CN1966772A - Composition for etching metal layer and method for forming metal pattern by using same - Google Patents
Composition for etching metal layer and method for forming metal pattern by using same Download PDFInfo
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- CN1966772A CN1966772A CN 200510114837 CN200510114837A CN1966772A CN 1966772 A CN1966772 A CN 1966772A CN 200510114837 CN200510114837 CN 200510114837 CN 200510114837 A CN200510114837 A CN 200510114837A CN 1966772 A CN1966772 A CN 1966772A
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Abstract
The invention discloses a composite for etching metal layer. The composite contains (by wt.%): 55-80 phosphonic acid, 3-15 nitric acid, 5-20 acetic acid, 0.5-10 phosphate, 0.1-5 chlorine compound, 0.01-4 diazo compound and water.
Description
Technical field
The present invention relates to a kind of composition that is used for etch metal layers, relate in particular to a kind of method that is used for the composition of etch metal layers and is formed for the metal pattern of liquid crystal display device.
Background technology
Etching work procedure is the step that forms fine pattern on substrate.Form the identical pattern of photoresist material (PR) pattern form that has with by developing and obtaining, for example metal wire by etching work procedure.Etching work procedure is categorized as wet etching type and dry etching type.In the wet etching operation, via PR pattern layer that exposes and the composition that comprises sour material interact and by its corrosion with the formation pattern.In the dry etching operation, the metal level that exposes via the PR pattern by the ion remaval of plasmoid to form pattern.Dry etching operation specific humidity etching work procedure is easier to control, and compares with the pattern that obtains by the wet etching operation by the pattern that the dry etching operation obtains, and has anisotropy section (profile).Yet the device that is used for the dry etching operation is relatively more expensive and be not easy to be applied to large-size substrate.And, because the etch-rate of dry etching operation is very low, reduced the throughput of dry etching operation.On the other hand, be easier to adopt the wet etching operation by wet etching operation more substrates of processing and large-size substrate.In addition, the device that is used for the wet etching operation is relatively more cheap and because the etch-rate height of wet etching operation makes the wet etching operation have bigger throughput.Yet the wet etching operation needs a large amount of etching reagent and deionization (DI) water, thereby produces a large amount of discard solutions.
Usually, because the dry etching operation needs additional plasma ashing operation to remove solidified PR pattern, the time increase and the output that form pattern reduce.Therefore, especially when forming metal pattern, the wet etching operation has obtained widespread use.In addition, according to the kind of the metal level that is used to form fine metal patterns, can use various etching reagents.For example, application number is a kind of etching reagent that comprises phosphoric acid, nitric acid, acetate, tensio-active agent and water that is used for etching aluminium (Al) layer of the korean patent application of 2000-0047933 and U.S. Patent Publication that the patent No. is No.4895617.Application number is that the korean patent application of 2000-0047933 discloses a kind of etching reagent that comprises phosphoric acid, nitric acid, acetate, water and fluorocarbon surfactant that is used for etching neodymium aluminium (AlNd) layer.In addition, application number is that the korean patent application of 2001-0030192 discloses a kind of etching reagent that comprises oxalic acid, hydrochloric acid, phosphoric acid, nitric acid and be used for the pH value of etching reagent is adjusted at the acid in 3 to 4.5 scopes that is used for etching aluminium (Al) layer and tin indium oxide (ITO) layer.Application number is that the korean patent application of 2001-0065327 discloses a kind of etching reagent that comprises phosphoric acid, nitric acid, acetate and oxygen potassium sulphide that is used for etching silver (Ag) layer and silver-colored (Ag) alloy layer, and application number is that the korean patent application of 2002-0010284 discloses a kind of etching reagent that comprises hydrochloric acid, acetate, blocker (blocker) and water that is used for etching oxidation indium tin (ITO).And application number is that the korean patent application of 2001-0018354 discloses a kind of etching reagent that comprises phosphoric acid, nitric acid, acetate, oxidation control agent and water that is used for etching molybdenum (Mo) layer and tungsten molybdenum (MoW) layer.
Along with the continuous expansion of thin film transistor-liquid-crystal display (TFT-LCD) device, the metal wire of transmission signal also prolongs in the TFT-LCD device.Therefore, the increase of the impedance of metal wire increase and this impedance produces signal delay.In order to prevent signal delay, proposed a kind of many metal levels, and studied a kind of multiwalled of etching simultaneously etching reagent that is used for to improve the efficient of device and operation.For example, application number is that the korean patent application of 2000-0002886 and 2001-0072758 discloses a kind of etching reagent that comprises phosphoric acid, nitric acid, acetate and oxidation control agent that is used for etching molybdenum/aluminium (Mo/Al) layer, molybdenum/neodymium aluminium (Mo/AlNd) layer and tungsten molybdenum/neodymium aluminium (MoW/AlNd) layer.In addition, application number is that the korean patent application of 2000-0013867 discloses a kind of phosphoric acid that comprises that is used for etching molybdenum/aluminium/molybdenum (Mo/Al/Mo) layer and molybdenum/neodymium aluminium/molybdenum (Mo/AlNd/Mo) layer, nitric acid, the etching reagent of acetate and oxidation control agent, and application number is that the korean patent application of 2002-0017093 discloses a kind of etching molybdenum/neodymium aluminium (Mo/AlNd) layer that is used for, tungsten molybdenum/neodymium aluminium (MoW/AlNd) layer, molybdenum/neodymium aluminium/molybdenum (Mo/AlNd/Mo) layer, tungsten molybdenum/neodymium aluminium/tungsten molybdenum (MoW/AlNd/MoW) layer, molybdenum (Mo) layer and tungsten molybdenum (MoW) layer comprise phosphoric acid, nitric acid, acetate, the etching reagent of molybdenum etching inhibitor (ammonium salt) and water.
Yet, when grid line, data line and the pixel electrode of LCD device have many metal levels, use the etching reagent of prior art to be difficult to obtain good section.In order to obtain good section, repeat dry etching operation and wet etching operation.Repeating of dry etching operation and wet etching operation can make output reduce and the increase production cost.
Summary of the invention
Therefore, the present invention relates to a kind of composition that is used for the many metal levels of etching, it has overcome one or more problems of bringing because of the limitation of prior art and shortcoming basically.
The invention has the advantages that provides the many metal levels of a kind of etching to have the composition of many metal patterns of good section with formation.
Another advantage of the present invention is to provide a kind of molybdenum/neodymium aluminium (Mo/AlNd) layer that can etching be used to form grid line, be used to form molybdenum (Mo) layer of data line and be used to form the composition of tin indium oxide (ITO) layer of pixel electrode.
An advantage more of the present invention is that the composition that provides a kind of use to be used for the many metal levels of etching forms the method for the metal pattern with good section.
Another advantage of the present invention is to provide a kind of and adopts the wet etching operation and do not need the method for the many metal patterns of formation of dry etching operation.
Another advantage of the present invention is to provide a kind of use to have low relatively capillary composition and forms the even metal method of patterning.
Attendant advantages of the present invention and feature will be illustrated in the description of back, by following description, will make them apparent to a certain extent for those of ordinary skills, perhaps can be familiar with them by putting into practice the present invention.These and other advantages of the present invention can realize by the structure of specifically noting in written description and claim and the accompanying drawing and obtain.
In order to realize these and other advantage, according to purpose of the present invention, to describe as concrete and generalized, a kind of composition that is used for etch metal layers comprises: weight ratio is about 55% to about 80% phosphoric acid; Weight ratio is about 3% to about 15% nitric acid; Weight ratio is about 5% to about 20% acetate; Weight ratio is about 0.5% to about 10% phosphoric acid salt; Weight ratio is about 0.1% to about 5% chlorine-containing compound; Weight ratio is about 0.01% to about 4% azo-compound; And water.
According to another aspect of the present invention, a kind of method of making the array substrate of liquid crystal display device comprises: form grid line and the grid that is connected to this grid line on substrate; On grid line and grid, form gate insulation layer; On gate insulation layer, form semiconductor layer corresponding to the grid place; On gate insulation layer, form data line, and on semiconductor layer, form source electrode and drain electrode; Form passivation layer in data line and source electrode and drain electrode, this passivation layer has the contact hole that exposes drain electrode; And on passivation layer, form pixel electrode, this pixel electrode is connected to drain electrode by drain contact hole, the composition that one of them employing at least of wherein said grid line, data line and pixel electrode is used for etch metal layers forms, and said composition comprises: weight ratio is about 55% to about 80% phosphoric acid; Weight ratio is about 3% to about 15% nitric acid; Weight ratio is about 5% to about 20% acetate; Weight ratio is about 0.5% to about 10% phosphoric acid salt; Weight ratio is about 0.1% to about 5% chlorine-containing compound; Weight ratio is about 0.01% to about 4% azo-compound; And water.
According to a further aspect, a kind of method that forms metal pattern comprises: form metal level on insulation layer; On metal level, form the photoresist material pattern; And by being used for this metal level of composition etching of etch metal layers, said composition comprises: weight ratio is about 55% to about 80% phosphoric acid; Weight ratio is about 3% to about 15% nitric acid; Weight ratio is about 5% to about 20% acetate; Weight ratio is about 0.5% to about 10% phosphoric acid salt; Weight ratio is about 0.1% to about 5% chlorine-containing compound; Weight ratio is about 0.01% to about 4% azo-compound; And water.
Should be appreciated that top generality is described and following detailed all is schematic and indicative, being intended to provides further explanation to claim of the present invention.
Description of drawings
The accompanying drawing that the application comprised is used for further understanding the present invention, and it combines and constitute the part of specification sheets with specification sheets, and described accompanying drawing is represented embodiments of the present invention and explained principle of the present invention with specification sheets.
In the accompanying drawings:
Fig. 1 shows the sectional view by scanning electronic microscope (SEM) picture that adopts the metal pattern that obtains according to exemplary composition etching oxidation indium tin of the present invention (ITO) layer;
Fig. 2 shows the sectional view by scanning electronic microscope (SEM) picture that adopts the metal pattern that obtains according to exemplary composition etching molybdenum of the present invention (Mo) individual layer;
Fig. 3 shows by adopting the sectional view according to scanning electronic microscope (SEM) picture of the double-deck metal pattern that obtains of exemplary composition etching molybdenum of the present invention/neodymium aluminium (Mo/AlNd);
Fig. 4 shows the sectional view by scanning electronic microscope (SEM) picture that adopts comparative composition 1 etching molybdenum/double-deck metal pattern that obtains of neodymium aluminium (Mo/AlNd);
Fig. 5 shows the sectional view by scanning electronic microscope (SEM) picture that adopts comparative composition 2 etchings molybdenum/double-deck metal pattern that obtains of neodymium aluminium (Mo/AlNd);
Fig. 6 shows the sectional view by scanning electronic microscope (SEM) picture that adopts comparative composition 3 etchings molybdenum/double-deck metal pattern that obtains of neodymium aluminium (Mo/AlNd);
Fig. 7 shows the sectional view by scanning electronic microscope (SEM) picture that adopts comparative composition 4 etchings molybdenum/double-deck metal pattern that obtains of neodymium aluminium (Mo/AlNd);
Fig. 8 shows the sectional view by scanning electronic microscope (SEM) picture that adopts comparative composition 5 etchings molybdenum/double-deck metal pattern that obtains of neodymium aluminium (Mo/AlNd); And
Fig. 9 shows the sectional view by scanning electronic microscope (SEM) picture that adopts comparative composition 6 etchings molybdenum/double-deck metal pattern that obtains of neodymium aluminium (Mo/AlNd).
Embodiment
To describe embodiments of the present invention in detail below, embodiment is shown in the drawings.Use similar Reference numeral to represent identical or similar part as much as possible, in the accompanying drawings.
The exemplary composition that is used for the many metal levels of etching according to the present invention can be used to form the many metal patterns that are used for showing such as liquid-crystal display (LCD) device, plasma display (PDP) device, electroluminescent display devices such as (ELD) device and Field Emission Display (FED) device.To be that example describes with the LCD device below.
Comprise according to the exemplary composition that is used for etch metal layers of the present invention: weight ratio is about 55% to about 80% phosphoric acid (H
3PO
4), weight ratio is about 3% to about 15% nitric acid (HNO
3), weight ratio is about 5% to about 20% acetate (CH
3COOH), weight ratio is that about 0.5% to about 10% phosphoric acid salt, weight ratio are that about 0.1% to about 5% chlorine-containing compound, weight ratio are about 0.01% to about 4% azo (azolic) compound and water.In the present invention, can have the purity that is suitable for semi-conductor manufacturing process such as the material of phosphoric acid, nitric acid, acetate and water, perhaps can be by using such as materials such as phosphoric acid, nitric acid, acetate and water after the purifying step.
Can comprise by weight for about 55% to about 80% and to be preferably weight ratio be about 65% to about 75% phosphoric acid (H according to the exemplary composition that is used for the etching metal pattern of the present invention
3PO
4).This phosphoric acid (H
3PO
4) dissolve by nitric acid (HNO
3) and the aluminum oxide (AL that generates of aluminium (Al) reaction
2O
3).Therefore, increased etch-rate and improved throughput.
The exemplary composition that is used for the etching metal pattern according to the present invention can comprise by weight for about 3% to about 15% and to be preferably weight ratio be about 5% to about 10% nitric acid (HNO
3).This nitric acid (HNO
3) react to produce aluminum oxide (AL with aluminium
2O
3).For example, when being used for etching molybdenum/neodymium aluminium (Mo/AlNd) according to composition of the present invention when double-deck, by weight ratio at about 3% nitric acid (HNO in about 15% scope
3) effectively adjust the etching ratio between double-deck and other layers of molybdenum/neodymium aluminium (Mo/AlNd).When composition comprises that weight ratio is less than 3% nitric acid (HNO
3) time, can produce undercutting, wherein the neodymium aluminium (AlNd) of lower floor layer gets more than molybdenum (Mo) the layer etching on upper strata.
The exemplary composition that is used for the etching metal pattern according to the present invention can comprise by weight for about 5% to about 20% and preferably weight ratio be about 8% to about 15% acetate (CH
3COOH).This acetate (CH
3COOH) be used as the buffer reagent of reaction speed best.Therefore, increased etch-rate and improved throughput.
The exemplary composition that is used for the etching metal pattern according to the present invention can comprise by weight for about 0.5% to about 10% and to be preferably weight ratio be about 1% to about 5% phosphoric acid salt.This phosphoric acid salt is regulated the etch-rate of molybdenum (Mo) and is dissolved by nitric acid (HNO
3) and the aluminum oxide (AL that produces of aluminium (Al) reaction
2O
3).For example, when being used for etching molybdenum/neodymium aluminium (Mo/AlNd) according to composition of the present invention when double-deck, neodymium aluminium (AlNd) layer that has prevented lower floor wherein gets more undercutting than molybdenum (Mo) the layer etching on upper strata and produces.In addition, even when being used for etching molybdenum (Mo) individual layer, also can form metal pattern with good section according to composition of the present invention.For example, phosphoric acid salt can comprise NaH
2PO
4, Na
2HPO
4, Na
3PO
4, NH
4H
2PO
4, (NH
4)
2HPO
4, (NH
4)
3PO
4, KH
2PO
4, K
2HPO
4, K
3PO
4, Ca (H
2PO
4)
2, Ca
2HPO
4And Ca
3PO
4One of them is preferably NH
4H
2PO
4And KH
2PO
4
The exemplary composition that is used for the etching metal pattern according to the present invention can comprise by weight for about 0.1% to about 5% and to be preferably weight ratio be about 0.5% to about 2% chlorine-containing compound.This chlorine-containing compound is regulated the etch-rate of tin indium oxide (ITO) and molybdenum (Mo).In addition, chlorine-containing compound is regulated the etching ratio between molybdenum/neodymium aluminium (Mo/AlNd) bilayer and other layers.For example, when being used for etching molybdenum/neodymium aluminium (Mo/AlNd) according to composition of the present invention when double-deck, can effectively regulate etching ratio between double-deck and other layers of molybdenum/neodymium aluminium (Mo/AlNd) by its weight ratio at about 0.1% chlorine-containing compound in about 5% scope, get more undercutting than molybdenum (Mo) the layer etching on upper strata with neodymium aluminium (AlNd) layer that prevents to produce lower floor wherein.In addition, even when being used for etching molybdenum (Mo) individual layer and tin indium oxide (ITO) individual layer, also can form metal pattern by suitably regulating etch-rate with good section according to composition of the present invention.For example, chlorine-containing compound can comprise HCl, NH
4Cl, KCl and FeCl
3One of them is preferably NH
4Cl and KCl one of them.
The exemplary composition that is used for the etching metal pattern according to the present invention can comprise by weight for about 0.01% to about 4% and to be preferably weight ratio be about 0.05% to about 1% azo-compound.This azo-compound is regulated the etch-rate of molybdenum (Mo) and neodymium aluminium (AlNd).For example, when being used for etching molybdenum/neodymium aluminium (Mo/AlNd) according to composition of the present invention when double-deck, can effectively regulate the etch-rate of the neodymium aluminium (AlNd) layer of molybdenum (Mo) layer on upper strata and lower floor at about 0.01% azo-compound in about 4% scope by its weight ratio.Therefore, can prevent to be created in molybdenum/neodymium aluminium (Mo/AlNd) bilayer molybdenum (Mo) layer at the middle and upper levels and the different step taper profile of neodymium aluminium (AlNd) inclination layer of lower floor, thereby in whole molybdenum/neodymium aluminium (Mo/AlNd) bilayer, have good section less than about 60 ° of inclination angles.In addition, owing to reduced critical size (CD) loss, can improve the processing tolerance limit.For example, azo-compound can comprise benzotriazole, benzaminic acid, aminobenzamide, 2-amino-5-nitrobenzoic acid, 1,2,3-benzo three nitrogen-4 (3H)-ketone (benzazimide), Methylbenzotriazole, amino tetrazole, methylamino acid fat, benzotriazole carboxylic acid, CobraTec98, CobraTec99 and CobraTec928 are preferably amino tetrazole.
The exemplary composition that is used for the etching metal pattern according to the present invention can comprise water.This water dissolution is by nitric acid (HNO
3) and the aluminum oxide (AL that produces of aluminium (Al) reaction
2O
3), and the dilution said composition.For example, this water can comprise that by the filtering deionization of ion exchange resin (DI) water preferably, this DI glassware for drinking water has the resistivity greater than about 18 megaohms centimetre (M Ω cm).
The invention provides the composition that a kind of employing is used for etch metal layers and form the method for the metal pattern of liquid crystal display device, and the method that is used for the composition manufacturing liquid crystal display device of etch metal layers.
Liquid-crystal display (LCD) device comprises first substrate, second substrate and is clipped in liquid crystal layer between first and second substrates.On first substrate, form grid line and data line.Grid line and data line are intersected with each other to limit pixel region.Form pixel electrode and as the thin film transistor (TFT) of switching element at the pixel region of first substrate.Pixel electrode is formed by the transparent conductive material such as tin indium oxide (ITO) and indium zinc oxide (IZO).TFT " T " is connected to grid line and data line.Form black matrix on second substrate and on black matrix, forming the color filter layer that comprises the sub-colour filter of red, green and blue.On color filter layer, form public electrode.Here, grid line, data line and pixel electrode do not need additional dry etching operation to be formed by the electro-conductive material such as metal by adopting according to the wet etching operation of composition of the present invention at least.For example, grid line can be by molybdenum/neodymium aluminium (Mo/AlNd) bilayer forms and data line can be formed by molybdenum (Mo) individual layer.In addition, pixel electrode can be formed by tin indium oxide (ITO) layer.
Formed by adopting the wet etching operation according to composition of the present invention by the double-deck grid line that constitutes of molybdenum/neodymium aluminium (Mo/AlNd), neodymium aluminium (AlNd) layer molybdenum (Mo) the layer etching than the upper strata of lower floor gets more undercutting and can not produce wherein.And, form by adopting wet etching operation by the data line of molybdenum (Mo) individual layer formation and by the pixel electrode that tin indium oxide (ITO) layer constitutes, to have good conical in shape according to composition of the present invention.Therefore, prevent the circuit breaker in the subsequent conductive layer above the metal pattern that comprises grid line and pixel electrode and produce at metal pattern and the electrical short between the subsequent conductive layer above this metal pattern such as data line.In addition, because the data line that constitutes by the double-deck grid line that constitutes of molybdenum/neodymium aluminium (Mo/AlNd), by molybdenum (Mo) individual layer and adopted by the pixel electrode that tin indium oxide (ITO) layer constitutes forms according to identical composition of the present invention, can simplify manufacturing process, raising plant efficiency and reduce production costs.And, owing to reduce, can spread said composition well and improve the etch uniformity in the large-size substrate according to the surface tension of composition of the present invention.
Employing forms metal patterns according to exemplary composition of the present invention and six kinds of comparative composition, and these compositions of explained later and such as the result of transversal profile.
Comprise by weight according to exemplary composition of the present invention and to be: about 65% phosphoric acid (H
3PO
4), about 8% nitric acid (HNO
3), about 12% acetate (CH
3COOH), about 2% phosphoric acid salt, about 1% chlorine-containing compound, about 0.1% azo-compound and water.In addition, six kinds of comparative composition comprise by weight and are: about 50% to about 65% phosphoric acid (H
3PO
4), about 2% to about 8% nitric acid (HNO
3), about 12% to about 25% acetate (CH
3COOH), about 2% phosphoric acid salt, about 1% chlorine-containing compound, about 0.1% to about 5% azo (azolic) compound and water.
Table 1 shows according to composition of the present invention and six kinds of comparative composition.
[table 1]
| Composition (weight %) | Exemplary composition | | | Comparative composition 3 | Comparative composition 4 | Comparative composition 5 | Comparative composition 6 |
| Phosphoric acid (H 3PO 4) | 65 | 6 | 50 | 65 | 65 | 65 | 65 |
| Nitric acid (HNO 3) | 8 | 8 | 8 | 2 | 8 | 8 | 8 |
| Acetate (CH 3COOH) | 12 | 12 | 12 | 12 | 25 | 12 | 12 |
| Phosphoric acid salt | 2 | - | 2 | 2 | 2 | 2 | |
| Chlorine-containing | 1 | 1 | 1 | 1 | 1 | 1 | 1 |
| Azo-compound | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | - | 5 |
| Water | Rest part | ||||||
On substrate, form after the metal level such as molybdenum/neodymium aluminium (Mo/AlNd) bilayer, molybdenum (Mo) individual layer and tin indium oxide (ITO) layer, on metal level, form photoresist material (PR) pattern.Then, adopt according to exemplary composition of the present invention and six kinds of comparative composition this metal level composition to form metal pattern.By this metal level of injection method etching.Then, detect the transversal profile of this metal pattern by scanning electronic microscope (SEM).
Table 2 shows the result of the etching work procedure that adopts exemplary composition and six kinds of comparative composition.
As shown in table 2, when the metal level of, molybdenum (Mo) individual layer double-deck and tin indium oxide (ITO) layer such as molybdenum/neodymium aluminium (Mo/AlNd) by according to exemplary composition etching of the present invention the time, always can obtain to have the metal pattern of good section.
[table 2]
| Exemplary composition | | | Comparative composition 3 | Comparative composition 4 | Comparative composition 5 | Comparative composition 6 | |
| The result | ◎ | × | × | × | × | ○ | × |
| [note] ◎ (well): in the double-deck metal pattern that forms by molybdenum/neodymium aluminium (Mo/AlNd), do not observe undercutting and in each metal pattern that is formed by molybdenum (Mo) individual layer and tin indium oxide (ITO) layer, observe good cross-section profile zero (good): in double-deck some metal patterns that form by molybdenum/neodymium aluminium (Mo/AlNd), observe undercutting * (poor): in double-deck each metal pattern that forms by molybdenum/neodymium aluminium (Mo/AlNd), observe undercutting and in each metal pattern that is formed by molybdenum (Mo) individual layer and tin indium oxide (ITO) layer, observe relatively poor transversal profile | |||||||
Fig. 1 shows by adopting the sectional view according to scanning electronic microscope (SEM) picture of exemplary composition difference etching oxidation indium tin of the present invention (ITO) layer, molybdenum (Mo) individual layer and the double-deck metal pattern that obtains of molybdenum/neodymium aluminium (Mo/AlNd) to Fig. 3.Image to left shows the metal pattern that has photoresist material (PR) pattern on metal pattern, and Image to right shows the metal pattern that removal PR pattern does not have the PR pattern afterwards.
In Fig. 1, the metal pattern that is formed by tin indium oxide (ITO) layer has about 30 ° of good sections to about 60 ° of inclination angles, and in Fig. 2, the metal pattern that is formed by molybdenum (Mo) individual layer has about 45 ° of good sections to about 70 ° of inclination angles.In addition, not having wherein by the double-deck metal pattern that forms of molybdenum/neodymium aluminium (Mo/AlNd), neodymium aluminium (AlNd) layer molybdenum (Mo) the layer etching than the upper strata of lower floor gets more undercutting.
Fig. 4 shows sectional view by scanning electronic microscope (SEM) picture that adopts the double-deck metal pattern that obtains of comparative composition 1 to 6 etching molybdenum/neodymium aluminium (Mo/AlNd) respectively to Fig. 9.
As shown in Figure 4 and Figure 5, do not comprise phosphatic comparative composition 1 and comprise the phosphoric acid (H of weight ratio when adopting less than about 65%
3PO
4) 2 pairs of molybdenums of comparative composition/when neodymium aluminium (Mo/AlNd) bilayer carried out composition, this metal pattern had undercutting.In addition, even do not illustrate among Fig. 4 and Fig. 5, the metal pattern that is formed by molybdenum (Mo) individual layer has relatively poor section.
As shown in Figure 6, comprise that weight ratio is less than about 3% nitric acid (HNO when employing
3) 3 pairs of molybdenums of comparative composition/when neodymium aluminium (Mo/AlNd) bilayer carried out composition, this metal pattern had undercutting.In addition, even do not illustrate among Fig. 6, since the etch-rate height of molybdenum (Mo) individual layer, the very difficult critical size (CD) that obtains the metal pattern uniformity.CD at random can make production management become difficult.
And, shown in Fig. 7,8 and 9, when employing comprises that weight ratio is greater than about 20% acetate (CH
3COOH) comparative composition 4, do not comprise the comparative composition 5 of azo-compound and comprise weight ratio more than about 4% azo-compound respectively to molybdenum/when neodymium aluminium (Mo/AlNd) bilayer carried out composition, this metal pattern had undercutting.
Therefore, molybdenum/neodymium aluminium (Mo/AlNd) bilayer is carried out wet etching and do not need dry etching steps according to composition of the present invention by adopting, the grid line of liquid-crystal display (LCD) device has good section and does not have undercutting.Simultaneously, respectively molybdenum (Mo) individual layer and tin indium oxide (ITO) layer are carried out etching by adopting according to composition of the present invention, the data line and the pixel electrode of liquid-crystal display (LCD) device have good section.Because the data line that forms by the double-deck grid line that forms of molybdenum/neodymium aluminium (Mo/AlNd), by molybdenum (Mo) individual layer and form according to same combination of the present invention, so simplified manufacturing process, improved plant efficiency and reduced manufacturing cost by the pixel electrode employing that tin indium oxide (ITO) layer forms.In addition, do not have deterioration such as undercutting owing to metal pattern has good section, the succeeding layer that is formed on this metal pattern can not rupture.
Clearly, those skilled in the art can make amendment and change under the situation that does not break away from the spirit or scope of the present invention the present invention.Therefore, this invention is intended to cover the various modifications and variations that fall in claims of the present invention and the equivalent restricted portion thereof.
Claims (14)
1, a kind of composition that is used for etch metal layers comprises:
Weight ratio is 55% to 80% phosphoric acid;
Weight ratio is 3% to 15% nitric acid;
Weight ratio is 5% to 20% acetate;
Weight ratio is 0.5% to 10% phosphoric acid salt;
Weight ratio is 0.1% to 5% chlorine-containing compound;
Weight ratio is 0.01% to 4% azo-compound; And
Water.
2, composition according to claim 1 is characterized in that, described metal level comprises molybdenum/neodymium aluminium bilayer.
3, composition according to claim 1 is characterized in that, described metal level comprises the molybdenum individual layer.
4, composition according to claim 1 is characterized in that, described metal level comprises the tin indium oxide individual layer.
5, composition according to claim 1 is characterized in that, described phosphoric acid salt comprises NaH
2PO
4, Na
2HPO
4, Na
3PO
4, NH
4H
2PO
4, (NH
4)
2HPO
4, (NH
4)
3PO
4, KH
2PO
4, K
2HPO
4, K
3PO
4, Ca (H
2PO
4)
2, Ca
2HPO
4And Ca
3PO
4One of them.
6, composition according to claim 1 is characterized in that, described chlorine-containing compound comprises HCl, NH
4Cl, KCl and FeCl
3One of them.
7, composition according to claim 1, it is characterized in that, described azo-compound comprises benzotriazole, benzaminic acid, aminobenzamide, 2-amino-5-nitrobenzoic acid, 1,2,3-benzo three nitrogen-4 (3H)-ketone, Methylbenzotriazole, amino tetrazole, methylamino acid fat, benzotriazole carboxylic acid, CobraTec98, CobraTec99 and CobraTec928 one of them.
8, composition according to claim 1 is characterized in that, described water comprises deionized water.
9, a kind of method of making the array substrate of liquid crystal display device comprises:
On substrate, form grid line and the grid that is connected to grid line;
On grid line and grid, form gate insulation layer;
On gate insulation layer, form semiconductor layer corresponding to the grid place;
On gate insulation layer, form data line, and on semiconductor layer, form source electrode and drain electrode;
Form passivation layer in data line and source electrode and drain electrode, this passivation layer has the contact hole that exposes drain electrode; And
Form pixel electrode on passivation layer, this pixel electrode is connected to drain electrode by drain contact hole,
The composition that one of them employing at least of wherein said grid line, data line and pixel electrode is used for etch metal layers forms, and said composition comprises: weight ratio is 55% to 80% phosphoric acid; Weight ratio is 3% to 15% nitric acid; Weight ratio is 5% to 20% acetate; Weight ratio is 0.5% to 10% phosphoric acid salt; Weight ratio is 0.1% to 5% chlorine-containing compound; Weight ratio is 0.01% to 4% azo-compound; And water.
10, method according to claim 9 is characterized in that, described grid line comprises the neodymium aluminium lamination of lower floor and the molybdenum layer on upper strata.
11, method according to claim 9 is characterized in that, described data line comprises molybdenum layer.
12, method according to claim 9 is characterized in that, described pixel electrode comprises indium tin oxide layer.
13, a kind of method that forms metal pattern comprises:
On insulation layer, form metal level;
On metal level, form the photoresist material pattern; And
By being used for this metal level of composition etching of etch metal layers, said composition comprises: weight ratio is 55% to 80% phosphoric acid; Weight ratio is 3% to 15% nitric acid; Weight ratio is 5% to 20% acetate; Weight ratio is 0.5% to 10% phosphoric acid salt; Weight ratio is 0.1% to 5% chlorine-containing compound; Weight ratio is 0.01% to 4% azo-compound; And water.
14, method according to claim 13 is characterized in that, described metal level comprises one of them of molybdenum/neodymium aluminium bilayer, molybdenum individual layer and tin indium oxide individual layer.
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| CN102409342A (en) * | 2010-08-25 | 2012-04-11 | 普兰西公司 | Etching Agent Composite Used For Etching Conductive Multi-layer Film And Etching Method Using The Same |
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| CN112752867A (en) * | 2018-09-12 | 2021-05-04 | 富士胶片电子材料美国有限公司 | Etching composition |
| CN112752867B (en) * | 2018-09-12 | 2024-05-24 | 富士胶片电子材料美国有限公司 | Etching composition |
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