TW200804624A - Etching composition for TFT LCD - Google Patents

Abstract

To provide an etching composition of a thin-film transistor liquid crystal display device which is used to form an Mo/AlNd double film or an Mo/AlNd/Mo triple film which is a gate wiring material composing a TFT of the thin-film transistor liquid crystal display device using the same composition, in a single process without an undercut phenomenon on a lower film formed of AlNd or Mo and by a wet etching to acquire a superior taper, and also allows the formation of a superior profile in an Mo single film which is a source/drain wiring material, and in the Mo/AlNd/Mo triple film.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composition of a thin film transistor liquid crystal display device, and more particularly to a thin film transistor liquid crystal. The TFT 12 (thin film transistor) constituting the tantalum transistor liquid crystal display device is a Mo/AINd bilayer film or a Mo/AINd/Mo three-layer film using a gate wire material of the same composition. The AINd film layer or the Mo film layer of the lower part is subjected to wet etching for 10 times in a single process to obtain an excellent taper, and the tantalum single layer film of the source/digo wire material is The Mo/AINd/Mo three-layer film can form an excellent rim (pr〇me). BACKGROUND OF THE INVENTION A process for forming an extremely fine circuit on a substrate process substrate forms a metal pattern identical to that of a photoresist pattern formed by a development process. The etching process is roughly classified into wet etching and dry etching according to the manner of the etching, and the wet etching uses an acid-based chemical which is corroded by reaction with a metal or the like to dissolve a portion of the photoresist-free pattern; the dry etching is performed by accelerating ions. 20 removes the metal of the exposed portion to form a pattern. The dry etching has an anisotropic profile and a superior so-called etching control force than wet etching. However, the problem is that the equipment is expensive, it is difficult to face up, and the etching speed is slow, resulting in a low production volume (thr〇ughput). 5 200804624 · ; On the other hand, the above-mentioned wet etching has a so-called 矸, large amount and large batch processing compared to dry etching, and the etching speed is fast, so the production amount is high and the equipment is low.

Strengths. However, there is a problem that the amount of the etching liquid and the pure water used is large and the amount of the waste liquid is large. Table 5 Generally, in the case of dry etching, the light P which is hardened by the surface portion is removed and (photoresist) The main reason for the low production volume and weakened product competitiveness caused by the additional piasma ashing process is that the actual operation of the industry is mainly wet etching. The etching liquid used for φ and 'wet money engraving is applied to a specific metal type for etching according to a finer micro-micro circuit requiring finer. For example, an A1 single-layer film is used as an etching liquid for etching, and Patent Documents 1 and 2 below disclose an etching liquid composed of a dish of acid, nitric acid, acetic acid, a surfactant, and water. Further, the following Patent Document 3 discloses an etching liquid containing a phosphoric acid, a nitric acid, an acetic acid, a water, and a fluorocarbon surfactant for the AINd film, and the following Patent Document 4 discloses The following composition for the acid and hydrochloric acid, linic acid, and nitric acid having a pH of 3 to 4.5 in which oxalic acid and an adjustable composition are contained in aluminum and indium (tin oxide), Patent Document 5 discloses an etching liquid for a wire containing sulphuric acid, scutellite, acetic acid, and potassium oxysulfate for silver or silver alloy, and the following Patent Document 6 discloses An etchant composition comprising hydrochloric acid, acetic acid, an inhibitor, and water etched into an IZO (indium-zinc oxide). Further, Patent Document 7 below discloses phosphoric acid, retic acid, 6 200804624 acetic acid, an oxidation regulator, and water for etching the source and the drain electrode with Mo or MoW (alloy of molybdenum and tungsten). Etching liquid composition. However, the conventional etching liquid as described above is only suitable for etching a metal film, so that the effect on the efficiency of equipment and process is low, and therefore, research is continuously conducted on etching for most metal films simultaneously. 5 composition. In one of the examples, the following Patent Document 8 and Patent Document 9 disclose phosphoric acid, nitric acid, acetic acid, and an oxidation regulator for etching a two-layer film of Mo/Al or Mo/AINd and MoW/AINd. The etching solution, the following Patent Document 10 discloses that it is used for the 訄❹/eight! (AlNd) / M film etching package 10 etching solution containing phosphoric acid, nitric acid, acetic acid, and oxidation regulator. Further, Patent Document 11, Patent Document 12, and Patent Document 13 listed below are applicable to Mo/AINd, MoW/AINd, Mo/AINd/Mo, and the like.

MoW/AINd/MoW, Mo single layer film, and Mow single layer film are used as a residual solution containing phosphoric acid, nitric acid, acetic acid, molybdenum etching inhibitors (ammonium salts, potassium salts), 15 and water. However, when the etched film is etched by the metal film for the source/drain electrode of the thin film transistor liquid crystal display device by the conventional money engraving composition, the outline thereof causes a taper defect as shown in FIG. However, there are 20 problems in that the step coverage (Step c〇verage) of the film layer on the upper layer of the subsequent process is poor. Further, when the conventional etching composition is used to form a Mo/AINd double-layer film and a Mo/AINd/Mo three-layer film of a metal film for a gate electrode of a TFT constituting a thin film transistor liquid crystal display device, 9 The problem of the protrusion phenomenon of the upper M 〇 film and the undercut phenomenon of the lower AINd or Mo film in the figure. Therefore, in order to prevent the protrusion phenomenon of the above-mentioned upper film layer, it is necessary to perform an additional 200804624 process for removal to prevent the underlayer layer from being removed. The undercut phenomenon causes problems such as disconnection of the film layer on the inclined surface or short-circuiting of the upper and lower metal. Therefore, when the gate of the TFT of the conventional thin film transistor liquid crystal display device 0 and the metal film for the source/drain electrode are generally formed into a multilayer structure, the same applies to the wet process and the dry process. profile. However, such wet etching and dry etching together have disadvantages in terms of process trouble, low production volume, and cost increase. [Patent Document 1] Korean Patent Application No. 1/20〇2-〇〇47933 [Patent Document 2] US Patent No. 4,895,617 No. 10 [Patent Document 3] Korean Patent Application No. 10-2〇〇〇-〇〇 [Patent Document 4] Korean Patent Application No. 1〇-2〇〇1_〇〇3〇192 [Patent Document 5] Korean Patent Application No. 1〇-2〇〇1_〇〇65327 [Patent [6] Korean Patent Application No. 1〇-2〇〇2_〇〇1〇284 [Patent Document 7] Korean Patent Application No. 1〇-2〇〇1-〇〇18354 No. 15 [Patent Document 8] Korean Patent Application No. 10-2000-0002886 [Patent Document 9] Korean Patent Application No. 1〇-2〇〇1-〇〇72758 [Patent Document 10] Korean Patent Application No. 10_2000_0013867 [Patent Document 11] Korean Patent Application No. 1〇-2〇〇2_〇〇17〇93 [Patent Document 12] Korean Patent Application No. 1〇-2〇〇3_〇〇8〇557 No. 20 [Patent Document 13] Korea Patent Application No. 10-2004-0010404 C. 3 SUMMARY OF THE INVENTION In order to solve the problems of the prior art described above, the object of the present invention is Provided is an etching composition of a thin film transistor liquid crystal display device, 8 200804624. The TFT constituting the thin film transistor liquid crystal display device uses a M〇/AlNd double layer film of a gate-line material of the same composition or Mo/AINd/ The Mo three-layer film can obtain an excellent taper by a single-coating process in which the lower AINd film layer or the Mo film layer has no undercut phenomenon, and (4) the source/wave wire material 5 of the Mo single-layer film and chamber The three-layer membrane of the fine ship can form an excellent porch. Another object of the present invention is to provide a (four) composition of a thin film transistor liquid crystal display device, wherein the TFT constituting the thin film transistor liquid crystal display device uses a gate conductor material of the same composition as a 2M 〇/AiNd double layer film or 10 Mo/AINd/Mo three-layer film and source/drain wire material m〇 single layer film and M〇/A1Nd Yang three layer film are suitable for excellent etching effect, thereby increasing equipment efficiency and saving Cost. Another object of the present invention is to provide a lithographic composition of a thin film transistor liquid crystal display device, which is only a wet-etched gate wire material M0, which is not additionally applied after a wet type of engraving. /A1Nd two-layer film and Mo/AlNd/MG layer film and source/dipole wire material m〇 single film and M〇/A1Nd/M. The three-layer film is suitable for excellent engraving effects, and can be used to simplify the process, save costs, and effectively increase production. In order to solve the above problems, the present invention provides an etching composition for a thin film transistor liquid crystal display device characterized by comprising (a) 50% by weight to 80% by weight of phosphoric acid; (b) 2% by weight to 15% by weight of nitric acid (c) 3% by weight to 2% by weight of acetic acid; (d) 5% by weight of lithium-based compound 〇·〇; 9 200804624 (e) 酉1% by weight to 5 % by weight; and (f) the remaining proportion of water. Further, the present invention provides a method of producing a thin film transistor liquid crystal display device which is a step of etching by using the etching composition. 5 According to the present invention, even after the wet type, no dry residual is added,

The m〇/aiNcj bilayer film and Mo/AINd/M of the gate wiring material of the TFT of the thin film transistor liquid crystal display device which is formed by the wet-process only using the same composition. : The film can make the lower A1Nd film layer or film layer have no undercut phenomenon, and can obtain excellent taper. Therefore, it can prevent the wire breakage at the tilted 1 ' surface in the subsequent process, and the source/drain wire can be prevented. The material has a reverse taper phenomenon of the single layer film and can prevent the upper/lower layer from being short-circuited, and can form an angle of centimeter~(10)

The advantages of the excellent rim. Moreover, the M〇/Amd bilayer film using the polar conductor material between the same composition and the Mo monolayer film of the Saki-three-layer film and the source/dipole wire material are applicable, so that the process is simplistic and increased. The efficiency of the large equipment and the cost-saving effect. [Embodiment 3] DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described in detail. The composition of the money-forming composition of the Maoyue/special film transistor liquid crystal display device s ·, b) two, e) (four), d) (iv) compound, e) sulphate compound, and hydrophobic water. The use of the disc acid, acid, acetic acid, and water used in this April can be used as the purity f of the semiconductor system, and it is also possible to use commercially available materials or use by those skilled in the art. Well-known method of refining work 200804624 industry grade material. The phosphoric acid of the above a) used in the present invention acts on the decomposed alumina (AUO3), and such a phenomenon is a reaction mechanism according to the following reaction formula. [Reaction formula 1] 5 Al2〇3+2H3P〇4—2A1(P〇4)+3h2〇 The above-mentioned phosphoric acid is preferably from 5% by weight to 8% by weight of the engraved composition, and more preferably 62% by weight. From 0.01 to 75% by weight is preferred. When the content is within the above range, the etching rate of alumina (Al2?3) formed by the reaction of nitric acid with aluminum becomes faster, and the effect of increasing the throughput is obtained. 10 The nitric acid of the above b) used in the present invention reacts with aluminum to form an alumina (ΑΙΑ3). This phenomenon is in accordance with the reaction mechanism of the following Reaction Scheme 2. [Reaction formula 2] 4 A1 + 2HN034 2 A1203 + N2 + H2 The above nitric acid is preferably 2% by weight to 15% by weight of the etching composition, and 15 is more preferably 2.5% by weight to 8% by weight. When the content is within the above range, the Mo film of the upper film layer and the AINd film of the lower film layer can effectively adjust the selection ratio between the metal film and the other layers. In particular, when the nitric acid is less than 2% by weight, the Mo/AINd bilayer film and the Mo/AINd/Mo trilayer film have an undercut phenomenon; in the case of more than 15% by weight, 20 The problem of PR attack. The acetic acid of the above c) used in the present invention is a buffer for adjusting the reaction rate. The acetic acid is preferably from 3% by weight to 2% by weight of the etching composition, more preferably from 6% by weight to 15% by weight. When the content is within the range of the above-mentioned range 11 200804624, the reaction rate is appropriately adjusted to increase the etching rate, whereby the effect of increasing the throughput can be obtained. The lithium compound of the above d) used in the present invention can enhance the rim of the Mo single layer film, the Mo/AINd double layer film, and the Mo/AINd/Mo three layer film. 5 The lithium-based compound may be LiN03, CH3COOLi, C4H503Li, LiCl, LiF, Lil, C2HLi04, LiC104, Li202, Li2S04,

LiH2P〇4, or LiJO4, etc., especially those using LiN〇3 or CH3COOLi are preferred. The lithium-based compound is preferably 5% by weight to 3% by weight of 5% by weight of the composition of the composition, and more preferably 0.1% by weight to 2% by weight. The content is less than 0.05% by weight, which results in a reverse taper and shoulder phenomenon in the Mo monolayer film, and the Mo/AINd bilayer film with the gate wire material and the Mo/AINd/Mo layer. There is a problem that the AINd in the film produces an undercut phenomenon. When the content exceeds 3% by weight, the residual speed of the Mo single layer film becomes slow, and there are a three-layer film of 15 Mo/AINd and a three-layer film of Mo/AINd/Mo. A problem such as a stepped profile is produced. The phosphate compound of the above e) used in the present invention promotes decomposition of alumina which is oxidized by nitric acid, and the phenomenon is a reaction mechanism according to the following Reaction Scheme 3. 20 [Reaction formula 3] 2 Al2〇3 + 4P04 3 — — 4ΑΚΡΟ. + 3 02 The phosphate compound is preferably a compound which can dissociate P043-, and specifically, NaH2P〇4, Na2HP04, Na3P〇4, nh4h2p〇4, (nh4)2hpo4, (NH4)3P04, KH2P04, K2HP〇4, 12 200804624 Κ3Ρ〇4 ^ Ca(H2P04)2 > Ca2HP04 . ^€α3Ρ04# ^ νη4η2ρο4 or ΚΗ2Ρ04 is preferred. The phosphate compound is preferably from 01% by weight to 5% by weight of the etching composition, more preferably from 0.5% by weight to 3% by weight. In the case where the range of 5 is within the range of the description, the Mo/AINd double-layer film and the Mo/AlNd/Mo three-layer film have no undercut phenomenon in the A1Nd of the lower film layer, and the Mo single layer film may also be used. The advantage of forming an excellent contour. The water system of the other f) used in the present invention accounts for the remaining proportion of the etching composition, decomposes the alumina formed by the reaction of nitric acid with aluminum (Al2〇D, and achieves the effect of diluting the 10 etching composition. The amount of pure water filtered by the ion exchange resin is preferred, especially if ultrapure water having a specific resistance of 18 MDcm or more is used. Further, the present invention provides a method for manufacturing a thin film transistor liquid crystal display device. The method of manufacturing the thin film transistor liquid crystal display device of the present invention can be applied to a method for manufacturing a thin film transistor liquid crystal display device before and after the etching process by using the composition as described above. Of course, it can also be applied to a general process. The method for producing a thin film transistor liquid crystal display device of the present invention uses 20 etching compositions of the present invention containing the above-mentioned components, and after wet etching, dry etching is not additionally applied, and the same is used. a Mo/AlNd bilayer film of a gate wire material of a thin film transistor liquid crystal display device TFT which is composed of a composition and only a wet process The Mo/AINd/Mo three-layer film can provide an excellent taper without the undercut of the lower AINd film layer or the Mo film layer, so that the subsequent breakage of the inclined surface can be prevented in the subsequent manufacture of 13 200804624, and it can also be prevented. The reverse taper phenomenon of the Mo single-layer film of the source/drain wire material can prevent the upper/lower layer from being short-circuited, and can form the superiority of the excellent wheel corridor as shown in Fig. i. The angle is 40 to 70. The M〇/A double-layer film of the gate conductor material of the same composition and the (5) single-layer film of the 5 Mo/AINd/Mo two-layer film and the source/dimpolar wire material are all applicable. The simplification, the efficiency of the equipment, and the cost-saving effect. The following is a preferred embodiment of the present invention, but the following is only a preferred embodiment of the present invention, and cannot be limited thereto. The scope of the implementation of the present invention is 10. The implementation of your 丨1 phosphoric acid 68% by weight, nitric acid 4% by weight, acetic acid 13% by weight, LiN〇3U) weight ❶ / 〇, ΚΗ 2 Ρ〇 41 · 5 weight ❽ / 〇, the remaining proportion of water uniform The mixture is fabricated to form a composition. The result of applying the etching composition manufactured as described above to the Mo single layer film, as shown in Fig. 1, has an outline angle of 40 to 70. It can be confirmed that it is excellent. Further, the etching composition produced as described above is used for the result of the Mo/AINd double-layer film. As shown in Fig. 2, it has no undercut phenomenon and can have an excellent profile. Further, the etching composition produced as described above was used for the Mo/AINd/Mo three-layer film. As shown in Fig. 3, it was confirmed that there was no undercut phenomenon and it was excellent in wheel friction. Comparative Examples 1 to 4 In comparison with the above-mentioned Example 1, the comparative examples were produced in the same manner as in the above-described Example 1, except that the components and composition ratios shown in Table 1 below were used. The units in Table 1 below are % by weight. 14 200804624 [Table 1] Distinguishing Example 1 Comparative Example 1 2 3 4 - Phosphate 68 45 68 68 68 Nitric acid 4 4 1 4 4 ^Acetic acid 13 13 13 13 13 ^I I oxime 1.0 1.0 1.0 0.02 彳 1.0 One 1.5 1.5 1.5 1.5 0.05 --- The addition of the etching composition produced in the above Examples and Comparative Examples 1 to 4 to 100% by weight was carried out according to the following method, and the results were shown in Fig. 1 to 7 and γ are shown in Table 2. First, a test piece formed by patterning by photoresist coating after forming a Mo single layer film, a Mo/AINd double film, and a Mo/AINd/Mo three layer film by sputtering on a glass substrate, the foregoing embodiment 1. The etching composition produced in Comparative Examples 1 to 4 was subjected to a spray etching treatment. After the etching, the cross section was observed by a scanning electron microscope (SEM, S_4200 'Hitachi Co., Ltd.) to evaluate the performance of the etching composition. 【Table 2】

Differentiation Example 1 Comparative Example 1 2 3 4 Performance ◎ X X X X ‘Profile

Mo/AINd double-layer film, Mo/AINd/Mo three-layer film without undercut phenomenon, excellent taper angle X (bad): poor formation of Mo single layer film

Mo/AINd two-layer film, Mo/AINd/Mo three-layer film produced undercut phenomenon. As shown in Table 2, the etching of Example 1 manufactured according to the present invention is 15 200804624 Λ Composition and Comparative Examples 1 to 4 By comparison, it was confirmed that the Μο single layer film, the Mo/AlNd, the two-layer film, and the Mo/AlNd/Mo three-layer film all produced excellent etching effects. Further, the scanning micrograph of the etched cross section is as shown in Figs. 1 to 3, and the etching composition of the first embodiment manufactured according to the present invention is as shown in Figs. 2 and 3, and the gate wiring material is as shown in Figs. 2 and 3 . The Mo/AINd double-layer film and the Mo/AlNd/Mo three-layer film did not cause undercutting, and as shown in Fig. 1, it was confirmed that the source/drain wire material 2Mo single-layer film also formed an excellent profile. ^ On the other hand, in Comparative Example 1 in which the phosphoric acid content is less than 50% by weight, and in Comparative Example 2 in which the nitric acid content is less than 2% by weight, the "Mo/AINd double layer" is shown in Fig. 4 and Fig. 5 The film produces an undercut phenomenon. In the M〇/AlNd/Mo three-layer film, Mo of the lower film layer produces a tailing phenomenon. Further, in the case of Comparative Example 3 in which the lithium-based compound contained 0.05% by weight or less, as shown in Fig. 6, the Mo monolayer film formed a shoulder to form a defective profile, and the M〇/A1Nd bilayer film was produced. Undercut phenomenon. In addition, when the content of the phosphate compound is 15 in the case of Comparative Example 4 of less than 0.1% by weight, as shown in Fig. 7, • 0/8 (1 double layer and M〇/ The AlNd/Mo three-layer film produces an undercut phenomenon, and the M〇 single layer film generates a shoulder to form a poor profile. From the results, it is understood that the etching composition used in accordance with the present invention is more complex than the (10) composition. The present invention is excellent in step coverage 20 rate 0 [Comprehensive description of the country] Fig. 1 shows the composition of the composition prepared according to an embodiment of the present invention, which is suitable for the contour photograph of the Mo single layer film. The figure shows a remnant set 16 200804624 made in accordance with an embodiment of the present invention. The object is suitable for a contour photograph of a Mo/AINd bilayer film. 1 Fig. 3 shows an embodiment of the present invention. The engraved composition is suitable for the contour photograph of the Mo/AlNd/Mo three-layer film. Fig. 4 shows the etching composition of the comparative example using less phosphoric acid, suitable for Mo/AINd bilayer film and Mo /AlNd/Mo three-layer film outline photo. Figure 5 shows the composition of the comparative example using less acid, suitable The contour photograph of the Mo/AINd double-layer film and the Mo/AlNd/Mo three-layer film. Fig. 6 shows the etching group φ of the comparative example using less lining compounds, which is suitable for the Mo/AINd double-layer film and Profile 10 of the Mo/AlNd/Mo three-layer film. Fig. 7 shows the composition of the comparative example using a less phosphate compound, suitable for the Mo/AINd two-layer film and the Mo/AlNd/Mo three layer. Outline photo of the film. [Main component symbol description]

17

Claims (1)

200804624 X. Patent application scope: 1. An etching composition of a thin film transistor liquid crystal display device, comprising: (g) phosphoric acid 50% by weight to 8% by weight; 5 (h) nitric acid 2% by weight to 15 (i) acetic acid 3 weight y ❹ to 2 〇 weight 〇 / 〇; (j) lithium compound 〇〇 5 wt% to 3 wt%; (k) phosphate compound 〇 1 wt% to 5 wt%; And (l) the remaining proportion of water. 10 2. The surname composition of the thin film transistor liquid crystal display device of the above-mentioned patent range i, wherein the thin film transistor liquid crystal display device is a M〇/A1Nd bilayer film or M〇 of a TFT LCD gate wire material. /A1Nd/M〇 three-layer film. 3.·Shen Qing patent scope is the first! The composition of the thin film transistor liquid crystal display device of the present invention, wherein the thin film transistor liquid crystal display device is a TFT LCD source/dip wire material of the monolayer film. 4. For example, if the patent application is a patent for a thin film transistor liquid crystal display device, the (4) lithium-based compound is composed of LiN03, CH3COOLi, C4H5〇3Li, LiCl, LiF, Lil, C2HLi04, LiC104, 20 One or more of Ll2〇2, Ll2S〇4, LiH2P〇4, and Li3P〇4 are selected. 5. The etching composition of the thin film transistor liquid crystal display device of claim </ RTI> wherein the (e) phosphate compound is selected from the group consisting of NaH2P04, Na2HP〇4, Na3p〇4, Li 4H2p〇4, (NH4) 1) or more of 2Hp〇4, (nh4)3po4, kh2p〇4, K2HP〇4, K3p〇4, Ca(H2P〇4)2, 18 200804624 Ca2HP04, and €&amp;3?04 . A method of producing a thin film transistor liquid crystal display device comprising the step of etching using the etching composition according to any one of claims 1 to 5. 19 200804624 VII. Designation of representative representatives: (1) The representative representative of the case is: (1). (2) A brief description of the symbol of the representative figure: 8. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: