CN110922971A - Etching solution composition for aluminum-doped zinc oxide film - Google Patents
Etching solution composition for aluminum-doped zinc oxide film Download PDFInfo
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- CN110922971A CN110922971A CN201811100957.8A CN201811100957A CN110922971A CN 110922971 A CN110922971 A CN 110922971A CN 201811100957 A CN201811100957 A CN 201811100957A CN 110922971 A CN110922971 A CN 110922971A
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- C09K13/00—Etching, surface-brightening or pickling compositions
- C09K13/04—Etching, surface-brightening or pickling compositions containing an inorganic acid
- C09K13/06—Etching, surface-brightening or pickling compositions containing an inorganic acid with organic material
Abstract
The invention aims to develop the AZO film etching solution with excellent performance, can effectively control various performance indexes, and has the remarkable characteristics that: by optimizing the formulation, appropriate performance parameters can be obtained such as: CD loss, taper, residual, burr; low cost, safety and environmental protection. The invention provides an etching solution composition for an aluminum-doped zinc oxide film, which comprises at least two of the following components a, b and c, a component d and a component e, wherein: the component a is selected from phosphoric acid, nitric acid and hydrochloric acid; the component b is selected from oxalic acid, citric acid, malic acid, tartaric acid, phytic acid, lactic acid and acetic acid; component c is selected from ammonium chloride; the component d is selected from sodium dodecyl sulfate, maleic anhydride/acrylic acid copolymer, hexadecyl trimethyl ammonium bromide and ferric chloride; component e is selected from water. The etching solution composition provided by the invention can effectively control the performances such as etching rate, CD loss, taper angle and the like through specific compositions, and finally obtains a proper performance index.
Description
Technical Field
The invention relates to the field of etching of transparent conductive films in panel display devices, in particular to an etching solution composition for aluminum-doped zinc oxide (AZO) films.
Background
The ZnO film is an important photoelectron information material, not only has photoelectric properties similar to those of the traditional ITO film, but also has rich raw materials, low price, no toxicity and high thermal stability, has wide application prospect in the fields of solar cells, liquid crystal displays, photoelectric detectors and the like, can be used for manufacturing flexible substrate luminescent devices, plastic liquid crystal displays and amorphous silicon solar cells, and can also be used as a transparent heat-insulating material for plastic greenhouses, automobile glass and civil building glass pasting films. In particular, In the ITO transparent conductive film In the photoelectron industry, In element resources are rare and expensive, and a replaceable material is urgently needed to be found. ZnO is therefore considered as an alternative material to ITO.
Doping Al in a ZnO system to obtain ZnO: the Al transparent conductive film, namely the AZO film, has greatly improved conductivity after being doped, and the resistivity can be reduced to 10-4ohm cm, and the stability of the transparent conductive film AZO film In hydrogen plasma is superior to ITO, and simultaneously has the similar photoelectric characteristic as ITO, and the AZO film is convenient to prepare, has rich element resources compared with In elements, is nontoxic, and gradually becomes the best substitute of the ITO film, and the AZO film has been partially applied In flat panel displays and thin film solar cells. However, in the ZnO-based film wet etching, due to the crystal growth particularity of the metal oxide, etching burrs and uniformity problems generated in the etching process are always bottlenecks in popularization and application of doped oxide films such as Al and Ga, and therefore, development of an AZO film etching solution with excellent performance is necessary.
Disclosure of Invention
The invention aims to develop the AZO film etching solution with excellent performance, can effectively control various performance indexes, and has the remarkable characteristics that: by optimizing the formulation, appropriate performance parameters can be obtained such as: CD loss, taper, residual, burr; low cost, safety and environmental protection.
The technical scheme adopted by the invention for solving the technical problems is as follows:
an etching solution composition for an aluminum-doped zinc oxide (AZO) film is provided, which comprises at least two of the following components a, b and c, a component d and a component e, wherein:
the component a is selected from phosphoric acid, nitric acid and hydrochloric acid;
the component b is selected from oxalic acid, citric acid, malic acid, tartaric acid, phytic acid, lactic acid and acetic acid;
component c is selected from ammonium chloride;
the component d is selected from sodium dodecyl sulfate, maleic anhydride/acrylic acid copolymer, hexadecyl trimethyl ammonium bromide and ferric chloride;
component e is selected from water.
The AZO film etching solution is an acidic system, and the etching solution composition provided by the invention can effectively control the performances such as etching rate, CDloss, taper angle and the like through specific compositions, and finally obtain a proper performance index.
Preferably, the content of the component a is 1-5% by weight of the total weight of the etching solution composition; the content of the component b is 1-10%; the content of the component c is 10-20%; the content of the component d is 0.02 to 0.3 percent; the balance being water.
Preferably, the component a is selected from one of 1-4% phosphoric acid, 2-5% nitric acid and 1-5% hydrochloric acid.
Preferably, the component b is one selected from 1-10% of oxalic acid, 1-4% of citric acid, 1-5% of malic acid, 2-6% of tartaric acid, 2-6% of phytic acid, 1-10% of lactic acid and 1-6% of acetic acid.
Preferably, the content of the component c is 14 to 16%.
Preferably, the component d is one selected from 0.1-0.5% of sodium dodecyl sulfate, 0.05-0.2% of maleic anhydride/acrylic acid copolymer, 0.05-0.3% of hexadecyl trimethyl ammonium bromide and 0.02-0.1% of ferric chloride.
Preferably, the etching solution composition comprises at least two of 1-4% of phosphoric acid, 1-5% of malic acid and 14-16% of ammonium chloride, 0.1-0.5% of sodium dodecyl sulfate or 0.02-0.1% of ferric chloride, and the balance of water.
Drawings
FIG. 1 is an SEM image of an 800nm thin film etched by the etching solution of example 3 provided by the invention for 70 s;
FIG. 2 is an SEM image of the etching solution of example 2 provided by the present invention after etching a 800nm thin film for 70 s;
FIG. 3 is an SEM image of 300nm thin film etched by the etching solution of example 3 provided by the present invention for 60 s;
FIG. 4 is an SEM image of a 300nm thin film etched by the etching solution of example 2 provided by the present invention for 60 s.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects solved by the present invention more apparent, the present invention is further described in detail below with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The etching solution composition for the aluminum-doped zinc oxide (AZO) film comprises at least two of the following components a, b and c, a component d and a component e, wherein:
the component a is selected from phosphoric acid, nitric acid and hydrochloric acid;
the component b is selected from oxalic acid, citric acid, malic acid, tartaric acid, phytic acid, lactic acid and acetic acid;
component c is selected from ammonium chloride;
the component d is selected from sodium dodecyl sulfate, maleic anhydride/acrylic acid copolymer, hexadecyl trimethyl ammonium bromide and ferric chloride;
component e is selected from water.
In the present invention, the component a and the component b mainly play a role of etching metals and oxides. Wherein, the component a is selected from one of phosphoric acid, nitric acid and hydrochloric acid. The component b is one selected from oxalic acid, citric acid, malic acid, tartaric acid, phytic acid, lactic acid and acetic acid.
The content of the component a is 1-5% by taking the total weight of the etching solution composition as a reference; the content of the component b is 1-10%. Specifically, the component a is selected from one of 1-4% phosphoric acid, 2-5% nitric acid and 1-5% hydrochloric acid, preferably, a is selected from one of 2-3% phosphoric acid, 3-4% nitric acid and 2-4% hydrochloric acid. The component b is one selected from 1-10% oxalic acid, 1-4% citric acid, 1-5% malic acid, 2-6% tartaric acid, 2-6% phytic acid, 1-10% lactic acid, and 1-6% acetic acid. Preferably, the component b is one selected from 4-7% of oxalic acid, 2-3% of citric acid, 2-4% of malic acid, 4-5% of tartaric acid, 3-4% of phytic acid, 5-7% of lactic acid and 3-4% of acetic acid.
The content of the component c, namely ammonium chloride, is 10-20 percent based on the total weight of the etching solution composition; preferably 14-16%.
In the invention, the component d is used for reducing etching burrs, adjusting the etching appearance and ensuring the etching uniformity. The content of the component d is 0.02 to 0.3 percent by taking the total weight of the etching solution composition as a reference. Specifically, the component d is one selected from 0.1-0.5% of sodium dodecyl sulfate, 0.05-0.2% of maleic anhydride/acrylic acid copolymer, 0.05-0.3% of hexadecyl trimethyl ammonium bromide and 0.02-0.1% of ferric chloride. Preferably, the component d is one selected from 0.2-0.3% of sodium dodecyl sulfate, 0.1-0.15% of maleic anhydride/acrylic acid copolymer, 0.1-0.2% of hexadecyl trimethyl ammonium bromide and 0.03-0.08% of ferric chloride.
And the component e is water and is used as a solvent of the whole etching solution system. In the case where the etching solution has the above components and contents, the remaining component is water.
According to the present invention, it is preferable that the etching solution composition includes at least two of phosphoric acid of 1-4%, malic acid of 1-5%, ammonium chloride of 14-16%, and sodium dodecylsulfate of 0.1-0.5% or ferric chloride of 0.02-0.1%, and the balance of water, from the viewpoint of etching effect. As one preferable scheme, the etching solution composition comprises 2.5% of phosphoric acid, 3% of malic acid, 0.2% of sodium dodecyl sulfate and the balance of water. In another preferred embodiment, the etching solution composition comprises 2.5% of phosphoric acid, 10% of ammonium chloride, 0.05% of ferric chloride and the balance of water. As another preferred embodiment disclosed in the present invention, the etching solution composition comprises 4% of malic acid, 15% of ammonium chloride, 0.2% of sodium dodecyl sulfate and the balance of water.
The present invention will be further illustrated by the following examples.
Examples
This example illustrates the etchant composition disclosed in the present invention.
A desired resist pattern is formed on a glass substrate by sputtering, forming an AZO thin film containing ZnO as a main component and aluminum as a dopant component, and performing development and exposure processes.
The etching temperature of the glass substrate is 30-45 ℃, the etching time is 60-80 s, and after the etching is finished, rinsing is carried out by pure water and then drying is carried out.
Samples with the film thickness of 300-800nm are selected for testing.
The etching process conditions are as follows: the etching temperature was 35 ℃ and the etching time was 30% OE (OE means over-etch time, 30% OE is over-etch time 30% on the exact basis of the etching time).
Evaluation was made by etch rate (expressed as the exact etch time EPD, representing the time the film just etched clean), etch residue, spike Angle, CD Loss, etch uniformity.
The etching criteria were: taper Angle is more than or equal to 60 degrees and less than or equal to 80 degrees, and CD Loss is less than or equal to 1.00 mu m.
The results of the examples and comparative examples are shown in Table 1.
TABLE 1
The SEM pictures of the etching solution of example 2 after etching the 800nm thin film for 70s are shown in fig. 2, the SEM pictures of the etching solution of example 2 after etching the 300nm thin film for 60s are shown in fig. 4, the SEM pictures of the etching solution of example 3 after etching the 800nm thin film for 70s are shown in fig. 1, and the SEM pictures of the etching solution of example 3 after etching the 300nm thin film for 60s are shown in fig. 3. As can be seen from FIGS. 1 to 4, the etching solution provided by the present invention has good CD loss and tape angle, and no residue or burr.
As can be seen from the test results in table 1, the test results of examples 1 to 3 are significantly better than those of comparative examples 1 to 6. Among them, EPDs of examples 1 to 3 are shorter than those of comparative examples 1 to 6, and the etching rate is high. And no residue remained after etching in examples 1-3. Importantly, the Taper Angle of examples 1-3 all reached the standard, while comparative examples 1-6 show that the etching solution contained only one of phosphoric acid, malic acid and ammonium chloride, and the etching did not reach the standard. In addition, the etching uniformity of examples 1 to 3 was also excellent.
As can be seen from the results of comparing example 1 with comparative example 1, EPD increased significantly in the absence of phosphoric acid and resulted in residues, and Taper Angle was too small. Comparing the results of example 1 and comparative example 2, it can be seen that EPD increased significantly and Taper Angle was too large in the absence of malic acid. As can be seen from the results of comparing example 1 with comparative example 3, EPD is too long, Taper Angle does not meet the standard and etching is not uniform in the absence of sodium dodecylsulfate. As can be seen by comparing the results of example 3 and comparative example 4, EPD is too long and residues are produced in the absence of malic acid, and Taper Angle is too small. As can be seen by comparing the results of example 3 and comparative example 5, EPD is too long and residues are produced in the absence of malic acid, and Taper Angle is too small. As can be seen from the test results of comparative example 6, if only sodium dodecylsulfate is contained, etching cannot be performed.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (7)
1. The etching solution composition for the aluminum-doped zinc oxide film is characterized by comprising at least two of the following components a, b and c, a component d and a component e, wherein:
the component a is selected from phosphoric acid, nitric acid and hydrochloric acid;
the component b is selected from oxalic acid, citric acid, malic acid, tartaric acid, phytic acid, lactic acid and acetic acid;
component c is selected from ammonium chloride;
the component d is selected from sodium dodecyl sulfate, maleic anhydride/acrylic acid copolymer, hexadecyl trimethyl ammonium bromide and ferric chloride;
component e is selected from water.
2. The etching solution composition as claimed in claim 1, wherein the content of the component a is 1-5% by weight based on the total weight of the etching solution composition; the content of the component b is 1-10%; the content of the component c is 10-20%; the content of the component d is 0.02 to 0.3 percent; the balance being water.
3. The etching solution composition according to claim 1 or 2, wherein the component a is one selected from the group consisting of 1-4% phosphoric acid, 2-5% nitric acid, and 1-5% hydrochloric acid.
4. The etching solution composition according to claim 1 or 2, wherein the component b is one selected from the group consisting of 1-10% oxalic acid, 1-4% citric acid, 1-5% malic acid, 2-6% tartaric acid, 2-6% phytic acid, 1-10% lactic acid, and 1-6% acetic acid.
5. The etching solution composition according to claim 1 or 2, wherein the content of the component c is 14 to 16%.
6. The etching solution composition as claimed in claim 1 or 2, wherein the component d is selected from one of 0.1-0.5% sodium dodecyl sulfate, 0.05-0.2% maleic anhydride/acrylic acid copolymer, 0.05-0.3% cetyl trimethyl ammonium bromide, and 0.02-0.1% ferric chloride.
7. The etching solution composition of claim 1, wherein the etching solution composition comprises at least two of 1-4% phosphoric acid, 1-5% malic acid, 14-16% ammonium chloride, and 0.1-0.5% sodium dodecyl sulfate or 0.02-0.1% ferric chloride, and the balance water.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201811100957.8A CN110922971A (en) | 2018-09-20 | 2018-09-20 | Etching solution composition for aluminum-doped zinc oxide film |
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| CN201811100957.8A CN110922971A (en) | 2018-09-20 | 2018-09-20 | Etching solution composition for aluminum-doped zinc oxide film |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101208277A (en) * | 2005-07-04 | 2008-06-25 | 默克专利股份公司 | Medium for etching oxidic transparent conductive layers |
| CN101245462A (en) * | 2007-02-13 | 2008-08-20 | 峻科技有限公司 | Etching liquid composition and etching method |
| CN103980905A (en) * | 2014-05-07 | 2014-08-13 | 佛山市中山大学研究院 | Novel etching solution used in oxide material system, and etching method and application thereof |
| CN106637209A (en) * | 2016-12-29 | 2017-05-10 | 深圳市华星光电技术有限公司 | Etching solution composition and metal film etching method using same |
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2018
- 2018-09-20 CN CN201811100957.8A patent/CN110922971A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101208277A (en) * | 2005-07-04 | 2008-06-25 | 默克专利股份公司 | Medium for etching oxidic transparent conductive layers |
| CN101245462A (en) * | 2007-02-13 | 2008-08-20 | 峻科技有限公司 | Etching liquid composition and etching method |
| CN103980905A (en) * | 2014-05-07 | 2014-08-13 | 佛山市中山大学研究院 | Novel etching solution used in oxide material system, and etching method and application thereof |
| CN106637209A (en) * | 2016-12-29 | 2017-05-10 | 深圳市华星光电技术有限公司 | Etching solution composition and metal film etching method using same |
Non-Patent Citations (1)
| Title |
|---|
| D.-G. YOO等: ""Fabrication of the ZnO thin films using wet-chemical etching processes on application for organic light emitting diode (OLED) devices"", 《SURFACE AND COATINGS TECHNOLOGY》 * |
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Application publication date: 20200327 |