CN104611700A - Etching solution composition and etching method - Google Patents
Etching solution composition and etching method Download PDFInfo
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- CN104611700A CN104611700A CN201410571102.9A CN201410571102A CN104611700A CN 104611700 A CN104611700 A CN 104611700A CN 201410571102 A CN201410571102 A CN 201410571102A CN 104611700 A CN104611700 A CN 104611700A
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- acid
- etchant
- copper
- molybdenum
- etching
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- 238000000034 method Methods 0.000 title claims description 10
- 239000000203 mixture Substances 0.000 title abstract description 11
- 229910052802 copper Inorganic materials 0.000 claims abstract description 76
- 239000010949 copper Substances 0.000 claims abstract description 76
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 58
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- 239000011733 molybdenum Substances 0.000 claims abstract description 45
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- 239000004471 Glycine Substances 0.000 claims description 4
- FSVCELGFZIQNCK-UHFFFAOYSA-N N,N-bis(2-hydroxyethyl)glycine Chemical compound OCCN(CCO)CC(O)=O FSVCELGFZIQNCK-UHFFFAOYSA-N 0.000 claims description 4
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 claims description 4
- RBNPOMFGQQGHHO-UHFFFAOYSA-N -2,3-Dihydroxypropanoic acid Natural products OCC(O)C(O)=O RBNPOMFGQQGHHO-UHFFFAOYSA-N 0.000 claims description 3
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- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 claims description 3
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- CKLJMWTZIZZHCS-REOHCLBHSA-N L-aspartic acid Chemical compound OC(=O)[C@@H](N)CC(O)=O CKLJMWTZIZZHCS-REOHCLBHSA-N 0.000 claims description 3
- HNDVDQJCIGZPNO-YFKPBYRVSA-N L-histidine Chemical compound OC(=O)[C@@H](N)CC1=CN=CN1 HNDVDQJCIGZPNO-YFKPBYRVSA-N 0.000 claims description 3
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- KZSNJWFQEVHDMF-BYPYZUCNSA-N L-valine Chemical compound CC(C)[C@H](N)C(O)=O KZSNJWFQEVHDMF-BYPYZUCNSA-N 0.000 claims description 3
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- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 3
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 3
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- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 125000003368 amide group Chemical group 0.000 claims description 3
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- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 3
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- OQFSQFPPLPISGP-UHFFFAOYSA-N beta-carboxyaspartic acid Natural products OC(=O)C(N)C(C(O)=O)C(O)=O OQFSQFPPLPISGP-UHFFFAOYSA-N 0.000 claims description 3
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- HCPOCMMGKBZWSJ-UHFFFAOYSA-N ethyl 3-hydrazinyl-3-oxopropanoate Chemical compound CCOC(=O)CC(=O)NN HCPOCMMGKBZWSJ-UHFFFAOYSA-N 0.000 claims description 3
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- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 3
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- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 3
- IUGYQRQAERSCNH-UHFFFAOYSA-N pivalic acid Chemical compound CC(C)(C)C(O)=O IUGYQRQAERSCNH-UHFFFAOYSA-N 0.000 claims description 3
- 235000019260 propionic acid Nutrition 0.000 claims description 3
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- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 3
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Landscapes
- ing And Chemical Polishing (AREA)
- Weting (AREA)
Abstract
An etching solution composition for etching a multilayer film containing copper and molybdenum, the etching solution composition comprising hydrogen peroxide, a first organic acid or a salt thereof, a second organic acid or a salt thereof, and an alcohol amine compound. The chelating constant of the first organic acid and copper is greater than or equal to 0 and less than 6, and the adding proportion of the first organic acid is 5.5 to 17.5 weight percent based on 100 weight percent of the etching solution composition. The second organic acid has a chelation constant for copper of 6 or more and less than 18.5. The alcohol amine compound has more than one amine group and more than one hydroxyl group. The etching solution composition can be used for etching the copper-containing and molybdenum-containing multilayer film, and is beneficial to reducing metal residues.
Description
Technical field
The invention relates to a kind of etchant, and relate to a kind of for etching cupric and the etchant containing molybdenum multilayer film especially.
Background technology
The wiring material of small-medium size liquid-crystal display is at present based on aluminum or aluminum alloy, along with the development of large size panel, indicating meter needs lower resistor capacitor edge to postpone (RC delay), shorter duration of charging and lower aperture opening ratio, therefore seeks high conductivity, the better copper of anti-electromigration ability and alloy thereof on wiring material.
Containing the production method of copper wiring, be the multilayer film of deposition containing copper on substrate, and utilize photoresistance to determine the circuit pattern needed as light shield, then carry out anisotropic etching with the method for Wet-type etching.Aforenoted multi-layer film often adopts cupric and the multiple layer metal film containing molybdenum, and the multilayer film such as such as copper/molybdenum, copper/molybdenum nitride, molybdenum/copper/molybdenum nitride, molybdenum nitride/copper/molybdenum nitride or molybdenum nitride/copper/molybdenum, to overcome the disappearance that between silicon-containing layer and copper, tack is not good.
Etching performance need meet following demand: the section shape that (1) is good, the cone angle (taper) containing copper wiring section is required to be positive cone angle.(2) etching metal residue is few.(3) containing end distance photoresistance border (critical dimension bias, CD bias, CD is poor) of copper wiring under low copper concentration, the monolateral boundary that needs, in 0.8 to 1.1um, monolaterally under copper concentration is at least greater than 0.5um.In addition, due in etching process, metal can be dissolved in etching solution, therefore etching solution maintains the ability of etching performance and stability also must be listed in and considers, to extend the work-ing life of etching solution.
But, when using the etching of the etching solution containing hydrogen peroxide while when cupric and the multiple layer metal film containing molybdenum, copper is not identical with the etching condition needed for molybdenum, such as, the pH of etch copper is good with 2 ~ 4, and the pH of etching molybdenum is good with 4 ~ 7, therefore when the condition equaling 2 ~ 4 with pH etches, easily cause the residual of molybdenum, when the condition equaling 4 ~ 7 with pH etches, then cause the etch-rate of copper too low.For improving the residual phenomenon of molybdenum, see in etching solution and added fluoric-containing acid or add organo-alkali compound, but, fluoric-containing acid has corrodibility to silicon-containing layer and is unfavorable for processing procedure, part organo-alkali compound is as diethyl amino propylamine (Diethylaminopropylamine, DEAPA), then effect is unevident for propylene diamine, ammoniacal liquor, and even some organo-alkali compound can increase etching solution Jia Fanni current value and cause chamfering to produce, or reduces the solubleness of metal and cause the residual of small-particle.
In view of this, how to improve the composition of etching solution further, under the prerequisite not affecting silicon-containing layer, making etching solution be applicable to etch copper and molybdenum simultaneously and effectively can reduce metal residual, is the target that dealer makes great efforts.
Summary of the invention
An object of the present invention is to provide a kind of etchant, and it is applicable to cupric and the multiple layer metal film containing molybdenum simultaneously, and effectively can reduce metal residual, and then promotes etching performance.
An embodiment according to an aspect of of the present present invention is providing a kind of etchant, for etching cupric and the multilayer film containing molybdenum, be 100 weight percents based on etchant, etchant comprises hydrogen peroxide, the first organic acid or its esters, the second organic acid or its esters and alcohol amine compound.The chelating constant of the first organic acid and copper is greater than, equals 0 and be less than 6, and the first organic acid adding proportion is 5.5 weight percent to 17.5 weight percents.The chelating constant of the second organic acid and copper is greater than, equals 6 and be less than 18.5.Alcohol amine compound has more than one amido and more than one hydroxyl.
According to aforesaid etchant, the first organic acid can be formic acid, acetic acid, propionic acid, butyric acid, valeric acid, propanedioic acid, succinic acid, pentanedioic acid, hexanodioic acid, phenylformic acid, dehydroacetic acid (DHA), FUMARIC ACID TECH GRADE, toxilic acid, R-Glyceric acid, lactic acid, oxyacetic acid, oxysuccinic acid, trimethylacetic acid, pyruvic acid or tartrate.
According to aforesaid etchant, second organic acid can be citric acid, gluconic acid, nitrilotriacetic acid(NTA), glycine, iminodiethanoic acid, N, N-bis-(2-hydroxyethyl) glycine, N-(2-hydroxyethyl) iminodiethanoic acid (N-(2-hydroxyethyl) iminodiacetic acid, HIDA/EA), L-Ala, aspartic acid, halfcystine, gentisinic acid, L-glutamic acid, glycylglycine, NSC 206288, Histidine, leucine, tetra-sodium, Whitfield's ointment, sarkosine or α-amino-isovaleric acid.
According to aforesaid etchant, alcohol amine compound can be has at least one nitrogen-atoms, more than one hydroxyl and have the chain compound of 2 to 8 carbon atoms.Such as, alcohol amine compound can be trolamine, α-amino isopropyl alcohol, diglycolamine, isobutyl hydramine, diisopropanolamine (DIPA), 2-ethylamino ethanol or 2-methyl aminoethanol.
According to aforesaid etchant, can more comprise cyclic amine compound or derivatives thereof, such as, cyclic amine compound can be diazole (Diazole) or triazole (Triazole).
According to aforesaid etchant, more can comprise mineral acid, mineral acid gets rid of fluoric-containing acid, and such as, mineral acid can be sulfuric acid, phosphoric acid or nitric acid.
According to aforesaid etchant, can more comprise sulfocarbolic acid or derivatives thereof.
According to aforesaid etchant, be 100 weight percents based on etchant, etchant can comprise the hydrogen peroxide of 5.5 weight percent to 8.5 weight percents, first organic acid of 7 weight percent to 17 weight percents or its esters, second organic acid of 2 weight percent to 8 weight percents or its esters, the alcohol amine compound of 5 weight percent to 20 weight percents.Etchant more can comprise the water of 30 weight percent to 80.5 weight percents.In addition, the pH of etchant is 3 to 6.
An embodiment according to another aspect of the present invention is providing a kind of engraving method, comprise and use aforesaid etch combination etching cupric and the multilayer film containing molybdenum, wherein cupric and comprise at least one copper containing layer and at least one molybdenum-containing layer containing molybdenum multilayer film, and the thickness of copper containing layer is greater than the thickness of molybdenum-containing layer.
Accompanying drawing explanation
Figure 1A schemes in the SEM of low copper etching multilayer film gained according to the etchant of the embodiment of the present invention 1.
Figure 1B schemes in the SEM of high-copper etching multilayer film gained according to the etchant of the embodiment of the present invention 1.
Fig. 2 A is that the etchant of reference examples 2 ' is in the SEM figure of low copper etching multilayer film gained.
Fig. 2 B is that the etchant of reference examples 2 ' is in the SEM figure of high-copper etching multilayer film gained.
Fig. 3 is the SEM figure of the etchant etching multilayer film gained according to the embodiment of the present invention 1.
Fig. 4 is the SEM figure of the etchant etching multilayer film gained of reference examples 4 '.
Fig. 5 is the SEM figure of the etchant etching multilayer film gained of reference examples 2 '.
Fig. 6 is illustrated embodiments 1, the CD difference of embodiment 8 with embodiment 9 and the graph of a relation of copper ion concentration.
Embodiment
< etchant >
A kind of etchant, for etching cupric and the multilayer film containing molybdenum, specifically, can be used for the multilayer film such as etch copper/molybdenum, copper/molybdenum nitride, molybdenum/copper/molybdenum nitride, molybdenum nitride/copper/molybdenum nitride and molybdenum nitride/copper/molybdenum.
Etchant comprises hydrogen peroxide, first organic acid or its esters, second organic acid or its esters and alcohol amine compound, wherein, hydrogen peroxide, first organic acid or its esters and the second organic acid or its esters are in order to provide the etch capabilities to cupric and the multilayer film containing molybdenum, if only use the first organic acid or its esters, then there is poor (the critical dimension bias of CD, CD bias) too small disappearance, and when high-copper, cannot etch, or it is poor to etch CD, the present invention is by using the first organic acid or its esters and the second organic acid or its esters simultaneously, the CD that can reach 0.8um ~ 1.1um in mistake rate of etch (the Over etching rate) scope that reality produces line requirement is poor, and the etching that can maintain from low copper to high-copper shows.Alcohol amine compound can promote that the metal oxide layer be oxidized because of hydrogen peroxide dissolves, and contributes to the phenomenon improving metal residual (molybdenum is residual).
The pH of etchant is 3 to 6.
Be 100 weight percents based on etchant, the content of hydrogen peroxide can be 5.5 weight percent to 8.5 weight percents.When the content of hydrogen peroxide is less than 5.5 weight percents, then cannot etch.When the content of hydrogen peroxide is greater than 8.5 weight percents, then etch-rate can be reduced.
The chelating constant of aforementioned first organic acid and copper is greater than, equals 0 and be less than 6.Such as, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, propanedioic acid, succinic acid, pentanedioic acid, hexanodioic acid, phenylformic acid, dehydroacetic acid (DHA), FUMARIC ACID TECH GRADE, toxilic acid, R-Glyceric acid, lactic acid, oxyacetic acid, oxysuccinic acid, trimethylacetic acid, pyruvic acid or tartrate, aforesaid first organic acid can be used alone, or uses two or more simultaneously.In addition, the first organic acid or its esters only can use one, also can use two or more simultaneously.
Be 100 weight percents based on etchant, the content of the first organic acid or its esters is 5.5 weight percent to 17.5 weight percents, preferably, can be 7 weight percent to 17 weight percents.When the content of the first organic acid or its esters is less than 5.5 weight percents, cannot etch, though or can etch CD difference can be caused comparatively large, in addition, etchant declines to the surge capability of pH when high-copper, and affects etch-rate.When the content of the first organic acid or its esters is greater than 17.5 weight percents, then molybdenum is residual comparatively serious, and then the electrical properties of liquid-crystal display made by impact.
The chelating constant of aforementioned second organic acid and copper is greater than, equals 6 and be less than 18.5.Such as, citric acid, gluconic acid, nitrilotriacetic acid(NTA) (nitrilotriacetic acid, NTA), glycine (glycine), iminodiethanoic acid (iminodiacetic acid), N, N-bis-(2-hydroxyethyl) glycine (N, N-bis (2-hydroxyethyl) glycine, GA), N-(2-hydroxyethyl) iminodiethanoic acid (N-(2-hydroxyethyl) iminodiacetic acid, HIDA/EA), L-Ala, aspartic acid, halfcystine, gentisinic acid, L-glutamic acid, glycylglycine, NSC 206288, Histidine, leucine, tetra-sodium, Whitfield's ointment, sarkosine or α-amino-isovaleric acid, aforesaid second organic acid can be used alone, or use two or more simultaneously.In addition, the second organic acid or its esters only can use one, also can use two or more simultaneously.
Be 100 weight percents based on etchant, the content of the second organic acid or its esters can be 2 weight percent to 8 weight percents.When the content of the second organic acid or its esters is less than 2 weight percents, cannot etch, though or can etch molybdenum can be caused seriously residual, and then the electrical properties of liquid-crystal display made by impact.In addition, when low copper, be difficult to the standard of the CD difference reaching 0.8um ~ 1.1um within the scope of the mistake rate of etch required by reality product line, when high-copper, then cannot maintain etching performance, and have the problem of a large amount of heat release.When the content of the second organic acid or its esters is greater than 8 weight percents, cannot etch, though or can etch molybdenum can be caused seriously residual, and then the electrical properties of liquid-crystal display made by impact.
Aforementioned alcohol amine compound has more than one amido and more than one hydroxyl.In addition, alcohol amine compound can be the chain compound having at least one nitrogen-atoms Yu have 2 to 8 carbon atoms.Such as, trolamine, α-amino isopropyl alcohol, diglycolamine, isobutyl hydramine, diisopropanolamine (DIPA), 2-ethylamino ethanol or 2-methyl aminoethanol, aforesaid compound can be used alone, or uses two or more simultaneously.In other words, alcohol amine compound only can use one, also can use two or more simultaneously.
Be 100 weight percents based on etchant, the content of alcohol amine compound can be 5 weight percent to 20 weight percents.When the content of alcohol amine compound is less than 5 weight percents, cannot etch, though or can etch molybdenum can be caused seriously residual.When the content of alcohol amine compound is greater than 20 weight percents, will etch-rate be lowered, and then impact etching performance.
Etchant selectively comprises at least one additive, to promote its etching performance, such as, and cyclic amine compound or derivatives thereof, mineral acid or sulfocarbolic acid or derivatives thereof.Cyclic amine compound can be diazole (Diazole) or triazole (Triazole).Mineral acid gets rid of fluoric-containing acid, can be sulfuric acid, phosphoric acid or nitric acid.Aforementioned fluoric-containing acid refer to containing the fluorion that can dissociate and/or intangibility from the acid of fluorine atom, fluoric-containing acid can be but is not limited to hydrofluoric acid.
Etchant more can comprise water, and wherein the content of water is the water of 30 weight percent to 80.5 weight percents.Specifically, etchant is using water as solvent, and aforementioned water can be but is not limited to distilled water, deionized water, and is good with deionized water.In addition, the content of water can change with the content summation of other compositions in etchant, deposit in case at other compositions, adding water makes the content of etchant be 100 weight percents, in other words, the content summation of hydrogen peroxide, the first organic acid or its esters, the second organic acid or its esters, alcohol amine compound, additive and water is 100 weight percents.
" high-copper " in the present invention refers to that copper ion concentration is greater than 6000ppm." low copper " in the present invention refer to that copper ion concentration is greater than, equal 0 and be less than, equal 6000ppm.
< engraving method >
A kind of engraving method, comprises and uses aforesaid etch combination etching cupric and the multilayer film containing molybdenum, wherein cupric and comprise at least one copper containing layer and at least one molybdenum-containing layer containing molybdenum multilayer film, and the thickness of copper containing layer is greater than the thickness of molybdenum-containing layer.
According to above-mentioned embodiment, below proposition specific embodiment and reference examples are described in detail.
< embodiment and reference examples >
First, the etchant of embodiment 1 ~ 9 and the etchant of reference examples 1 ' ~ 5 ' is prepared.As shown in Table 1, as shown in Table 2, shown in the pH value table three of the etchant of reference examples 1 ' ~ 5 ', composition as shown in Table 4 for composition for the pH value of the etchant of embodiment 1 ~ 9.
Then, deposit on the glass substrate
layers of copper and
molybdenum layer, to form copper/molybdenum multilayer film, photoresistance is coated with on the glass substrate depositing multilayer film, and carry out exposing and develop to form light shield, again respectively with the etchant of embodiment 1 ~ 9, and the etchant of reference examples 1 ' ~ 5 ' etches at 30 DEG C ~ 35 DEG C, and assess respectively low copper and high-copper the metal rupture of membranes time (justetching time), etch that angle (taper), CD are poor, section shape and residual etc. the etching of bottom metal show, as shown in following table five A, following table five B and following table six.
In table five A, table five B and table six, the metal rupture of membranes time refers to and is started to be exposed to for the first time to glass substrate the time that etchant spends by etching.Total etching period (total etching time) refers to and is started to terminate to etching time of spending by etching, at this, assess that the etching angle of low copper and high-copper, CD are poor with identical total etching period, section shape and bottom metal residual.
It is sectional view after the glass substrate utilizing SEM to observe to deposit multilayer film etches via the etchant of embodiment 1 ~ 9 and the etchant of reference examples 1 ' ~ 5 ' respectively that etching angle, CD difference and section shape are assessed, the result of gained.Wherein, the measurement mode at etching angle, after being cut off by the glass substrate depositing multilayer film, measures the angle of the multilayer film section of gained section; Chamfering is then measure the angle that the bottom of multilayer film sections and glass substrate link, if be greater than 90 degree, is judged to be chamfering, if there is not chamfering, is then assessed as "○"; CD difference measures the horizontal throw of photoresistance end points to multilayer film bottom end point.For Figure 1A to Fig. 2 B, Figure 1A schemes in the SEM of low copper etching multilayer film gained according to the etchant of the embodiment of the present invention 1, Figure 1B schemes in the SEM of high-copper etching multilayer film gained according to the etchant of the embodiment of the present invention 1, Fig. 2 A is that the etchant of reference examples 2 ' is in the SEM figure of low copper etching multilayer film gained, Fig. 2 B is that the etchant of reference examples 2 ' is in the SEM figure of high-copper etching multilayer film gained, be can be observed the generation of chamfering by Fig. 2 B arrow, therefore be assessed as "×".
It is the situation that the multilayer film surface metal of glass substrate after etching utilizing SEM observation to deposit multilayer film remains that bottom metal remains assessment, if the region beyond photoresistance, without obviously residual, is assessed as "○", if the region beyond photoresistance is only slightly residual, be assessed as " △ ", if the region beyond photoresistance is residual serious, be assessed as "×".Illustrate with Fig. 3 to Fig. 5, Fig. 3 is the SEM figure of the etchant etching multilayer film gained according to the embodiment of the present invention 1, Fig. 4 is the SEM figure of the etchant etching multilayer film gained of reference examples 4 ', Fig. 5 is the SEM figure of the etchant etching multilayer film gained of reference examples 2 ', region wherein beyond Fig. 3 photoresistance is without obviously residual, therefore be assessed as "○", region beyond Fig. 4 photoresistance is only slightly residual, therefore be assessed as " △ ", region beyond Fig. 5 photoresistance is residual serious, therefore is assessed as, and is assessed as "×".The SEM figure of embodiment 2 ~ 9 is as Fig. 3, and the region beyond photoresistance without obviously residual, therefore is assessed as "○".The SEM figure of reference examples 3 ' is as Fig. 4, and the region beyond photoresistance is only slightly residual, therefore is assessed as " △ ".
Simultaneously with x-ray photoelectron spectroscopy (X-ray photoelectron spectroscopy, XPS) the residual situation of multilayer film surface metal is analyzed, show that the Mo atom content on the multilayer film surface of Fig. 3 is less than 2atom%, the Mo atom content on the multilayer film surface of Fig. 4 is greater than 3atom% and is less than 5atom%, the Mo atom content of the film surface of Fig. 5 is greater than 5atom%, and this analytical results can support the evaluation result of aforementioned SEM figure.
Please refer to lower list five A, table five B and table six, wherein table five A is the etching performance of embodiment 1 ~ 5, and table five B is the etching performance of embodiment 6 ~ 9, and table six is etching performances of reference examples 1 ' ~ 5 '.In table six, reference examples 1 ' and 5 ' cannot etch when low copper, the assessment such as therefore cannot carry out that follow-up total etching period, etching angle, CD are poor, section shape and bottom metal remain.
From table five A and table five B, use according to the etchant etching cupric of the embodiment of the present invention 1 ~ 9 and the multilayer film containing molybdenum, when low copper and high-copper, etch angle minimum be 23 degree, be 40 degree to the maximum, CD difference is minimum is 0.56um, be 1.09um to the maximum, all can conformance with standard, in addition, neither chamfering can be produced, and bottom metal remains assessment is all "○", obviously still can maintain etching performance when high-copper according to etchant of the present invention and there is longer work-ing life, and effectively can solve the problem of metal residual.
Please refer to Fig. 6, it is illustrated embodiments 1, the embodiment 8 CD difference with embodiment 9 and the graph of a relation of copper ion concentration, wherein puts up the best performance with the CD difference of embodiment 8 when high-copper.In addition, the gap that the CD difference of the low copper concentration of embodiment 1 and the gap of the CD difference of copper concentration are 0.47um, the CD of the low copper concentration of embodiment 8 is poor and the gap of the CD difference of copper concentration is 0.14, the CD of the low copper concentration of embodiment 9 difference is poor with the CD of copper concentration is 0.53um, and the gap that wherein CD that is low with embodiment 8, copper concentration is poor is less than 0.2um and puts up the best performance.The composition of comparing embodiment 1 and embodiment 8, the etchant of known embodiment 8, by interpolation sulfocarbolic acid, can promote the performance of etchant CD difference when high-copper.Another comparing embodiment 1 and embodiment 9, the etchant of embodiment 9 separately adds the hydrogen peroxide tranquilizer phenylurea commonly used, embodiment 1 and embodiment 9 etch show equal to each other, the etching performance that obvious etchant of the present invention does not need interpolation hydrogen peroxide tranquilizer just can reach excellent, meaning and etch combination of the present invention are by hydrogen peroxide, first organic acid or its esters, second organic acid or its esters and alcohol amine compound addition to each other, contribute to the stability promoting hydrogen peroxide, and it is good to produce aforementioned mentioned section shape, still can maintain etching performance when high-copper and effectively can alleviate the phenomenon of metal residual.
Although the present invention discloses as above with embodiment; so itself and be not used to limit the present invention, anyly have the knack of this those skilled in the art, without departing from the spirit and scope of the present invention; when being used for a variety of modifications and variations, therefore protection scope of the present invention is when being as the criterion depending on the accompanying claim person of defining.
Claims (15)
1. an etchant, for etching cupric and containing the multilayer film of molybdenum, be wherein 100 weight percents based on this etchant, this etchant comprises:
Hydrogen peroxide;
First organic acid or its esters, the chelating constant of this first organic acid and copper is greater than, equals 0 and be less than 6, and this first organic acid adding proportion is 5.5 weight percent to 17.5 weight percents;
Second organic acid or its esters, the chelating constant of this second organic acid and copper is greater than, equals 6 and be less than 18.5; And
Alcohol amine compound, this alcohol amine compound has more than one amido and more than one hydroxyl.
2. etchant as claimed in claim 1, wherein this first organic acid is formic acid, acetic acid, propionic acid, butyric acid, valeric acid, propanedioic acid, succinic acid, pentanedioic acid, hexanodioic acid, phenylformic acid, dehydroacetic acid (DHA), FUMARIC ACID TECH GRADE, toxilic acid, R-Glyceric acid, lactic acid, oxyacetic acid, oxysuccinic acid, trimethylacetic acid, pyruvic acid or tartrate.
3. etchant as claimed in claim 1, wherein this second organic acid is citric acid, gluconic acid, nitrilotriacetic acid(NTA), glycine, iminodiethanoic acid, N, N-bis-(2-hydroxyethyl) glycine, N-(2-hydroxyethyl) iminodiethanoic acid (N-(2-hydroxyethyl) iminodiacetic acid, HIDA/EA), L-Ala, aspartic acid, halfcystine, gentisinic acid, L-glutamic acid, glycylglycine, NSC 206288, Histidine, leucine, tetra-sodium, Whitfield's ointment, sarkosine or α-amino-isovaleric acid.
4. etchant as claimed in claim 1, wherein this alcohol amine compound is have at least one nitrogen-atoms, more than one hydroxyl and have the chain compound of 2 to 8 carbon atoms.
5. etchant as claimed in claim 4, wherein this alcohol amine compound is trolamine, α-amino isopropyl alcohol, diglycolamine, isobutyl hydramine, diisopropanolamine (DIPA), 2-ethylamino ethanol or 2-methyl aminoethanol.
6. etchant as claimed in claim 1, more comprises:
Cyclic amine compound or derivatives thereof.
7. etchant as claimed in claim 6, wherein this cyclic amine compound is diazole (Diazole) or triazole (Triazole).
8. etchant as claimed in claim 1, more comprises:
Mineral acid, this mineral acid gets rid of fluoric-containing acid.
9. etchant as claimed in claim 8, wherein this mineral acid is sulfuric acid, phosphoric acid or nitric acid.
10. etchant as claimed in claim 1, more comprises:
Sulfocarbolic acid or derivatives thereof.
11. etchants according to any one of claim 1 to 10, be wherein 100 weight percents based on this etchant, this etchant comprises:
This hydrogen peroxide of 5.5 weight percent to 8.5 weight percents;
This first organic acid or its esters of 7 weight percent to 17 weight percents;
This second organic acid or its esters of 2 weight percent to 8 weight percents; And
This alcohol amine compound of 5 weight percent to 20 weight percents.
12. etchants as claimed in claim 11, more comprise:
The water of 30 weight percent to 80.5 weight percents.
13. etchants according to any one of claim 1 to 10, wherein the pH of this etchant is 3 to 6.
14. 1 kinds of engraving methods, comprise:
The etch combination according to any one of claim 1 to 10 is used to etch this cupric and the multilayer film containing molybdenum, wherein this cupric and comprise at least one copper containing layer and at least one molybdenum-containing layer containing molybdenum multilayer film, and the thickness of this copper containing layer is greater than the thickness of this molybdenum-containing layer.
15. 1 kinds of engraving methods, comprise:
Use etch combination as claimed in claim 11 to etch this cupric and containing the multilayer film of molybdenum, wherein this cupric and comprise at least one copper containing layer and at least one molybdenum-containing layer containing molybdenum multilayer film, and the thickness of this copper containing layer is greater than the thickness of this molybdenum-containing layer.
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| TW102139792A TWI495763B (en) | 2013-11-01 | 2013-11-01 | Etchant composition and etching method |
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| CN112080747A (en) * | 2020-09-02 | 2020-12-15 | Tcl华星光电技术有限公司 | Etching solution composition for etching molybdenum/copper/molybdenum or molybdenum alloy/copper/molybdenum alloy three-layer metal wiring structure and application thereof |
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|---|---|
| TWI495763B (en) | 2015-08-11 |
| TW201518547A (en) | 2015-05-16 |
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