TWI681076B - Etchant composition and method of forming metal pattern using the same - Google Patents
Etchant composition and method of forming metal pattern using the same Download PDFInfo
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- 239000000203 mixture Substances 0.000 title claims abstract description 41
- 238000000034 method Methods 0.000 title claims abstract description 28
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 20
- 239000002184 metal Substances 0.000 title claims abstract description 20
- 229910001182 Mo alloy Inorganic materials 0.000 claims abstract description 61
- 238000005530 etching Methods 0.000 claims abstract description 45
- 229910000838 Al alloy Inorganic materials 0.000 claims abstract description 35
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 30
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 29
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 29
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 15
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- DTSBBUTWIOVIBV-UHFFFAOYSA-N molybdenum niobium Chemical group [Nb].[Mo] DTSBBUTWIOVIBV-UHFFFAOYSA-N 0.000 claims description 17
- 239000000758 substrate Substances 0.000 claims description 11
- 239000004094 surface-active agent Substances 0.000 claims description 7
- UBSJOWMHLJZVDJ-UHFFFAOYSA-N aluminum neodymium Chemical group [Al].[Nd] UBSJOWMHLJZVDJ-UHFFFAOYSA-N 0.000 claims description 5
- 239000004973 liquid crystal related substance Substances 0.000 claims description 4
- 239000010409 thin film Substances 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 230000007797 corrosion Effects 0.000 claims description 3
- 238000005260 corrosion Methods 0.000 claims description 3
- 239000003112 inhibitor Substances 0.000 claims description 3
- NXLSGYSTDQCZQM-UHFFFAOYSA-N [O-2].[Nb+5].[Mo+4] Chemical compound [O-2].[Nb+5].[Mo+4] NXLSGYSTDQCZQM-UHFFFAOYSA-N 0.000 claims description 2
- CFJRGWXELQQLSA-UHFFFAOYSA-N azanylidyneniobium Chemical compound [Nb]#N CFJRGWXELQQLSA-UHFFFAOYSA-N 0.000 claims 1
- 229920002120 photoresistant polymer Polymers 0.000 abstract description 14
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 238000005336 cracking Methods 0.000 abstract description 4
- 239000010410 layer Substances 0.000 description 95
- 229910052782 aluminium Inorganic materials 0.000 description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 8
- 229910052750 molybdenum Inorganic materials 0.000 description 8
- 239000011733 molybdenum Substances 0.000 description 8
- 238000012545 processing Methods 0.000 description 5
- 239000000654 additive Substances 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 238000001312 dry etching Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000001039 wet etching Methods 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000010955 niobium Substances 0.000 description 2
- 229910000484 niobium oxide Inorganic materials 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 238000003491 array Methods 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
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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
- C23F1/44—Compositions for etching metallic material from a metallic material substrate of different composition
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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
-
- 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
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- 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
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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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having 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
- H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
- H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
- H01L21/30604—Chemical etching
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having 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
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- Thin Film Transistor (AREA)
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- Internal Circuitry In Semiconductor Integrated Circuit Devices (AREA)
Abstract
Description
本發明涉及蝕刻劑組合物，其包含磷酸、硝酸、 乙酸、硫酸和水以便蝕刻包含鋁合金和鉬合金的多層，以及利用所述蝕刻劑組合物形成金屬圖案的方法。 The present invention relates to an etchant composition, which contains phosphoric acid, nitric acid, Acetic acid, sulfuric acid, and water in order to etch multiple layers including aluminum alloys and molybdenum alloys, and methods of forming metal patterns using the etchant composition.
在製作薄膜電晶體-液晶顯示器(TFT-LCD)陣列中，在基板上形成金屬線路通常包括利用濺射形成金屬層、施加光刻膠、進行曝光和顯影使得在選定的區域上形成光刻膠、和進行蝕刻，在其各個獨立的工序前後進行淨化工序。進行蝕刻工序使得利用所述光刻膠作為掩模在選定的區域上留下所述金屬層，並且所述蝕刻工序可包括利用等離子體等的乾蝕刻、或利用蝕刻液的濕蝕刻。作為TFT-LCD的線路材料的金屬通常是鋁或鋁合金。純鋁對化學品的耐受性低並且在後續加工中可引起線路黏合問題。因此，優選有用的是鋁合金，或者被構造成順序形成鋁或鋁合金層和由例如鉬、鉻、鎢、錫等製成的另一個金屬層的多層結構。 In the manufacture of thin-film transistor-liquid crystal display (TFT-LCD) arrays, the formation of metal lines on the substrate usually includes the formation of a metal layer by sputtering, the application of photoresist, exposure and development so that the photoresist is formed on the selected area , And etching, the purification process before and after each independent process. The etching process is performed so that the metal layer is left on the selected area using the photoresist as a mask, and the etching process may include dry etching using plasma or the like, or wet etching using an etchant. The metal used as the circuit material of the TFT-LCD is usually aluminum or aluminum alloy. Pure aluminum has low resistance to chemicals and can cause wire bonding problems in subsequent processing. Therefore, it is preferably useful to be an aluminum alloy, or a multilayer structure configured to sequentially form an aluminum or aluminum alloy layer and another metal layer made of, for example, molybdenum, chromium, tungsten, tin, or the like.
例如，鉬/鋁雙層可利用主要由磷酸組成的鋁蝕刻蝕刻劑來蝕刻，由於所述兩個層之間蝕刻速率的差異可發生鉬的突出，這樣的突出在後續加工中被乾蝕刻。 For example, the molybdenum/aluminum bilayer can be etched using an aluminum etching etchant mainly composed of phosphoric acid, and the protrusion of molybdenum can occur due to the difference in the etching rate between the two layers, and such protrusion is dry-etched in subsequent processing.
當以這種方式提供多層結構形式的用於TFT-LCD線路的金屬層時，所述濕法和乾法二者都應用，因而通常減輕了這兩種方法的弊病。 When a metal layer for a TFT-LCD circuit in the form of a multi-layer structure is provided in this way, both the wet method and the dry method are applied, and thus the disadvantages of these two methods are generally alleviated.
當鉬/鋁雙層利用常規的鋁蝕刻蝕刻劑濕蝕刻時，上鉬層的蝕刻速率小於鋁合金層的蝕刻速率，不利地導致差的輪廓，所述輪廓的橫截面中上鉬層突出於下鋁層之外。由於這種差的輪廓，台階覆蓋在後續加工中可能變差，並且所述上層可在傾斜側斷開，或者所述上和下金屬可能短路。在這種情況下，兩步法通常以下述的方式實行：首先進行利用鋁蝕刻蝕刻劑的濕蝕刻，然後對由於蝕刻速率不同而未被蝕刻並突出所述下層之外的上層進行乾蝕刻，這不利地使過程複雜化，從而引起例如生產率差、成本高和產品受損的問題。在這方面，本申請人提交的韓國專利申請No.1999-0041119(韓國專利申請公佈No.2001-0028729)，公開了主要由磷酸組成的蝕刻劑，其中特別設定了磷酸、硝酸和乙酸的組分比，由此可消除在橫截面中上鉬層突出於下鋁合金層之外的差的輪廓，並且可獲得達到了免去額外乾蝕刻的程度的優異輪廓，從而與常規的兩步法相比能夠簡單且經濟地蝕刻。 When the molybdenum/aluminum bilayer is wet etched with a conventional aluminum etching etchant, the etching rate of the upper molybdenum layer is less than that of the aluminum alloy layer, which disadvantageously results in a poor profile in which the upper molybdenum layer protrudes beyond Outside the lower aluminum layer. Due to this poor profile, the step coverage may become worse in subsequent processing, and the upper layer may be disconnected on the inclined side, or the upper and lower metals may be short-circuited. In this case, the two-step method is usually implemented in the following manner: first, wet etching using an aluminum etching etchant is performed, and then dry etching is performed on the upper layer that is not etched due to different etching rates and protrudes beyond the lower layer, This disadvantageously complicates the process, causing problems such as poor productivity, high cost, and product damage. In this regard, Korean Patent Application No. 1999-0041119 filed by the applicant (Korean Patent Application Publication No. 2001-0028729) discloses an etchant mainly composed of phosphoric acid, in which the groups of phosphoric acid, nitric acid and acetic acid are specifically set The ratio can thereby eliminate the poor profile of the upper molybdenum layer protruding beyond the lower aluminum alloy layer in the cross-section, and can obtain an excellent profile to the extent that additional dry etching is eliminated, thus being in line with the conventional two-step method It is easier and more economical to etch.
然而，因為所述金屬層以包括單層和多層、包含鋁或鋁合金和/或鉬或鉬合金的各種形式提供，並且另外， 隨著玻璃基板的尺寸增加，對利用常規蝕刻劑進行一步蝕刻造成了限制，並且可不利地形成尖端。 However, because the metal layer is provided in various forms including single layers and multiple layers, including aluminum or aluminum alloys and/or molybdenum or molybdenum alloys, and in addition, As the size of the glass substrate increases, one-step etching with conventional etchant is limited, and the tip may be disadvantageously formed.
韓國專利申請案公開No.2001-0028729 Korean Patent Application Publication No. 2001-0028729
因此，著眼於相關領域中存在的問題完成了本發明，本發明的目的是提供蝕刻劑組合物，其能夠一步蝕刻被構造成順序形成鉬合金層、鋁合金層、鉬合金層和鉬合金氧化物層的多層，並且防止光刻膠破裂和在上鉬合金層中的尖端形成。 Therefore, the present invention has been completed focusing on the problems in the related art, and the object of the present invention is to provide an etchant composition capable of one-step etching configured to sequentially form a molybdenum alloy layer, an aluminum alloy layer, a molybdenum alloy layer, and a molybdenum alloy oxidation Multiple layers of the object layer, and prevent the photoresist from cracking and forming a tip in the upper molybdenum alloy layer.
本發明提供了用於蝕刻多層的蝕刻劑組合物，其包含：50至70wt%的磷酸、6至8wt%的硝酸、5至25wt%的乙酸、2至4wt%的硫酸、和餘量的水，其中包含的硝酸和硫酸的含量比為1.5至2.5：1，並且所述多層被構造成順序形成鉬合金層、鋁合金層、鉬合金層和鉬合金氧化物層。 The present invention provides an etchant composition for etching multiple layers, which includes: 50 to 70 wt% phosphoric acid, 6 to 8 wt% nitric acid, 5 to 25 wt% acetic acid, 2 to 4 wt% sulfuric acid, and the balance of water , The content ratio of nitric acid and sulfuric acid contained therein is 1.5 to 2.5:1, and the multilayer is configured to sequentially form a molybdenum alloy layer, an aluminum alloy layer, a molybdenum alloy layer, and a molybdenum alloy oxide layer.
在示例性的實施方式中，所述鉬合金層可以是鉬-鈮(MoNb)層，所述鋁合金層可以是鋁-釹(AlNd)層，並且所述鉬合金氧化物層可包括選自鉬-鈮氧化物層(MoNbO)、鉬-鈮氮化物(MoNbN)層和鉬-鈮氧氮化物層中的至少一種，其中所述鉬-鈮氧氮化物是MoNbOxNy，其中MoNbOxNy層的x和y之和是1。 In an exemplary embodiment, the molybdenum alloy layer may be a molybdenum-niobium (MoNb) layer, the aluminum alloy layer may be an aluminum-neodymium (AlNd) layer, and the molybdenum alloy oxide layer may include At least one of a molybdenum-niobium oxide layer (MoNbO), a molybdenum-niobium nitride (MoNbN) layer, and a molybdenum-niobium oxynitride layer, wherein the molybdenum-niobium oxynitride is MoNbO x N y , where MoNbO x The sum of x and y in the N y layer is 1.
在另一種示例性的實施方式中，所述多層可用作 觸控面板的橋連導線。 In another exemplary embodiment, the multilayer can be used as The bridging wire of the touch panel.
在又一種示例性的實施方式中，所述蝕刻劑組合物還可包括選自表面活性劑、隱蔽劑和腐蝕抑制劑中的至少一種。 In yet another exemplary embodiment, the etchant composition may further include at least one selected from a surfactant, a concealing agent, and a corrosion inhibitor.
另外，本發明提供了形成金屬圖案的方法，所述方法包括：在基板上形成包括鋁合金和鉬合金的多層；和利用上述蝕刻劑組合物蝕刻所述多層。 In addition, the present invention provides a method of forming a metal pattern, the method comprising: forming a multilayer including an aluminum alloy and a molybdenum alloy on a substrate; and etching the multilayer using the above etchant composition.
在示例性的實施方式中，所述多層可被構造成順序形成鉬合金層、鋁合金層、鉬合金層和鉬合金氧化物層。 In an exemplary embodiment, the multiple layers may be configured to sequentially form a molybdenum alloy layer, an aluminum alloy layer, a molybdenum alloy layer, and a molybdenum alloy oxide layer.
在另一種示例性的實施方式中，可在液晶顯示器的薄膜電晶體(TFT)陣列基板上形成所述金屬圖案。 In another exemplary embodiment, the metal pattern may be formed on a thin film transistor (TFT) array substrate of a liquid crystal display.
根據本發明，所述蝕刻劑組合物能夠一步蝕刻被構造成順序形成鉬合金層、鋁合金層、鉬合金層和鉬合金氧化物層的多層，並可防止光刻膠破裂和在上鉬合金層中的尖端形成。 According to the present invention, the etchant composition can be etched in one step to form multiple layers of a molybdenum alloy layer, an aluminum alloy layer, a molybdenum alloy layer, and a molybdenum alloy oxide layer in sequence, and can prevent the photoresist from cracking and depositing molybdenum alloy The tip in the layer is formed.
本發明的上述和其他目標、特徵和優點將從以下結合附圖的詳細說明中更清楚地瞭解，所述附圖中：圖1示出了利用實施例1的蝕刻劑組合物蝕刻的所述多層的掃描電子顯微鏡(SEM)圖像；圖2示出了利用比較例1的蝕刻劑組合物蝕刻的所述多層的SEM圖像；圖3示出了利用比較例2的蝕刻劑組合物蝕刻的所述多層的SEM圖像； 圖4示出了利用比較例3的蝕刻劑組合物蝕刻的所述多層的SEM圖像；和圖5示出了利用比較例4的蝕刻劑組合物蝕刻的所述多層的SEM圖像； The above and other objects, features, and advantages of the present invention will be more clearly understood from the following detailed description in conjunction with the accompanying drawings, in which: FIG. 1 shows the etching by using the etchant composition of Example 1 Scanning electron microscope (SEM) image of the multilayer; FIG. 2 shows the SEM image of the multilayer etched with the etchant composition of Comparative Example 1; FIG. 3 shows etching with the etchant composition of Comparative Example 2 SEM images of the multilayer; 4 shows an SEM image of the multilayer etched with the etchant composition of Comparative Example 3; and FIG. 5 shows an SEM image of the multilayer etched with the etchant composition of Comparative Example 4;
本發明涉及蝕刻劑組合物，其包含磷酸、硝酸、乙酸、硫酸和水以便蝕刻包括鋁合金和鉬合金的多層，以及利用所述蝕刻劑組合物形成金屬圖案的方法。根據本發明的蝕刻劑組合物包括特定含量比的硝酸和硫酸，因而能夠一步蝕刻包含順序形成的鉬合金層、鋁合金層、鉬合金層和鉬合金氧化物層的多層，並防止光刻膠破裂和在上鉬合金層中的尖端形成。 The present invention relates to an etchant composition including phosphoric acid, nitric acid, acetic acid, sulfuric acid, and water in order to etch a multilayer including aluminum alloy and molybdenum alloy, and a method of forming a metal pattern using the etchant composition. The etchant composition according to the present invention includes a specific content ratio of nitric acid and sulfuric acid, and thus can etch a multilayer including a molybdenum alloy layer, an aluminum alloy layer, a molybdenum alloy layer, and a molybdenum alloy oxide layer that are sequentially formed, and prevent photoresist Cracking and tip formation in the upper molybdenum alloy layer.
在下文中，將給出本發明的詳細說明。 In the following, a detailed description of the invention will be given.
本發明涉及蝕刻多層的蝕刻劑組合物，其包含：50至70wt%的磷酸、6至8wt%的硝酸、5至25wt%的乙酸、2至4wt%的硫酸、和餘量的水，其中包含的硝酸和硫酸的含量比為1.5至2.5：1，並且所述多層被構造成順序形成鉬合金層、鋁合金層、鉬合金層和鉬合金氧化物層。 The present invention relates to an etchant composition for etching multiple layers, comprising: 50 to 70 wt% phosphoric acid, 6 to 8 wt% nitric acid, 5 to 25 wt% acetic acid, 2 to 4 wt% sulfuric acid, and the balance of water, which contains The content ratio of nitric acid and sulfuric acid is 1.5 to 2.5:1, and the multilayer is configured to sequentially form a molybdenum alloy layer, an aluminum alloy layer, a molybdenum alloy layer, and a molybdenum alloy oxide layer.
所述多層可用作觸控面板的橋連導線。在所述多層中，所述鉬合金層可以是鉬-鈮(MoNb)層，所述鋁合金層可以是鋁-釹(AlNd)層，並且所述鉬合金氧化物層可以包括選自鉬-鈮氧化物層(MoNbO)、鉬-鈮氮化物(MoNbN)層和鉬-鈮氧氮化物(MoNbOxNy)層中的至少一種，其中鉬-鈮氧氮 化物(MoNbOxNy)層的x和y之和是1。 The multiple layers can be used as bridge wires for touch panels. In the multilayer, the molybdenum alloy layer may be a molybdenum-niobium (MoNb) layer, the aluminum alloy layer may be an aluminum-neodymium (AlNd) layer, and the molybdenum alloy oxide layer may include a material selected from molybdenum- At least one of a niobium oxide layer (MoNbO), a molybdenum-niobium nitride (MoNbN) layer, and a molybdenum-niobium oxynitride (MoNbO x N y ) layer, wherein the molybdenum-niobium oxynitride (MoNbO x N y ) layer The sum of x and y is 1.
在所述蝕刻劑組合物中，磷酸起到氧化所述鋁合金層的作用，並且基於所述組合物的總重量，包含的量為50至70wt%。如果磷酸的量小於50wt%，則可降低所述鋁合金層的蝕刻速率，不利地產生蝕刻殘餘物。另一方面，如果磷酸的量大於70wt%，可過度增加鋁合金層的蝕刻速率，而鉬合金層的蝕刻速率可相對於此降低，因而在鉬合金層中明顯形成尖端。 In the etchant composition, phosphoric acid functions to oxidize the aluminum alloy layer, and is included in an amount of 50 to 70 wt% based on the total weight of the composition. If the amount of phosphoric acid is less than 50 wt%, the etching rate of the aluminum alloy layer may be reduced, and etching residues are disadvantageously generated. On the other hand, if the amount of phosphoric acid is more than 70% by weight, the etching rate of the aluminum alloy layer may be excessively increased, and the etching rate of the molybdenum alloy layer may be reduced relative thereto, so that a sharp tip is clearly formed in the molybdenum alloy layer.
在所述蝕刻劑組合物中，硝酸起到氧化所述鋁合金層和鉬合金層的表面的作用，並且基於所述組合物的總重量，包含的量為6.0至8.0wt%。如果硝酸的量小於6.0wt%，可降低鉬合金層的蝕刻速率，不利地在所述鉬合金層中形成尖端。另一方面，如果硝酸的量超過8.0%，則光刻膠可破裂，並因此可滲透化學品，不利地使所述鉬合金層和鋁合金層短路。此外，所述鉬合金層和鋁合金層可由於過蝕刻而損失，不利地失去橋連導線功能性。 In the etchant composition, nitric acid functions to oxidize the surfaces of the aluminum alloy layer and the molybdenum alloy layer, and is included in an amount of 6.0 to 8.0 wt% based on the total weight of the composition. If the amount of nitric acid is less than 6.0 wt%, the etching rate of the molybdenum alloy layer may be reduced, and a tip is disadvantageously formed in the molybdenum alloy layer. On the other hand, if the amount of nitric acid exceeds 8.0%, the photoresist may be broken, and thus may penetrate chemicals, disadvantageously short-circuiting the molybdenum alloy layer and the aluminum alloy layer. In addition, the molybdenum alloy layer and the aluminum alloy layer may be lost due to over-etching, disadvantageously losing the functionality of the bridge wire.
為了除去所述鉬合金層中的尖端，硝酸在所述蝕刻劑中與硫酸一起以特定的含量比包含在內，並且硝酸和硫酸優選以1.5至2.5：1的含量比包含在內。 In order to remove the tip in the molybdenum alloy layer, nitric acid is included in the etchant together with sulfuric acid in a specific content ratio, and nitric acid and sulfuric acid are preferably included in a content ratio of 1.5 to 2.5:1.
在所述蝕刻劑組合物中，乙酸起到降低磷酸黏度的作用，並且基於所述組合物的總重量，包含的量為5至25wt%。如果乙酸的量小於5wt%，則可增加磷酸黏度，使得不可能得到均勻的蝕刻特性。另一方面，如果乙酸的量超過25wt%，則可降低磷酸的黏度，因此蝕刻速率可變得 非常緩慢，此外，可遺留所述鋁合金層和鉬合金層，不利地引起缺陷。 In the etchant composition, acetic acid plays a role in reducing the viscosity of phosphoric acid, and based on the total weight of the composition, it is included in an amount of 5 to 25 wt%. If the amount of acetic acid is less than 5 wt%, the phosphoric acid viscosity can be increased, making it impossible to obtain uniform etching characteristics. On the other hand, if the amount of acetic acid exceeds 25 wt%, the viscosity of phosphoric acid can be reduced, so the etching rate can become Very slowly, in addition, the aluminum alloy layer and the molybdenum alloy layer may be left behind, disadvantageously causing defects.
在所述蝕刻劑組合物中，硫酸起到氧化所述鉬合金層表面的作用，並且基於所述組合物的總重量，包含的量為2.0至4.0wt%。如果硫酸的量小於2.0wt%，可降低鉬合金層的蝕刻速率，因而在所述鉬合金層中形成尖端。另一方面，如果硫酸的量超過4.0%，則光刻膠可破裂，並因此可滲透化學品，不利地使所述鉬合金層和鋁合金層短路。此外，所述鉬合金層和鋁合金層可由於過蝕刻而損失，不利地失去橋連導線功能性。 In the etchant composition, sulfuric acid functions to oxidize the surface of the molybdenum alloy layer, and based on the total weight of the composition, it is included in an amount of 2.0 to 4.0 wt%. If the amount of sulfuric acid is less than 2.0 wt%, the etching rate of the molybdenum alloy layer may be reduced, thus forming a tip in the molybdenum alloy layer. On the other hand, if the amount of sulfuric acid exceeds 4.0%, the photoresist may be broken, and thus may penetrate chemicals, disadvantageously short-circuiting the molybdenum alloy layer and the aluminum alloy layer. In addition, the molybdenum alloy layer and the aluminum alloy layer may be lost due to over-etching, disadvantageously losing the functionality of the bridge wire.
在所述蝕刻劑組合物中，水優選是去離子水，其適合於半導體加工並具有18MΩ/cm或更高的電阻率。 In the etchant composition, the water is preferably deionized water, which is suitable for semiconductor processing and has a resistivity of 18 MΩ/cm or higher.
除上述組分之外，根據本發明的蝕刻劑組合物還可包含通常的添加劑。所述添加劑的例子可包括表面活性劑、隱蔽劑和腐蝕抑制劑。 In addition to the above-mentioned components, the etchant composition according to the present invention may contain usual additives. Examples of the additives may include surfactants, concealing agents, and corrosion inhibitors.
所述表面活性劑負責降低表面張力，從而增加蝕刻均勻性。任何表面活性劑都可以使用，沒有限制，只要它能夠承受所述蝕刻劑並以相容的形式提供即可。其例子可包括陰離子、陽離子、兩性和非離子型表面活性劑。所述表面活性劑以氟基表面活性劑為例。 The surfactant is responsible for reducing the surface tension, thereby increasing the etching uniformity. Any surfactant can be used without limitation, as long as it can withstand the etchant and be provided in a compatible form. Examples thereof may include anionic, cationic, amphoteric and nonionic surfactants. The surfactant is exemplified by a fluorine-based surfactant.
所述添加劑不限於此，並且為了進一步提高本發明的效果，可以任選地添加本領域中已知的其他添加劑。 The additives are not limited thereto, and in order to further improve the effect of the present invention, other additives known in the art may be optionally added.
另外，本發明涉及形成金屬圖案的方法，所述方法包括：在基板上形成包括鋁合金和鉬合金的多層並利用 本發明的蝕刻劑組合物蝕刻所述多層。 In addition, the present invention relates to a method of forming a metal pattern, the method comprising: forming a multilayer including an aluminum alloy and a molybdenum alloy on a substrate and using The etchant composition of the present invention etches the multilayer.
在本發明的優選實施方式中，所述多層被構造成順序形成鉬合金層、鋁合金層、鉬合金層和鉬合金氧化物層。所述形成金屬圖案的方法可高效地用於製作液晶顯示器的薄膜電晶體(TFT)陣列基板。 In a preferred embodiment of the present invention, the multilayer is configured to sequentially form a molybdenum alloy layer, an aluminum alloy layer, a molybdenum alloy layer, and a molybdenum alloy oxide layer. The method for forming a metal pattern can be efficiently used for manufacturing a thin film transistor (TFT) array substrate of a liquid crystal display.
因此，利用所述蝕刻劑組合物蝕刻所述多層可以採用本領域已知的任何方法進行，例如浸漬、傾注等。所述蝕刻方法在20至50℃、並優選地30至45℃下進行。然而，蝕刻條件不限於此，並可以由本領域技術人員考慮其他加工條件和因素，根據需要適當改變。 Therefore, etching the multilayer with the etchant composition can be performed by any method known in the art, such as dipping, pouring, and the like. The etching method is performed at 20 to 50°C, and preferably 30 to 45°C. However, the etching conditions are not limited to this, and other processing conditions and factors can be considered by those skilled in the art and appropriately changed as needed.
即使當利用根據本發明的蝕刻劑組合物蝕刻大面積金屬層或多層金屬層時，也可以通過一步濕蝕刻法而不是常規的濕-乾兩步蝕刻法獲得均勻的蝕刻輪廓，有利地滿足成本和生產率要求。 Even when a large-area metal layer or a multi-layer metal layer is etched using the etchant composition according to the present invention, a uniform etching profile can be obtained by a one-step wet etching method instead of the conventional wet-dry two-step etching method, advantageously meeting the cost And productivity requirements.
本發明通過以下實施例、比較例和試驗例來詳細說明，提出它們僅僅是為了舉例說明本發明，但本發明不限於所述實施例、比較例和試驗例，並且可以被各種修改和變更。 The present invention is described in detail by the following examples, comparative examples, and test examples, which are proposed only to illustrate the present invention, but the present invention is not limited to the examples, comparative examples, and test examples, and can be variously modified and changed.
利用在下面表1中顯示的組分和量(wt%)製備蝕刻劑組合物。 The etchant composition was prepared using the components and amounts (wt%) shown in Table 1 below.
製備包含鉬-鈮(Nb)/鋁合金/鉬-鈮(Nb)/鉬-鈮氧化物層(MoNbO)的四層基板。將實施例和比較例的各蝕刻劑組合物放中噴霧蝕刻機(ETCHER(TFT)，由SEMES製造)中，然後升溫至40℃的溫度。當溫度達到40±0.5℃時，進行蝕刻工序。因此，過蝕刻(O/E)的程度基於墊部的端點檢測(EPD)被設置為30%。所述基板被放在蝕刻機中，然後經受噴霧蝕刻工序。完成蝕刻後，所述基板從蝕刻機取出，用去離子水清潔，然後利用熱風乾燥機乾燥，其後利用PR剝離劑除去光刻膠(PR)。清潔和乾燥後，利用SEM(S-4700，由HITACHI製造)對蝕刻輪廓評價傾角、MoNb尖端、蝕刻殘餘物和PR破裂。結果在下面表2和圖1至5中顯示。 A four-layer substrate including molybdenum-niobium (Nb)/aluminum alloy/molybdenum-niobium (Nb)/molybdenum-niobium oxide layer (MoNbO) was prepared. Each etchant composition of Examples and Comparative Examples was placed in a spray etching machine (ETCHER (TFT), manufactured by SEMES), and then heated to a temperature of 40°C. When the temperature reaches 40±0.5℃, the etching process is performed. Therefore, the degree of over-etching (O/E) is set to 30% based on the end point detection (EPD) of the pad portion. The substrate is placed in an etching machine and then subjected to a spray etching process. After the etching is completed, the substrate is taken out from the etching machine, cleaned with deionized water, and then dried with a hot air dryer, and then the photoresist (PR) is removed using a PR stripper. After cleaning and drying, the etching profile was evaluated for inclination angle, MoNb tip, etching residue, and PR fracture using SEM (S-4700, manufactured by HITACHI). The results are shown in Table 2 below and Figures 1 to 5.
從表2和圖1至4顯而易見，鉬合金層中的尖端在實施例1中沒有形成但在比較例1至3中形成。此外，在比較例4中PR破裂。 As is apparent from Table 2 and FIGS. 1 to 4, the tip in the molybdenum alloy layer was not formed in Example 1 but formed in Comparative Examples 1 to 3. In addition, in Comparative Example 4, the PR broke.
雖然已經出於說明性的目的公開了本發明的優選實施方式，但本領域技術人員將領會，在不悖離所附申請專利範圍中公開的本發明的範圍和精神之下，各種修改、添加和取代是可能的。 Although the preferred embodiments of the present invention have been disclosed for illustrative purposes, those skilled in the art will appreciate that various modifications and additions can be made without departing from the scope and spirit of the present invention disclosed in the scope of the appended patent application And replacement is possible.
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| KR20160109568A (en) | 2016-09-21 |
| CN105970227A (en) | 2016-09-28 |
| TW201638391A (en) | 2016-11-01 |
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