CN117867501A - Molybdenum-aluminum dual-purpose etching solution and preparation method of substrate patterning metal layer - Google Patents
Molybdenum-aluminum dual-purpose etching solution and preparation method of substrate patterning metal layer Download PDFInfo
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- CN117867501A CN117867501A CN202410277691.3A CN202410277691A CN117867501A CN 117867501 A CN117867501 A CN 117867501A CN 202410277691 A CN202410277691 A CN 202410277691A CN 117867501 A CN117867501 A CN 117867501A
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- 238000005530 etching Methods 0.000 title claims abstract description 184
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 42
- 239000002184 metal Substances 0.000 title claims abstract description 42
- 239000000758 substrate Substances 0.000 title claims abstract description 33
- ZXTFQUMXDQLMBY-UHFFFAOYSA-N alumane;molybdenum Chemical compound [AlH3].[Mo] ZXTFQUMXDQLMBY-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000000059 patterning Methods 0.000 title claims abstract description 8
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 54
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 52
- 239000011733 molybdenum Substances 0.000 claims abstract description 52
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 36
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 34
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 32
- -1 carboxylic acid compounds Chemical class 0.000 claims abstract description 32
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 32
- 239000010410 layer Substances 0.000 claims abstract description 29
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000005695 Ammonium acetate Substances 0.000 claims abstract description 27
- 229940043376 ammonium acetate Drugs 0.000 claims abstract description 27
- 235000019257 ammonium acetate Nutrition 0.000 claims abstract description 27
- 238000005260 corrosion Methods 0.000 claims abstract description 21
- 230000007797 corrosion Effects 0.000 claims abstract description 21
- 239000003112 inhibitor Substances 0.000 claims abstract description 21
- 239000002356 single layer Substances 0.000 claims abstract description 21
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 17
- 239000007788 liquid Substances 0.000 claims abstract description 12
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 12
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 12
- 239000004094 surface-active agent Substances 0.000 claims abstract description 11
- UNQHSZOIUSRWHT-UHFFFAOYSA-N aluminum molybdenum Chemical compound [Al].[Mo] UNQHSZOIUSRWHT-UHFFFAOYSA-N 0.000 claims abstract description 4
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 6
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 6
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 6
- 239000003093 cationic surfactant Substances 0.000 claims description 5
- XJWSAJYUBXQQDR-UHFFFAOYSA-M dodecyltrimethylammonium bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](C)(C)C XJWSAJYUBXQQDR-UHFFFAOYSA-M 0.000 claims description 5
- 150000003242 quaternary ammonium salts Chemical group 0.000 claims description 5
- FMCUPJKTGNBGEC-UHFFFAOYSA-N 1,2,4-triazol-4-amine Chemical compound NN1C=NN=C1 FMCUPJKTGNBGEC-UHFFFAOYSA-N 0.000 claims description 4
- KLSJWNVTNUYHDU-UHFFFAOYSA-N Amitrole Chemical compound NC1=NC=NN1 KLSJWNVTNUYHDU-UHFFFAOYSA-N 0.000 claims description 4
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 3
- WZUUZPAYWFIBDF-UHFFFAOYSA-N 5-amino-1,2-dihydro-1,2,4-triazole-3-thione Chemical compound NC1=NNC(S)=N1 WZUUZPAYWFIBDF-UHFFFAOYSA-N 0.000 claims description 3
- CXRFDZFCGOPDTD-UHFFFAOYSA-M Cetrimide Chemical compound [Br-].CCCCCCCCCCCCCC[N+](C)(C)C CXRFDZFCGOPDTD-UHFFFAOYSA-M 0.000 claims description 3
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 3
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 3
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 3
- 235000015165 citric acid Nutrition 0.000 claims description 3
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 3
- NMHMDUCCVHOJQI-UHFFFAOYSA-N lithium molybdate Chemical compound [Li+].[Li+].[O-][Mo]([O-])(=O)=O NMHMDUCCVHOJQI-UHFFFAOYSA-N 0.000 claims description 3
- 239000001630 malic acid Substances 0.000 claims description 3
- 235000011090 malic acid Nutrition 0.000 claims description 3
- 239000001384 succinic acid Substances 0.000 claims description 3
- 235000011044 succinic acid Nutrition 0.000 claims description 3
- 239000011975 tartaric acid Substances 0.000 claims description 3
- 235000002906 tartaric acid Nutrition 0.000 claims description 3
- CEYYIKYYFSTQRU-UHFFFAOYSA-M trimethyl(tetradecyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCC[N+](C)(C)C CEYYIKYYFSTQRU-UHFFFAOYSA-M 0.000 claims description 3
- APTHSBLGVMYQRL-UHFFFAOYSA-N 4-amino-1h-pyrrole-2-carboxylic acid Chemical compound NC1=CNC(C(O)=O)=C1 APTHSBLGVMYQRL-UHFFFAOYSA-N 0.000 claims 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 abstract description 21
- 238000001039 wet etching Methods 0.000 abstract description 4
- 239000010408 film Substances 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 15
- 239000011521 glass Substances 0.000 description 10
- 238000010586 diagram Methods 0.000 description 8
- 230000008569 process Effects 0.000 description 7
- 238000005240 physical vapour deposition Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000001755 magnetron sputter deposition Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- DNAUJKZXPLKYLD-UHFFFAOYSA-N alumane;molybdenum Chemical group [AlH3].[Mo].[Mo] DNAUJKZXPLKYLD-UHFFFAOYSA-N 0.000 description 3
- 238000007747 plating Methods 0.000 description 3
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- VXAPDXVBDZRZKP-UHFFFAOYSA-N nitric acid phosphoric acid Chemical compound O[N+]([O-])=O.OP(O)(O)=O VXAPDXVBDZRZKP-UHFFFAOYSA-N 0.000 description 2
- 229910017464 nitrogen compound Inorganic materials 0.000 description 2
- QLSWIGRIBOSFMV-UHFFFAOYSA-N 1h-pyrrol-2-amine Chemical compound NC1=CC=CN1 QLSWIGRIBOSFMV-UHFFFAOYSA-N 0.000 description 1
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- 229920001621 AMOLED Polymers 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000001312 dry etching Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000007733 ion plating Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 235000019633 pungent taste Nutrition 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000009469 supplementation Effects 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000000427 thin-film deposition Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/16—Acidic compositions
- C23F1/26—Acidic compositions for etching refractory metals
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/02—Local etching
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/16—Acidic compositions
- C23F1/20—Acidic compositions for etching aluminium or alloys thereof
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- ing And Chemical Polishing (AREA)
Abstract
The invention belongs to the field of wet etching, and particularly relates to a molybdenum-aluminum dual-purpose etching solution and a preparation method of a substrate patterning metal layer. The etching solution provided by the invention comprises the following components: phosphoric acid, nitric acid, carboxylic acid compounds, corrosion inhibitors and surfactants; the corrosion inhibitor at least comprises ammonium acetate; the content of phosphoric acid in the etching liquid is 30-70wt%, the content of nitric acid in the etching liquid is 8-20wt%, the content of carboxylic acid compound in the etching liquid is 1-20wt%, and the content of ammonium acetate in the etching liquid is 5-17wt%. The etching solution does not contain acetic acid, and ammonium acetate is introduced to improve the nitric acid content, prolong the service life of the etching solution, avoid frequent nitric acid replacement and effectively control the tip angle. In addition, the amino-nitrogen azole corrosion inhibitor is compounded with ammonium acetate, so that the method can be widely applied to aluminum-molybdenum single-layer or multi-layer metal etching; and the relative etching rate of metal molybdenum and aluminum is adjusted by introducing lithium salt, so that the shape after etching is improved.
Description
Technical Field
The invention belongs to the field of wet etching, and particularly relates to a molybdenum-aluminum dual-purpose etching solution and a preparation method of a substrate patterning metal layer.
Background
In photolithography, etching is an essential element in order to precisely transfer the pattern on the photolithographic reticle to the surface of the wafer. The etching process is mainly divided into two types, namely dry etching and wet etching.
Currently, wet etching processes are widely used in the field of TFT-LCD and AMOLED substrates. Since there are many thin layers on the substrate, if aluminum or aluminum alloy is used as the base film, the adhesion with the glass substrate is poor, so that in practical production, metallic molybdenum is mostly used as the connection, such as a single-layer molybdenum, molybdenum aluminum molybdenum structure. Currently, most molybdenum aluminum etching solutions are a triacid system, namely phosphoric acid, nitric acid, acetic acid and additives, and the following problems generally exist: (1) Acetic acid has strong volatility, needs to be continuously replenished with liquid in the use process, has strong pungent taste and has poor production operation environment; (2) The method is limited by the requirement on etching rate, the concentration of nitric acid in a triacid system cannot be too high, but nitric acid is the main etchant, so that liquid supplementation is often required in the use process; (3) etching angle (tip angle) is difficult to control effectively.
Disclosure of Invention
In view of the above, the present invention aims to provide a molybdenum-aluminum dual-purpose etching solution and a method for preparing a patterned metal layer of a substrate, wherein the etching solution provided by the present invention does not contain acetic acid component, has a longer service life, does not need frequent nitric acid replacement, and can effectively control a taper angle.
The invention provides a molybdenum-aluminum dual-purpose etching solution, which comprises the following components: phosphoric acid, nitric acid, carboxylic acid compounds, corrosion inhibitors and surfactants; the corrosion inhibitor at least comprises ammonium acetate; the content of phosphoric acid in the etching solution is 30-70wt%, the content of nitric acid in the etching solution is 8-20wt%, the content of carboxylic acid compound in the etching solution is 1-20wt%, and the content of ammonium acetate in the etching solution is 5-17wt%.
Preferably, the carboxylic acid compound is at least one of citric acid, tartaric acid, malic acid and succinic acid;
and/or the content of the phosphoric acid in the etching solution is 40-70wt%;
and/or the content of the nitric acid in the etching solution is 10-20wt%;
and/or the content of the carboxylic acid compound in the etching solution is 5-20wt%;
and/or the content of the ammonium acetate in the etching solution is 7-15 wt%.
Preferably, the surfactant is a quaternary ammonium salt cationic surfactant.
Preferably, the quaternary ammonium salt cationic surfactant is at least one of dodecyl trimethyl ammonium bromide, tetradecyl trimethyl ammonium bromide and tetradecyl trimethyl ammonium chloride; and/or the content of the surfactant in the etching solution is below 0.5 wt%.
Preferably, the corrosion inhibitor further comprises an amino-azole compound.
Preferably, the amino-nitrogen compound is at least one of 3-amino-1, 2, 4-triazole, 4-amino-1, 2, 4-triazole, 5-amino-4-triazole, 3-amino-5-mercapto-1, 2, 4-triazole and 5-carboxyl-3-amino-nitrogen; and/or the content of the amino-azole compound in the etching solution is below 3 wt%.
Preferably, the etching solution further comprises a regulator; the regulator is lithium salt.
Preferably, the lithium salt is at least one of lithium acetate, lithium nitrate, lithium molybdate and lithium chloride; and/or the content of the lithium salt in the etching solution is below 3 wt%.
The invention provides a preparation method of a substrate patterning metal layer, which comprises the following steps:
the metal layer of the substrate is contacted with etching liquid for etching, so that a patterned metal layer is obtained; the metal layer of the substrate contains aluminum and/or molybdenum;
when the substrate contains a single-layer aluminum film or a single-layer molybdenum film structure, the etching solution is any one of the molybdenum-aluminum dual-purpose etching solutions in the technical scheme;
when the substrate contains an aluminum-molybdenum multilayer structure, the etching solution is the molybdenum-aluminum dual-purpose etching solution with the corrosion inhibitor containing the amino-nitrogen azole compound in the technical scheme; the multilayer structure comprises a molybdenum/aluminum bilayer or a molybdenum/aluminum/molybdenum trilayer structure.
Preferably, the etching temperature is 30-45 ℃.
Compared with the prior art, the invention provides a molybdenum-aluminum dual-purpose etching solution and a preparation method of a substrate patterning metal layer, and the etching solution comprises the following components: phosphoric acid, nitric acid, carboxylic acid compounds, corrosion inhibitors and surfactants; the corrosion inhibitor at least comprises ammonium acetate; the content of phosphoric acid in the etching solution is 30-70wt%, the content of nitric acid in the etching solution is 8-20wt%, the content of carboxylic acid compound in the etching solution is 1-20wt%, and the content of ammonium acetate in the etching solution is 5-17wt%. According to the invention, the composition of the components and the content of each component of the etching solution are optimized, so that the etching solution has longer service life without introducing acetic acid components, frequent nitric acid replacement is not needed, and the TAPER angle can be effectively controlled. More specifically, the etching solution provided by the invention has the following technical advantages:
(1) The carboxylic acid compound used for the molybdenum-aluminum dual-purpose etching solution replaces acetic acid, so that the problem of large acetic acid smell in the traditional aluminum etching solution is solved, the taper angle after single-layer molybdenum etching can be controlled to be 30-65 degrees, and after multi-layer etching, the top is free from shrinking and the bottom is free from inscription.
(2) The etching speed of the traditional etching liquid is too high, so that the etching of the middle and edge positions of the glass substrate is uneven, and the cdloss and taper angle are difficult to control; according to the etching solution, the etching rate of the metal molybdenum is controlled by adding the ammonium acetate with higher content, so that the etching rate is reduced, and the difference is effectively improved; in addition, the etching solution provided by the invention adopts ammonium acetate as a main component of the corrosion inhibitor, so that on one hand, the introduction of impurity ions is reduced, and the influence of metal ions on a glass substrate is reduced, and on the other hand, the ammonium acetate and nitric acid can form ionization balance, and the etching solution comprises the following components:
；
due to the action of ammonium acetate, the etching liquid of the invention has higher nitric acid content than the traditional etching liquid, but the etching rate is not obviously accelerated. When the nitric acid is consumed, the balance moves leftwards, so that the concentration change caused by the consumption of the nitric acid in the etching process can be avoided, the liquid supplementing times are reduced, and the service life is prolonged. And the direct use of ammonium nitrate is avoided, and the safety is higher.
(3) The etching solution provided by the invention not only can be applied to the etching of single-layer molybdenum, but also can be used for the etching of molybdenum aluminum or molybdenum aluminum molybdenum multilayer metal; for multi-layer metal etching, the invention adopts the corrosion inhibitor compounded by ammonium acetate and amino-nitrogen azole compounds to simultaneously control the etching rate of metal molybdenum and aluminum, thereby achieving an ideal gradient angle.
(4) The etching solution provided by the invention can change the relative etching rate of metal molybdenum and aluminum by introducing the lithium salt regulator, improve the shape after etching, and solve the problems of T shape and I shape.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required to be used in the embodiments or the description of the prior art will be briefly described below, and it is obvious that the drawings in the following description are only embodiments of the present invention, and that other drawings can be obtained according to the provided drawings without inventive effort for a person skilled in the art.
FIG. 1 is an SEM-FIB diagram of a single layer of metallic molybdenum of example 1 etching solution at four different etching times;
FIG. 2 is an SEM-FIB diagram of a single layer of metallic molybdenum of example 2 etching solution at four different etching times;
FIG. 3 is an SEM-FIB diagram of a single layer of metallic molybdenum of example 4 etching solution at four different etching times;
FIG. 4 is an SEM-FIB diagram of the metal Mo/Al/Mo of example 5 etching solution at four different etching times;
FIG. 5 is an SEM-FIB diagram of the metal Mo/Al/Mo of the etching solution of example 5' at four different etching times;
FIG. 6 is an SEM-FIB diagram of the metal Mo/Al/Mo of example 8 etchant at four different etching times;
FIG. 7 is an SEM-FIB diagram of a single layer of metallic molybdenum of comparative example 3 etching solution at four different etching times;
FIG. 8 is an SEM-FIB diagram of a comparative example 4 etchant for metallic molybdenum/aluminum/molybdenum at four different etching times;
fig. 9 is an SEM-FIB plot of the metal molybdenum/aluminum/molybdenum for comparative example 5 etchant at four different etching times.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Unless otherwise indicated, all starting materials and reagents in the examples herein were purchased commercially. Examples and comparative examples, the FIB of the samples were characterized using a Hitachi SU-8020 model field emission scanning electron microscope.
The invention provides a molybdenum-aluminum dual-purpose etching solution, which comprises the following components: phosphoric acid, nitric acid, carboxylic acid compounds, corrosion inhibitors and surfactants.
In the etching solution provided by the invention, the content of the phosphoric acid in the etching solution is 30-70 wt%, preferably 40-70 wt%, and specifically 30wt%, 31wt%, 32wt%, 33wt%, 34wt%, 35wt%, 36wt%, 37wt%, 38wt%, 39wt%, 40wt%, 41wt%, 42wt%, 43wt%, 44wt%, 45wt%, 46wt%, 47wt%, 48wt%, 49wt%, 50wt%, 51wt%, 52wt%, 53wt%, 54wt%, 55wt%, 56wt%, 57wt%, 58wt%, 59wt%, 60wt%, 61wt%, 62wt%, 63wt%, 64wt%, 65wt%, 66wt%, 67wt%, 68wt%, 69wt% or 70wt%.
In the etching solution provided by the invention, the content of the nitric acid in the etching solution is 8-20wt%, preferably 10-20wt%, and specifically can be 8wt%, 9wt%, 10wt%, 11wt%, 12wt%, 13wt%, 14wt%, 15wt%, 16wt%, 17wt%, 18wt%, 19wt% or 20wt%.
In the etching solution provided by the invention, the carboxylic acid compound is preferably at least one of citric acid, tartaric acid, malic acid and succinic acid; the content of the carboxylic acid compound in the etching solution is 1 to 20wt%, preferably 5 to 20wt%, and specifically may be 1wt%, 2wt%, 3wt%, 4wt%, 5wt%, 6wt%, 7wt%, 8wt%, 9wt%, 10wt%, 11wt%, 12wt%, 13wt%, 14wt%, 15wt%, 16wt%, 17wt%, 18wt%, 19wt% or 20wt%.
In the etching solution provided by the invention, the corrosion inhibitor at least comprises ammonium acetate; the content of the ammonium acetate in the etching solution is 5-17 wt%, preferably 7-15 wt%, and specifically may be 5wt%, 6wt%, 7wt%, 8wt%, 9wt%, 10wt%, 11wt%, 12wt%, 13wt%, 14wt%, 15wt%, 16wt% or 17wt%.
In the etching solution provided by the invention, the corrosion inhibitor preferably further comprises an amino-nitrogen azole compound; the amino-nitrogen compound is preferably at least one of 3-amino-1, 2, 4-triazole, 4-amino-1, 2, 4-triazole, 5-amino-4-triazole, 3-amino-5-mercapto-1, 2, 4-triazole and 5-carboxyl-3-amino-nitrogen; the content of the amino-azole compound in the etching solution is 3wt% or less, preferably 1wt% or less, more preferably 0.01 to 1wt%, and specifically may be 0.01wt%, 0.05wt%, 0.1wt%, 0.2wt%, 0.3wt%, 0.4wt%, 0.5wt%, 0.6wt%, 0.7wt%, 0.8wt%, 0.9wt% or 1wt%.
In the etching solution provided by the invention, the surfactant is preferably a quaternary ammonium salt cationic surfactant, and more preferably at least one of dodecyl trimethyl ammonium bromide, tetradecyl trimethyl ammonium bromide and tetradecyl trimethyl ammonium chloride; the content of the surfactant in the etching solution is preferably 0.5wt% or less, more preferably 0.01 to 0.1wt%, and particularly may be 0.01wt%, 0.02wt%, 0.03wt%, 0.04wt%, 0.05wt%, 0.06wt%, 0.07wt%, 0.08wt%, 0.09wt%, or 0.1wt%.
In the etching solution provided by the invention, the components preferably further comprise a regulator; the modifier is preferably a lithium salt, more preferably at least one of lithium acetate, lithium nitrate, lithium molybdate and lithium chloride; the content of the lithium salt in the etching solution is 3% or less, preferably 1% or less, more preferably 0.01 to 1% by weight, and specifically may be 0.01% by weight, 0.05% by weight, 0.1% by weight, 0.2% by weight, 0.3% by weight, 0.4% by weight, 0.5% by weight, 0.6% by weight, 0.7% by weight, 0.8% by weight, 0.9% by weight, or 1% by weight.
Currently, thin film deposition processes are largely classified into physical vapor deposition and chemical vapor deposition. Physical vapor deposition principles can be broadly divided into evaporation plating, sputtering plating, ion plating, and the like. Different deposition processes may result in different etch rates of the metal. Therefore, the same etching solution etches metal layers of different manufacturers, and different morphologies can appear even if the thicknesses of the metal layers are the same. If the H-shaped or T-shaped appearance appears in the etching process, the etching rate of the molybdenum and aluminum can be adjusted by adding the lithium salt additionally, so that the etched result is improved.
In the etching solution provided by the invention, the balance of the components is water.
The invention provides a preparation method of a substrate patterning metal layer, which comprises the following steps:
and (3) contacting the metal layer of the substrate with the etching solution for both molybdenum and aluminum to etch, thereby obtaining the patterned metal layer.
In the preparation method provided by the invention, the substrate comprises, but is not limited to, a glass substrate; the metal layer is a metal layer containing aluminum and/or molybdenum, and can be of a single-layer structure or a multi-layer composite structure; the monolayer structure includes, but is not limited to, an aluminum monolayer or a molybdenum monolayer, and the multilayer composite structure includes, but is not limited to, a molybdenum/aluminum bilayer or a molybdenum/aluminum/molybdenum trilayer.
In the preparation method provided by the invention, when the substrate contains a single-layer aluminum film or a single-layer molybdenum film structure, the etching solution can be any one of the etching solutions for both molybdenum and aluminum in the technical scheme; when the substrate contains an aluminum-molybdenum multilayer structure, the etching solution is preferably a molybdenum-aluminum dual-purpose etching solution in which the corrosion inhibitor contains an amino-azole compound in the above technical scheme.
In the production method of the present invention, the etching temperature is preferably 30 to 45 ℃, and specifically 30 ℃, 31 ℃, 32 ℃, 33 ℃, 34 ℃, 35 ℃, 36 ℃, 37 ℃, 38 ℃, 39 ℃, 40 ℃, 41 ℃, 42 ℃, 43 ℃, 44 ℃, or 45 ℃.
In the preparation method provided by the invention, the etching rate is preferably less than or equal to 80A/s, and more preferably 40-80A/s.
In the production method of the present invention, the substrate provided with the metal layer is preferably immersed in the molybdenum-aluminum dual-purpose etching solution and left to stand for etching.
For the sake of clarity, the following examples and comparative examples are described in detail.
Example 1
The etching solution provided by the embodiment is obtained by adding 52% of phosphoric acid, 10% of nitric acid, 5% of carboxylic acid compound and 7% of ammonium acetate, adding 0.05% of dodecyl trimethyl ammonium bromide and the balance of water, uniformly mixing and stirring for 10 min.
Examples 2 to 9, comparative examples 1 to 4
Referring to the preparation procedure of example 1, only the individual raw materials of example 1 were replaced and added as shown in table 1, to obtain etching solutions provided in examples 2 to 9 and comparative examples 1 to 4.
TABLE 1 composition of etching solution (mass percent content)
In Table 1, A is 5-amino-4-triazole, B is 3-amino-1, 2, 4-triazole, C is 4-amino-1, 2, 4-triazole, and D is dodecyltrimethylammonium bromide.
Performance index detection
(1) The etching rate (the etching rates obtained are all the etching rates of the film by the magnetron sputtering method and are single film layers) is determined by the following specific method:
forming a molybdenum metal film with the thickness of 3500A on a glass substrate by adopting a PVD magnetron sputtering method; the substrate was left to stand and immersed in the etchant composition shown in table 1 at 35 ℃ for etching until transparent, the recording time was je, taken out for washing with water, dried with nitrogen gas, and the molybdenum etching rate (unit: a/s) was calculated according to the following formula: etch rate=3500/je;
as above, an aluminum metal film having a thickness of 5000 a is formed using PVD magnetron sputtering to obtain an aluminum etching rate (unit: a/s): etch rate = 5000/je;
specifically, the aluminum metal film etched in example 5' was deposited by vacuum plating, so that the measured aluminum etching rate was faster than that in example 5.
(2) The etching angle (taper angle) and critical dimension loss (cd loss) were measured as follows:
for single-layer metal molybdenum, forming a molybdenum metal film with the thickness of 3500 angstroms on a glass substrate by adopting a PVD magnetron sputtering method; before etching, the etching solution is subjected to water bath temperature rising treatment, and the water bath constant temperature time is 30min; the substrate was etched at 35 ℃ in the etchant composition shown in table 1 until it was transparent, the recording time was je, then 20% (OE 20%), 30% (OE 30%) and 50% (OE 50%) of the glass pieces were overetched, and the glass pieces were taken out for 4 etching times, washed with water, dried with nitrogen, and the etching effect (mainly the tip angle and the cd loss) of the etchant on the film was observed with an electron microscope (SEM-FIB);
in the same way, for the molybdenum-aluminum-molybdenum structure, a molybdenum/aluminum/molybdenum film with the thickness of 200/3500/800A is formed on a glass substrate by adopting a PVD magnetron sputtering method, and a taper angle and a cdloss are observed;
in the taper angle and cdloss measurements, examples 1-4 and comparative examples 1-3 etched single layer molybdenum films, with the remainder etched multi-layer films (molybdenum/aluminum/molybdenum films of 200/3500/800 a).
(3) Determination of phosphoric acid and nitric acid concentration: the concentration of the phosphoric acid and the nitric acid is directly dripped by adopting a T5 tester of Metrele.
(4) The measurement results show that:
the etching rates, the taper angles, and the cd loss of the etching solutions of examples 1 to 9 and comparative examples 1 to 5 are shown in table 2, the taper angles of the etching solutions of examples 1,2,4, 5', 8 and comparative examples 3, 4, 5, and the SEM-FIB results observed during the cd loss measurement are shown in fig. 1 to 9, and the acid concentration changes before and after etching of the etching solutions of example 3 and comparative example 3 are shown in table 3.
TABLE 2 comparison of etching effects
TABLE 3 T5 test phosphoric acid nitric acid concentration variation table (unit: concentration/wt%)
(5) Analysis of measurement results:
as can be seen from table 2, when the etching solution of the present invention is used to etch single-layer metal molybdenum, the taper angle can be accurately controlled to be 30 ° to 60 ° at OE of 50% or less, and the uniformity of etching (in terms of gradient angle) is facilitated due to the extension of etching time; also, for multi-layer metal etching, a slope angle of less than 60 ° can be achieved below OE 30%.
From examples 1 to 4 and comparative example 1, it is known that ammonium acetate is not added as a corrosion inhibitor, the etching rate is too fast, and the taper angle is generally large; after ammonium acetate is added, the taper angle can be between 30 degrees and 60 degrees, and the taper angle shows an increasing trend along with the increase of etching time, so that different manufacturers can control the required taper angle according to the etching time.
As is clear from examples 3 and 2, the ammonium acetate content of 2% and the nitric acid content of 10% resulted in an excessively high etching rate, and therefore, only by increasing the ammonium acetate content of the additive, the etching rate was decreased, thereby obtaining an etching solution having a high nitric acid concentration but a slow etching rate.
It is apparent from example 3 and comparative example 3 that the theoretical content of nitric acid added was increased and the increase in metal etching rate was not significant when the ammonium acetate content was increased, and also, from table 3, it is apparent that the concentrations of phosphoric acid nitric acid were measured to be close to those of example 3 before etching, but after etching 10 and 20 glass sheets, the concentrations of phosphoric acid were close to each other, but the decrease in nitric acid concentration of comparative example 3 was significant, so that the prior art required the addition of nitric acid, while the decrease in nitric acid concentration of example 3 was not significant, so that the acid addition was not required, and the etching life was longer.
From examples 5 to 7, and comparative examples 4 and 5, it is known that the ideal taper angle cannot be obtained by singly adding ammonium acetate or an amino-azole corrosion inhibitor; only if ammonium acetate and amino-nitrogen azole are added simultaneously to compound to obtain a corrosion inhibitor, the etching speed of the metal molybdenum aluminum can be regulated, and an ideal TAPER angle is obtained.
As is clear from example 5', the aluminum film by vacuum evaporation has an excessively high etching rate, which leads to an increase in the taper angle and an i-shaped structure (fig. 5).
It can be seen from examples 8 to 9 that the etching rate of metal molybdenum aluminum can be increased simultaneously by adding metal lithium salt, but the etching rate of metal molybdenum is increased relatively faster, so that the i-shape can be improved (fig. 6).
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (10)
1. The etching solution for both molybdenum and aluminum is characterized by comprising the following components: phosphoric acid, nitric acid, carboxylic acid compounds, corrosion inhibitors and surfactants; the corrosion inhibitor at least comprises ammonium acetate; the content of phosphoric acid in the etching solution is 30-70wt%, the content of nitric acid in the etching solution is 8-20wt%, the content of carboxylic acid compound in the etching solution is 1-20wt%, and the content of ammonium acetate in the etching solution is 5-17wt%.
2. The etching solution for both molybdenum and aluminum according to claim 1, wherein the carboxylic acid compound is at least one of citric acid, tartaric acid, malic acid, and succinic acid;
and/or the content of the phosphoric acid in the etching solution is 40-70wt%;
and/or the content of the nitric acid in the etching solution is 10-20wt%;
and/or the content of the carboxylic acid compound in the etching solution is 5-20wt%;
and/or the content of the ammonium acetate in the etching solution is 7-15 wt%.
3. The etching solution for both molybdenum and aluminum according to claim 1, wherein the surfactant is a quaternary ammonium salt type cationic surfactant.
4. The etching solution for molybdenum and aluminum as defined in claim 3, wherein the quaternary ammonium salt cationic surfactant is at least one of dodecyl trimethyl ammonium bromide, tetradecyl trimethyl ammonium bromide and tetradecyl trimethyl ammonium chloride; and/or the content of the surfactant in the etching solution is below 0.5 wt%.
5. The etching solution for both molybdenum and aluminum according to claim 1, wherein the corrosion inhibitor further comprises an amino azole compound.
6. The etching solution for molybdenum and aluminum as defined in claim 5, wherein the amino-azole compound is at least one of 3-amino-1, 2, 4-triazole, 4-amino-1, 2, 4-triazole, 5-amino-4-triazole, 3-amino-5-mercapto-1, 2, 4-triazole and 5-carboxyl-3-amino-azole; and/or the content of the amino-azole compound in the etching solution is below 3 wt%.
7. The etching solution for both molybdenum and aluminum according to claim 5, wherein the etching solution further comprises a regulator; the regulator is lithium salt.
8. The etching solution for both molybdenum and aluminum according to claim 7, wherein the lithium salt is at least one of lithium acetate, lithium nitrate, lithium molybdate, and lithium chloride; and/or the content of the lithium salt in the etching solution is below 3 wt%.
9. The preparation method of the substrate patterning metal layer is characterized by comprising the following steps of:
the metal layer of the substrate is contacted with etching liquid for etching, so that a patterned metal layer is obtained; the metal layer of the substrate contains aluminum and/or molybdenum;
when the substrate contains a single-layer aluminum film or a single-layer molybdenum film structure, the etching solution is the molybdenum-aluminum dual-purpose etching solution according to any one of claims 1 to 8;
when the substrate contains an aluminum-molybdenum multilayer structure, the etching solution is the molybdenum-aluminum dual-purpose etching solution according to any one of claims 5 to 8; the multilayer structure comprises a molybdenum/aluminum bilayer or a molybdenum/aluminum/molybdenum trilayer structure.
10. The method according to claim 9, wherein the etching temperature is 30-45 ℃.
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