 ITO 막 식각액은 기존의 식각액에 비하여 식각속도의 조절이 온도변화로서 뿐만 아니라 첨가제의 양으로도 조절 가능하게 되어, 무기산을 첨가제로 이용하지만, 낮은 온도에서 식각액의 사용이 용이하며 식각액의 증발량이 감소되었다. 따라서, 식각액 증발에 의한 유해물질이 작업환경을 오염시키는 것을 감소시킬 수 있다. 또한 산화보조제를 첨가함으로써 기존 옥살산 형태 식각액에서 나타나는 패턴 주변부 잔사 문제를 해결 할 수 있다.According to the present invention, the amorphous ITO membrane etchant can control the etching rate not only as the temperature change but also as the amount of the additive, compared to the conventional etchant. The inorganic acid is used as the additive, but the etching solution is easy to use at low temperatures. The evaporation amount of the etchant was reduced. Therefore, it is possible to reduce the contamination of the working environment by the harmful substances by the etching liquid evaporation. In addition, the addition of an oxidizing aid can solve the problem of the pattern periphery residue in the existing oxalic acid type etching solution.
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| US7329365B2 (en) | 2004-08-25 | 2008-02-12 | Samsung Electronics Co., Ltd. | Etchant composition for indium oxide layer and etching method using the same |
| KR101191405B1 (en) * | 2005-07-13 | 2012-10-16 | 삼성디스플레이 주식회사 | Etchant and method for fabricating liquid crystal display using the same |
| KR200489564Y1 (en) | 2019-02-13 | 2019-07-04 | 이희경 | Led module for light |
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