CN103806000A - Etchant composition, array substrate and method for manufacturing the array substrate - Google Patents
Etchant composition, array substrate and method for manufacturing the array substrate Download PDFInfo
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- CN103806000A CN103806000A CN201310552933.7A CN201310552933A CN103806000A CN 103806000 A CN103806000 A CN 103806000A CN 201310552933 A CN201310552933 A CN 201310552933A CN 103806000 A CN103806000 A CN 103806000A
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/136—Liquid crystal cells structurally associated with a semi-conducting layer or substrate, e.g. cells forming part of an integrated circuit
- G02F1/1362—Active matrix addressed cells
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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
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- Internal Circuitry In Semiconductor Integrated Circuit Devices (AREA)
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- Thin Film Transistor (AREA)
Abstract
The invention relates to an etchant composition, an array substrate and a method for manufacturing the array substrate. The etchant composition is used for Cu-based metal film, and based on total weight of the composition, the etchant composition comprises the components of: A) peroxide (H2O2), B) pH regulator and C) water. When the etchant composition of the invention is used for etching single metal layer or multiple metal layers composed of the Cu-based metal film, a pattern can be formed through batch etching. The etched Cu-based metal film has no interference deformation, and furthermore a conical contour with excellent linearity can be obtained.
Description
The cross reference of related application
The application requires the rights and interests of the korean patent application 10-2012-0127269 submitting on November 12nd, 2012, and therefore, this application by reference and entirety is incorporated to the application.
Technical field
The application relates to a kind of etching agent composition, a kind of a kind of method and method of manufacturing for the array substrate of liquid-crystal display (LCD) of utilizing described etching agent composition to form wiring; Wherein, described etching agent composition in batches etching (batch etching) comprises the metal level of the single or multiple lift form of Cu-Base Metal film, may not can cause the interface deformation of the Cu-Base Metal film of etching, can obtain having the tapered profiles (taper profile) of good linear, and can not produce residue, therefore avoid comprising the problem of brightness of electrical short, undesirable wiring, reduction etc.
Background technology
The operation that forms metal line on substrate in semiconducter device generally includes: utilize the formation metallic membranes such as sputter, apply photoresist material, expose and develop, thereby form photoresist material and carry out etching on the region of selecting; Wherein, before or after implementing each self-contained process, carry out cleaning process.Described etching process relates to utilizes photoresist material as mask, metallic membrane can be stayed in the region of selection, and etching process typically comprises the wet etching erosion that utilizes the dry etching of plasma body or analogue or utilize etching agent composition.
At present, the main focus of this semiconducter device is the resistance of metal line.This be because, thin film transistor-liquid crystal display (TFT-LCD) in the situation that, it is important solving that RC signal delay problem is considered to the size for increasing panel and obtains high resolving power, wherein, this RC signal delay is mainly caused by resistance.Therefore, increase the size of TFT-LCD in order to reduce its essential demand of RC signal delay, must develop and there is low-resistance material.For this reason, the Cr(resistivity generally having used: 12.7 × 10
-8Ω m), Mo(resistivity: 5 × 10
-8Ω m), Al(resistivity: 2.65 × 10
-8Ω m) and their alloy be difficult to use in the grid wiring and data arrange of large-sized TFT-LCD.
Under this background, one has low-resistance metal film, for example, and Cu-Base Metal film (for example Cu film and Cu-Mo film) and receiving publicity for the etching agent composition of this metallic membrane.Although can obtain at present the various etching agent compositions for Cu-Base Metal film, but they can not meet user's demand.
In this regard, korean patent application publication number 10-2010-0090535 discloses a kind of etching agent composition for Cu-Base Metal film, and this etching agent composition comprises the hydrogen peroxide as primary oxidant.Utilize the etching agent for Cu film of hydrogen peroxide wet etching to lose and formation pattern.But, if for the pH of the etching agent of Cu film lower than 1.6, in the time of etching metallic membrane, etching may be in the aggravation of the metallic region place of local weakness, thus the local cloth thread breakage that may occur not to be supposed to.
[citing document]
[patent documentation]
Korean patent application publication number 10-2010-0090535.
Summary of the invention
Therefore, the present invention has paid close attention to the above-mentioned problems in the prior art, and the object of this invention is to provide a kind of etching agent composition, the pH that this etching agent composition has is applicable to prevent when Cu-Base Metal film being carried out to wet etching when erosion, because the aggravation of local etching causes the fracture of wiring.
Another object of the present invention is to provide a kind of etching agent composition for Cu-Base Metal film, and this etching agent composition can carry out the etching in batch of gate electrode, grid wiring, source/drain and the data arrange of the TFT of TFT-LCD.
Further aim of the present invention is to provide a kind of method and a kind of method of above-mentioned etching agent composition manufacture for the array substrate of liquid-crystal display of utilizing of utilizing above-mentioned etching agent composition etching Cu-Base Metal film.
To achieve these goals, the invention provides a kind of etching agent composition for Cu-Base Metal film, this etching agent composition comprises A) hydrogen peroxide (H
2o
2), B) pH adjusting agent and C) water, the pH of wherein said composition is 1.6～3.Preferably, the pH of described composition is 1.6～2.4.
In addition, the invention provides a kind of method of etching Cu-Base Metal film, comprising: I) on substrate, form Cu-Base Metal film; II) on described Cu-Base Metal film, optionally leave photochromics; And, III) utilize according to Cu-Base Metal film described in etching agent composition etching of the present invention,
In addition, the invention provides the method for a kind of manufacture for the array substrate of liquid-crystal display, comprising: a) on substrate, form grid wiring; B) on the described substrate with described grid wiring, form gate insulator; C) on described gate insulator, form semiconductor layer; D) on described semiconductor layer, form source electrode and drain electrode; And the pixel electrode that e) formation is connected with described drain electrode, wherein, formation grid wiring in a) is included in and on described substrate, forms Cu-Base Metal film and utilize according to Cu-Base Metal film described in etching agent composition etching of the present invention, and formation source electrode in d) and drain electrode are included in and on described semiconductor layer, form Cu-Base Metal film and utilize Cu-Base Metal film described in etching agent composition etching according to the present invention.
In addition, the invention provides a kind of array substrate for liquid-crystal display, described array substrate comprise one or more be selected from utilize according to grid wiring and the source/drain of etching agent composition etching of the present invention.
Accompanying drawing explanation
From the detailed description below in conjunction with accompanying drawing, will more clearly understand above-mentioned purpose of the present invention and other objects, feature and advantage, wherein:
Fig. 1 shows scanning electron microscope (SEM) image of the Cu-Base Metal film of the etching agent composition etching of utilizing embodiment 1; And
Fig. 2 shows the SEM image of the Cu-Base Metal film of the etching agent composition etching of utilizing comparative example 1.Embodiment
To describe the present invention below in detail.
The present invention proposes a kind of etching agent composition for Cu-Base Metal film, comprising: A) hydrogen peroxide (H
2o
2); B) pH adjusting agent; And C) water, the pH of wherein said composition is 1.6～3.
Preferably, the pH of described composition is 1.6～2.4.
Term used herein " Cu-Base Metal film " refers to the film containing Cu, comprises unitary film and comprises the multilayer film of duplicature etc.For example, Cu-Base Metal film comprises Cu or the Cu alloy of individual layer, Cu-Mo film, the Cu-Mo alloy film etc. of multilayer.Cu-Mo film comprises Mo layer and is formed on the Cu layer on Mo layer, and Cu-Mo alloy film comprises Mo alloy layer and is formed on the Cu layer on Mo alloy layer.Mo alloy layer is by Mo and one or more alloy compositions that form that select in the group that free Ti, Ta, Cr, Ni, Nd and In form.
In etching agent composition according to the present invention, A) hydrogen peroxide (H
2o
2) be used as the major constituent of etching Cu-Base Metal film, and A is set) hydrogen peroxide (H
2o
2) content to make the pH of said composition as 1.6～3, and be preferably 1.6～2.4.If the A using) hydrogen peroxide (H
2o
2) amount make the pH of said composition lower than 1.6, may aggravate the etching of Cu-Base Metal film that weakens, and therefore Cu wiring may local fracture.On the contrary, if the content of this component makes the pH of said composition exceed 3.0, etching may not be carried out or etch rate can become very low, thereby is difficult to control this process.
In etching agent composition according to the present invention, B) pH adjusting agent comprises organic acid and the mineral acid that can reduce pH, and alkali and the neutral salt of the pH that can raise.At B) in pH adjusting agent, the content of the compound that reduces pH is set to make the pH of said composition as 1.6 or higher.Make the pH of this etching agent composition lower than 1.6 if the content of this component using is greater than the amount of bases material or neutral salt material, may aggravate the etching of Cu-Base Metal film, and therefore Cu wiring may local fracture.Equally, at B) in pH adjusting agent, the content of compound of rising pH is set to make the pH of composition as 3.0 or lower, and is preferably 2.4 or lower.If the content of this component using is greater than mineral acid or organic acid content exceedes 3.0 with the pH that makes composition, etching may not be carried out or etch rate can become very low, thereby is difficult to control this process.
B) enforcement of pH adjusting agent comprises: comprise 1-hydroxy ethylene-1,1-bisphosphate (HEDP), the organic acid of oxyacetic acid, acetic acid, butyric acid, citric acid, formic acid, gluconic acid, propanedioic acid, oxalic acid, valeric acid etc.; Comprise the mineral acid of phosphoric acid etc.; Comprise the salt of phosphoric acid salt (for example SODIUM PHOSPHATE, MONOBASIC, potassium primary phosphate etc.); Fluorochemical etc.; Comprise: the azole compounds of amino tetrazole, benzotriazole, tolyltriazole, pyrazoles, pyrroles, imidazoles, glyoxal ethyline, 2-ethyl imidazol(e), 2-propyl imidazole, 2-aminooimidazole, 4-methylimidazole, 4-ethyl imidazol(e), 4-propyl imidazole etc.; Indoles, purine, pyrazoles, pyridine, pyrimidine, pyrroles, tetramethyleneimine, pyrroline and other water-soluble cyclic amine compounds, these materials can use separately, or two or more are combined with.
In etching agent composition according to the present invention, C) water is not particularly limited, but preferably includes deionized water.What be particularly useful is the deionized water with the 18M of being at least Ω/cm resistivity (, removing the degree of ion from water).In addition, use C with remaining amount) water is 100wt% thereby make according to the total amount of etching agent composition of the present invention.
Except said components, above-mentioned etching agent composition can further use conventional additives, and this additive for example comprises sequestrant, corrosion inhibitor etc.
In the present invention, can pass through the etching agent composition of conventional known method for the preparation of Cu-Base Metal film, this etching agent composition comprises A) hydrogen peroxide (H
2o
2), B) pH adjusting agent and C) water, and this etching agent composition preferably has the purity for semiconductor machining.
Can carry out etching in batches to the gate electrode, grid wiring, source/drain and the data arrange that form by Cu-Base Metal in liquid-crystal display according to etching agent composition of the present invention.
In addition, the present invention proposes a kind of method of etching Cu-Base Metal film, comprises I) on substrate, form Cu-Base Metal film; II) on described Cu-Base Metal film, optionally leave photochromics; III) use according to Cu-Base Metal film described in etching agent composition etching of the present invention.
In lithographic method according to the present invention, preferably, photochromics is conventional photoresist material material, and this photochromics utilizes rotine exposure and development optionally to be stayed.
In addition, the present invention proposes the method for a kind of manufacture for the array substrate of liquid-crystal display, comprise: a) on substrate, form grid wiring, b) on the substrate with described grid wiring, form gate insulator, c) on described gate insulator, form semiconductor layer, d) on described semiconductor layer, form source electrode and drain electrode, and e) form the pixel electrode being connected with described drain electrode; Wherein, formation grid wiring in a) is included in and on described substrate, forms Cu-Base Metal film and utilize according to Cu-Base Metal film described in etching agent composition etching of the present invention, forms source electrode and drain electrode and be included in and on described semiconductor layer, form Cu-Base Metal film and utilization according to Cu-Base Metal film described in etching agent composition etching of the present invention in d).
Array substrate for liquid-crystal display may be tft array substrate.
Can use ordinary method known in the art (for example comprise flood, sprinkling etc.) to utilize according to etching agent composition etching Cu Base Metal film of the present invention.Can be at 20～50 ℃, and preferably at the temperature of 30～45 ℃, carry out etching process, and if need, can be according to other processing conditionss or because of definite suitable processing temperature usually.
Utilize the etching agent composition etching Cu-Base Metal required time of film to change, this depends on the thickness of temperature and film, but this required time is arranged on the scope of several seconds to dozens of minutes conventionally.
In addition, the present invention proposes a kind of array substrate for liquid-crystal display, and this array substrate comprises that utilization is according to source electrode and the grid of etching agent composition etching of the present invention.
To describe in more detail of the present invention by the following example and comparative example below.
< embodiment >
the preparation of etching agent composition
Utilize the etching agent composition of the composition Preparation Example 1 shown in following table 1 and embodiment 2 and comparative example 1 and comparative example 2.
[table 1]
| Unit: wt% | H 2O 2 | ATZ | HEDP | Phosphoric acid | Oxyacetic acid | Deionized water | pH |
| Embodiment 1 | 18 | 0.6 | 1.0 | 3.0 | - | Surplus | 2.10 |
| Embodiment 2 | 19 | 0.6 | 5.0 | 1.0 | - | Surplus | 1.65 |
| Comparative example 1 | 19 | 0.5 | 5.0 | 0.1 | - | Surplus | 1.50 |
| Comparative example 2 | 21 | 0.5 | 5.0 | 1.0 | 1.0 | Surplus | 1.17 |
* ATZ: amino tetrazole
* HEDP:1-hydroxy ethylene-1,1-bisphosphate
test case and compare test example: the Performance Evaluation of etching agent composition
Cu film is deposited on to chip glass (100mm × 100mm) upper, and utilizes subsequently photolithography on this wafer, to form the photoresist material with predetermined pattern, utilize respectively subsequently the composition etching Cu film of embodiment 1 and embodiment 2 and comparative example 1 and comparative example 2.For this reason, use injection-type etching test set (ETCHER(TFT), purchased from SEMES company), by extremely approximately 30 ° of C of the Temperature Setting of the etching agent composition in etching process.Etching process continues to carry out approximately 30～180sec.Utilize SEM(S-4700, purchased from HITACHI company) observe the profile of Cu-Base Metal film of etching in the fracture of wiring and etching process.The results are shown in following table 2.
[table 2]
Remarks) O: splendid linearity and good tapered profiles when etching
X: poor linearity and undesirable tapered profiles when etching
As obviously shown in table 2 and Fig. 1 and Fig. 2, all etching agents of embodiment 1 and embodiment 2 all present good etching performance, and pH demonstrates cloth thread breakage lower than 1.6 comparative example 1 and the etching agent of comparative example 2.
As mentioned before, the invention provides the method for a kind of manufacture for the array substrate of liquid-crystal display.In the time utilizing etching agent composition etching according to the present invention to comprise the metal level of single or multiple lift form of Cu-Base Metal film, can form pattern via etching in batch, there is not interface deformation in the Cu-Base Metal film of etching, can obtain having the tapered profiles of good linear, and can not produce residue, therefore etching composition of the present invention does not comprise the problem of brightness of electrical short, undesirable wiring, reduction etc.
Equally, in the time that utilization is used for the array substrate of liquid-crystal display according to etching agent composition of the present invention manufacture, can etching grid, grid wiring, source/drain also can etching data arranges, therefore simplified etching process, and maximized production productive rate.
Therefore, can effectively utilize very much according to etching agent composition of the present invention at the array substrate of manufacturing for liquid-crystal display, thereby obtain the circuit for giant-screen and high brightness.
Although disclose the preferred embodiment of the present invention for task of explanation, those skilled in the art are in the situation that not deviating from the disclosed scope and spirit of the present invention of appended claim by what know, multiple change, increase and to substitute be possible.
Claims (11)
1. manufacture is for a method for the array substrate of liquid-crystal display, and described method comprises:
A) on substrate, form grid wiring;
B) on the described substrate with described grid wiring, form gate insulator;
C) on described gate insulator, form semiconductor layer;
D) on described semiconductor layer, form source electrode and drain electrode; And
E) form the pixel electrode being connected with described drain electrode,
Wherein, the described grid wiring of formation in a) is included in and on described substrate, forms Cu-Base Metal film and utilize Cu-Base Metal film described in etching agent composition etching,
The described source electrode of formation in d) and described drain electrode are included in and on described semiconductor layer, form Cu-Base Metal film and utilize Cu-Base Metal film described in described etching agent composition etching, and
Described etching agent composition is the etching agent composition for Cu-Base Metal film, and based on the gross weight of described composition, described etching agent composition comprises A) H
2o
2, B) pH adjusting agent and C) water, and the pH of described etching agent composition is 1.6～3.
2. method according to claim 1 wherein, is thin-film transistor array base-plate for the described array substrate of liquid-crystal display.
3. method according to claim 1, wherein, the pH of described composition is 1.6～2.4.
4. for an etching agent composition for Cu-Base Metal film, comprising:
A）H
2O
2；
B) pH adjusting agent; And
C) water,
Wherein, described composition has 1.6～3 pH.
5. etching agent composition according to claim 4, wherein, the pH of described composition is 1.6～2.4.
6. etching agent composition according to claim 4, wherein, B) described pH adjusting agent is organic acid, mineral acid, salt, azole compounds or water-soluble cyclic amine compound.
7. etching agent composition according to claim 4, wherein, B) described pH adjusting agent is 1-hydroxy ethylene-1,1-bisphosphate, oxyacetic acid, phosphoric acid, phosphoric acid salt, amino tetrazole or fluorochemical.
8. etching agent composition according to claim 4, further comprises sequestrant or corrosion inhibitor.
9. a method for etching Cu-Base Metal film, comprising:
I) on substrate, form Cu-Base Metal film;
II) on described Cu-Base Metal film, optionally leave photochromics;
III) utilize Cu-Base Metal film described in etching agent composition etching,
Wherein, described etching agent composition is the etching agent composition for Cu-Base Metal film, and described etching agent composition comprises A) H
2o
2, B) pH adjusting agent and C) water, and the pH of described etching agent composition is 1.6～3.
10. method according to claim 9, wherein, the pH of described composition is 1.6～2.4.
11. 1 kinds of array substrates for liquid-crystal display, comprise the source electrode and the drain electrode that utilize the etching agent composition etching described in claim 4.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR10-2012-0127269 | 2012-11-12 | ||
| KR1020120127269A KR20140060679A (en) | 2012-11-12 | 2012-11-12 | Manufacturing method of an array substrate for liquid crystal display |
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|---|---|
| CN103806000A true CN103806000A (en) | 2014-05-21 |
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| CN201310552933.7A Pending CN103806000A (en) | 2012-11-12 | 2013-11-08 | Etchant composition, array substrate and method for manufacturing the array substrate |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105316678A (en) * | 2014-06-27 | 2016-02-10 | 东友精细化工有限公司 | Etching solution composition and method of preparing array substrate for liquid crystal display using same |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR102639571B1 (en) * | 2019-03-29 | 2024-02-22 | 동우 화인켐 주식회사 | A manufacturing method of an array substrate for liquid crystal display |
| KR102639573B1 (en) * | 2019-03-29 | 2024-02-22 | 동우 화인켐 주식회사 | A manufacturing method of an array substrate for liquid crystal display |
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| CN1510169A (en) * | 2002-12-12 | 2004-07-07 | Lg.菲利浦Lcd株式会社 | Etching solution for multi-layer copper and molybdenum and etching method therewith |
| US20060292888A1 (en) * | 2005-06-22 | 2006-12-28 | Samsung Electronics Co., Ltd. | Etchant, method for fabricating interconnection line using the etchant, and method for fabricating thin film transistor substrate using the etchant |
| JP2010265524A (en) * | 2009-05-15 | 2010-11-25 | Kanto Chem Co Inc | Etchant for copper-containing stacked film |
| CN102566121A (en) * | 2010-12-10 | 2012-07-11 | 东友Fine-Chem股份有限公司 | Manufacture method of liquid crystal display array substrate |
| CN102576170A (en) * | 2009-08-20 | 2012-07-11 | 东友Fine-Chem股份有限公司 | Method of fabricating array substrate for liquid crystal display |
| CN102762770A (en) * | 2010-02-15 | 2012-10-31 | 三菱瓦斯化学株式会社 | Etching solution for multilayer thin film having copper layer and molybdenum layer contained therein |
-
2012
- 2012-11-12 KR KR1020120127269A patent/KR20140060679A/en active Application Filing
-
2013
- 2013-11-08 CN CN201310552933.7A patent/CN103806000A/en active Pending
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| CN1510169A (en) * | 2002-12-12 | 2004-07-07 | Lg.菲利浦Lcd株式会社 | Etching solution for multi-layer copper and molybdenum and etching method therewith |
| US20060292888A1 (en) * | 2005-06-22 | 2006-12-28 | Samsung Electronics Co., Ltd. | Etchant, method for fabricating interconnection line using the etchant, and method for fabricating thin film transistor substrate using the etchant |
| JP2010265524A (en) * | 2009-05-15 | 2010-11-25 | Kanto Chem Co Inc | Etchant for copper-containing stacked film |
| CN102576170A (en) * | 2009-08-20 | 2012-07-11 | 东友Fine-Chem股份有限公司 | Method of fabricating array substrate for liquid crystal display |
| CN102762770A (en) * | 2010-02-15 | 2012-10-31 | 三菱瓦斯化学株式会社 | Etching solution for multilayer thin film having copper layer and molybdenum layer contained therein |
| CN102566121A (en) * | 2010-12-10 | 2012-07-11 | 东友Fine-Chem股份有限公司 | Manufacture method of liquid crystal display array substrate |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105316678A (en) * | 2014-06-27 | 2016-02-10 | 东友精细化工有限公司 | Etching solution composition and method of preparing array substrate for liquid crystal display using same |
| CN105316678B (en) * | 2014-06-27 | 2019-01-22 | 东友精细化工有限公司 | Etchant and the method for manufacturing array substrate for liquid crystal display using it |
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|---|---|
| KR20140060679A (en) | 2014-05-21 |
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Application publication date: 20140521 |