CN103282549A - Composition for etching metal films - Google Patents

Composition for etching metal films Download PDF

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CN103282549A
CN103282549A CN2011800471220A CN201180047122A CN103282549A CN 103282549 A CN103282549 A CN 103282549A CN 2011800471220 A CN2011800471220 A CN 2011800471220A CN 201180047122 A CN201180047122 A CN 201180047122A CN 103282549 A CN103282549 A CN 103282549A
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etching
acid
composition
metallic membrane
molybdenum
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CN103282549B (en
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张郁
朴种熙
金知燦
韩志贤
杨世仁
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OCI Holdings Co Ltd
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DC Chemical Co Ltd
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    • 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
    • C23F1/18—Acidic compositions for etching copper or alloys thereof
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
    • H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
    • H01L21/321—After treatment
    • H01L21/3213—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer
    • H01L21/32133—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only
    • H01L21/32134—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only by liquid etching only
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L29/00—Semiconductor devices specially adapted for rectifying, amplifying, oscillating or switching and having potential barriers; Capacitors or resistors having potential barriers, e.g. a PN-junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
    • H01L29/66—Types of semiconductor device ; Multistep manufacturing processes therefor
    • H01L29/66007—Multistep manufacturing processes
    • H01L29/66075—Multistep manufacturing processes of devices having semiconductor bodies comprising group 14 or group 13/15 materials
    • H01L29/66227—Multistep manufacturing processes of devices having semiconductor bodies comprising group 14 or group 13/15 materials the devices being controllable only by the electric current supplied or the electric potential applied, to an electrode which does not carry the current to be rectified, amplified or switched, e.g. three-terminal devices
    • H01L29/66409—Unipolar field-effect transistors
    • H01L29/66477—Unipolar field-effect transistors with an insulated gate, i.e. MISFET
    • H01L29/66742—Thin film unipolar transistors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L29/00—Semiconductor devices specially adapted for rectifying, amplifying, oscillating or switching and having potential barriers; Capacitors or resistors having potential barriers, e.g. a PN-junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
    • H01L29/40—Electrodes ; Multistep manufacturing processes therefor
    • H01L29/43—Electrodes ; Multistep manufacturing processes therefor characterised by the materials of which they are formed
    • H01L29/45—Ohmic electrodes
    • H01L29/456—Ohmic electrodes on silicon
    • H01L29/458—Ohmic electrodes on silicon for thin film silicon, e.g. source or drain electrode
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L29/00—Semiconductor devices specially adapted for rectifying, amplifying, oscillating or switching and having potential barriers; Capacitors or resistors having potential barriers, e.g. a PN-junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
    • H01L29/40—Electrodes ; Multistep manufacturing processes therefor
    • H01L29/43—Electrodes ; Multistep manufacturing processes therefor characterised by the materials of which they are formed
    • H01L29/49—Metal-insulator-semiconductor electrodes, e.g. gates of MOSFET
    • H01L29/4908—Metal-insulator-semiconductor electrodes, e.g. gates of MOSFET for thin film semiconductor, e.g. gate of TFT

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Abstract

The present invention relates to a composition for etching metal films, and more specifically, to an etchant composition comprising an oxidant, an etching controller, a chelating agent, an undercut inhibitor, a copper corrosion inhibitor, a residue remover and the balance of water, for collectively wet etching metal films used as a gate electrode and a data electrode within a thin film transistor for a flat display, particularly, a single-layered film or a multilayered film consisting of one or more materials selected from copper, molybdenum, titanium and a molybdenum-titanium alloy. The composition of the present invention inhibits the rapid reaction of an oxidant and a copper ion when applied to an etching process through the use of a novel chelating agent, thereby providing an etchant with excellent lifetime and stability, an etched metal film with a gentle slope angle, suitable control of CD loss, and a good etching profile inhibiting the residue of a lower molybdenum, titanium or molybdenum-titanium alloy film. In addition, if a volatilization inhibitor is further added, precipitate and foreign matter generation is greatly reduced in etching equipment, and thus it is possible to improve productivity with respect to etching equipment operation and to reduce failure rates.

Description

The composition that is used for etching sheet metal
Technical field
The present invention relates to a kind ofly be used for etching as the gate electrode of the thin film transistor of flat-panel monitor and the metallic membrane of data electrode by wet etching in batch, particularly comprise one or more the composition of single or multiple lift film that is selected from copper, molybdenum, titanium and molybdenum-titanium alloy.
Background technology
Thin film transistor obtains by forming metal wire at substrate.Generally speaking, form metallic membrane by physical adsorption, use photo-resist to pass through exposure and patterning and etching, the film of preparation patterning subsequently.In them, etching technics is a kind of wherein according to the technology of the pattern that forms in exposure technology with the metallic membrane selective etch.
Because the Thin Film Transistor-LCD that requirement has better performance, the therefore metallic membrane that need have low resistance for fast driving.In order to satisfy this requirement, use metallic substance for example copper and the silver-colored metal line that is used for thin film transistor.At present, copper is widely used in industrial application.Because pure copper is difficult to be deposited on the substrate, therefore at first deposit usually molybdenum, titanium or molybdenum-titanium alloy and then deposited copper to form multilayer film.When use comprises hydrogen peroxide and as the copper etching agent of main ingredient this multilayer film wet etching, because the difference of etch rate in copper, molybdenum and the titanium film, therefore obtain the etching form of difference usually.For example, the below that molybdenum or titanium the rest on the copper layer for example short circuit in resume module subsequently that may throw into question reduces productive rate thus.
For example in the open No.10-2006-0134380 of Korean Patent and Korean Patent Registration No.10-0839428, hydrofluoric acid is added etching agent to remove remaining molybdenum.But, because the hf etching glass substrate, so the thickness evenness of thin film transistor greatly damages.In order to address this problem, the open No.10-2007-0097922 of Korean Patent replaces hydrofluoric acid with fluoride salt, and it is the etching glass substrate less.
In the time will comprising the wet etching of one or more the single or multiple lift film that is selected from copper, molybdenum, titanium and molybdenum-titanium alloy, in etching agent, prepare various additives to overcome following problem: the etching homogeneity of the reduction of etch rate, entire substrate and pattern between the different metal layer, and the hyperreactive problem between cupric ion and the hydrogen peroxide, etc.
The open No.10-2004-0051502 of Korean Patent use organic acid for example oxyacetic acid as the etching control agent.Yet the film of etching shows precipitous cone angle, and the reactivity between cupric ion and the hydrogen peroxide can not reduce effectively.The open No.10-2006-0099089 of Korean Patent discloses a kind of etching agent, its comprise vitriol as etching control agent, phosphoric acid salt as sapping (undercut) inhibitor and acetoxyl sequestrant as sequestrant.Although it provides the excellent results of reacting between inhibition cupric ion and the hydrogen peroxide, deposition appears easily in venting port and the flushing unit of etching device, reduce productive rate thus.
Most of etching agents of having developed the film that is used for copper, molybdenum, titanium or molybdenum-titanium alloy are with the residue problems of the film that improves molybdenum, titanium or molybdenum-titanium alloy, by the etching form that obtains of etch rate of control copper, and reduce reaction between cupric ion and the hydrogen peroxide.Although realized the many improvement about resistates and stability problem, the deposition in the etching device remains problem.In addition, need guarantee that better stability is to improve productive rate.
Summary of the invention
Technical task
The present inventor has attempted developing for the metallic membrane of etching as the metal electrode of the thin film transistor of flat-panel monitor, particularly comprise one or more the etching agent composition of single or multiple lift film that is selected from copper, molybdenum, titanium and molybdenum-titanium alloy, described composition has the deposition and the foreign matter (moss) that reduce in molybdenum, titanium and the molybdenum-titanium alloy resistates of the reactivity that reduces between good etching form and characteristic, the homogeneity of guaranteeing, cupric ion and the hydrogen peroxide, minimizing and the etching device and forms.They have developed the composition that comprises oxygenant, etching control agent, sequestrant, sapping inhibitor (under-cut inhibition), copper etching inhibitor, residue remover and water, and the proof said composition can not need special processing and is used for etching and comprises one or more the single or multiple lift film that is selected from copper, molybdenum, titanium and molybdenum-titanium alloy.
Solve the scheme of problem
One total aspect, the invention provides a kind of composition for the etching metallic membrane, it comprises:
The oxygenant of 7-30wt%;
The etching control agent of 0.1-5wt%;
The sequestrant of 0.1-5wt%;
The sapping inhibitor of 0.01-3wt%;
The copper etching inhibitor of 0.01-5wt%;
The residue remover of 0.01-5wt%; With
The water of q.s is to the gross weight of 100wt%.
The invention effect
When be used for gate electrode and the data electrode of etching as the thin film transistor of flat-panel monitor, when comprising one or more the various single or multiple lift film substrate that is selected from copper, molybdenum, titanium and molybdenum-titanium alloy, composition for the etching metallic membrane of the present invention can provide good etching form and characteristic, and the homogeneity of guaranteeing.In addition, if further comprise evaporation suppressor, then can improve productive rate, because the foreign matter that forms in the etching device and deposition reduce.The copper max ionic concn that employing is higher than existing copper etching agent, composition of the present invention provide improved etching agent stability and have reduced cost, because can handle more metallic membrane substrate with it.In addition, adopt the cone angle lower than existing etching agent, be expected at that defective proportion will reduce in the technology of back.In addition, because the projection of bottom is controlled in the multilayer film that comprises copper, molybdenum, titanium and molybdenum-titanium alloy, therefore guarantee better etching form.In addition, even when thin film deposition processes middle level thickness changes, also can obtain good etching form.
The accompanying drawing summary
Fig. 1 represents the deposition that forms when the venting port that uses when having the existing etching agent of forming at etching device.
Fig. 2 represents and compares when using existing composition to be used for etching, and when using according to the etching agent that comprises evaporation suppressor of the present invention, deposition problems is significantly improved; With
Fig. 3 be expression use copper/molybdenum-titanium alloy multilayer film according to etching agent composition of the present invention (embodiment 12) etching (the copper layer:
Figure GDA00003446980400031
Alloy layer:
Figure GDA00003446980400032
) the electron photomicrograph of etching form.
Describe in detail
To explain the present invention hereinafter.
The invention provides a kind of composition for the etching metallic membrane, it comprises oxygenant, etching control agent, sequestrant, sapping inhibitor, copper etching inhibitor, residue remover and water.
Oxygenant makes the surface oxidation of copper film.Especially, can use hydrogen peroxide.It can 7-30wt% quantity be included in the composition.When content is lower than 7wt%, because the copper etch rate that reduces, so process efficiency may reduce.And when it surpassed 30wt%, because the stability of cupric ion difference, therefore the number of the glass of processing may be limited.
The etching control agent makes the oxidized surface ionization of copper film, so that cupric ion separates from film surface.Especially, can use organic acid.The organic acid object lesson can comprise that one or more have the acid of one or more carboxyls, for example acetic acid, citric acid, oxalic acid, toxilic acid, oxyacetic acid, Succinic Acid, tartrate, fumaric acid, Whitfield's ointment, oxysuccinic acid, trimethylacetic acid etc.Particularly, the quantity that the etching control agent can 0.1-5wt% is included in the composition.When the content of etching control agent was lower than 0.1wt%, etch rate may reduce.And when it surpassed 5wt%, (CD) loss of etching form-critical size and cone angle may be unsatisfactory.
Sequestrant makes the cupric ion chelating that is dissolved in the etching agent, protects cupric ion thus and avoids with oxidant reaction and improve oxygenant and the stability of etching agent.It has improved with the glass number of etching agent processing and by preventing that hydrogen peroxide from decomposing fast and has improved security.Generally speaking, can use sequestrant, the sequestrant based on phosphonic acids, amino acid based on acetic acid, or their mixture.More specifically, example based on the sequestrant of acetic acid can comprise complexon I (NTA), iminodiethanoic acid (IDA), methyliminodiacetic acid (MIDA), hydroxyethyliminodiacetic acid (HIDA), diethylene triaminepentaacetic acid(DTPA) (DPTA), ethylenediamine tetraacetic acid (EDTA) (EDTA), N-hydroxyethyl ethylenediamine tetraacetic acid (EDTA) (HEDTA), methylethylenediaminetetraacetic acid (MEDTA), triethylenetetraaminehexaacetic acid (TTHA) etc., example based on the sequestrant of phosphonic acids can comprise ethylenediamine tetramethylene phosphonic acid (EDTPA), diethylenetriamine pentamethylenophosphonic acid(DTPP) (DTPMPA), hydroxy ethylene diphosphonic acid (HEDP), Amino Trimethylene Phosphonic Acid (ATMP) etc., and amino acid whose example can comprise glycine, arginine, L-glutamic acid, L-Ala, halfcystine, glutamine, glyphosate and Padil (glycylic acid) etc.Particularly, the quantity that sequestrant can 0.1-5wt% is included in the composition for the etching metallic membrane.When the content of sequestrant is lower than 0.1wt%, because the overreaction between oxygenant and the cupric ion, so stability may reduce.And when it surpassed 5wt%, etching form-CD loss and cone angle may be unsatisfactory.
The sapping inhibitor is regulated the redox-potential of metal, prevents local store battery reaction thus and guarantees uniform etch rate in the metal level of the multilayer film that comprises copper, molybdenum, titanium etc.In the present invention, can use inorganic phosphate and organic acid ammonium salt as the sapping inhibitor.In existing etching agent, mainly use inorganic phosphate, but they often cause in etching device by being combined based on organic additive with other foreign matter to form.In the present invention, by organic acid ammonium salt is used with inorganic phosphate, can significantly reduce foreign matter and form.Inorganic phosphate can be to be selected from one or more of ammonium phosphate, ammonium hydrogen phosphate, primary ammonium phosphate, sodium phosphate, sodium hydrogen phosphate and SODIUM PHOSPHATE, MONOBASIC, and organic acid ammonium salt can be to be selected from one or more of ammonium acetate, halogenated acetic acids ammonium and ammonium citrate.Particularly, the weight ratio of inorganic phosphate and organic acid ammonium salt can be 1:0.25-2.If the part by weight of organic acid ammonium salt is too small, then in etching device, may form foreign matter.On the contrary, if excessive, owing to the CD loss reduces, so the etching form may be unsatisfactory.The content of sapping inhibitor can be 0.01-3wt% in the composition.If the content of sapping inhibitor is too small, then in molybdenum, titanium or molybdenum-titanium layer sapping may appear.On the contrary, if surpass 3wt%, then be difficult to the etching form that obtains to wish.
Copper etching inhibitor is used for the etch rate of control copper, and this etch rate is faster than molybdenum and titanium, to obtain good etching form.Generally speaking, can use heterocyclic amine.Particularly, can use amino tetrazole, imidazoles, indoles, purine, pyrazoles, pyridine, pyrimidine, pyrroles, tetramethyleneimine, tetramethyleneimine, benzotriazole or their mixture.Copper etching inhibitor can 0.01-5wt% amount be included in the composition.If content is too small, then owing to the copper etch rate that improves, therefore the etching form may be unsatisfactory in multilayer film.On the contrary, if surpass 5wt%, then owing to the etch rate that reduces, so productive rate may reduce.
Residue remover is removed molybdenum, titanium and molybdenum-titanium alloy resistates.Can use inorganic fluoride as residue remover.Particularly, can use one or more that are selected from Neutral ammonium fluoride, ammonium bifluoride, Sodium Fluoride, Potassium monofluoride, ammonium bifluoride, sodium bifluoride and potassium hydrogen fluoride.Residue remover can 0.01-5wt% quantity be included in composition for the etching metallic membrane.If content is lower than 0.01wt%, then resistates of molybdenum etc. may keep.On the contrary, if surpass 5wt%, then layer and following glass substrate may be etched.
If necessary, the composition for the etching metallic membrane according to the present invention can further comprise evaporation suppressor.Evaporation suppressor has suppressed the evaporation of etching agent, keeps the solvability of the deposition that obtained by etching thus, therefore reduces deposition.By adding evaporation suppressor, near the deposition the venting port of etching device can significantly reduce.Evaporation suppressor can be the polyvalent alcohol with two or more hydroxyls.For example, can make spent glycol, propylene glycol, polyoxyethylene glycol or their mixture.Evaporation suppressor can 0.1-7wt% quantity add.If addition is lower than 0.1wt%, may not fully suppress the evaporation of etching agent.On the contrary, even addition surpasses 7wt%, its effect may be also not obvious.Therefore, preferably keep above-mentioned scope.
Except said components, can also add the water of sufficient amount to the gross weight of 100wt%, to obtain the composition for the etching metallic membrane of the present invention.
When being used for etching and comprising one or more the single or multiple lift that is selected from copper, molybdenum, titanium and molybdenum-titanium alloy, good etching form can be provided etching agent composition of the present invention and foreign matter forms and deposition improves productive rate by reducing.In addition, compare with conventional etching agent, can guarantee lower cone angle.
Now embodiment and experiment will be described.Following examples and experiment only are used for illustration purpose and are not intended to restriction the scope of the present disclosure.
Embodiment
Embodiment 1-18 and comparative example 1-2
Preparation comprises the composition that is used for etching of oxygenant, etching control agent, sequestrant, sapping inhibitor, copper etching inhibitor, residue remover and water.Details about component and composition provides in table 1.
Table 1
Figure GDA00003446980400061
Figure GDA00003446980400071
The evaluation of etching performance
In order to test the performance according to etching agent composition of the present invention, the double-deck substrate of preparation copper/molybdenum-titanium alloy.Molybdenum-titanium alloy has the 1:1 weight ratio.By as the sputter in the LCD glass substrate manufacturing process copper and molybdenum-titanium alloy being deposited on the substrate.The copper layer deposits with two kinds of different thickness with molybdenum-titanium alloy layer.Thickness is respectively copper
Figure GDA00003446980400072
/ molybdenum-titanium
Figure GDA00003446980400073
And copper
Figure GDA00003446980400076
Molybdenum-titanium
With the heating in the wet etching device (Etcher (TFT), KC Tech) of ejection-type of each etching agent among embodiment 1-18 and the comparative example 1-2, and be accompanied by the double-deck substrate of the temperature etching that remains on 33 ± 0.5 ℃.For each layer, substrate exceeds end point determination (EPD) 60% overetch (O/E).When etching finished, substrate cleaned and uses the drying machine drying with ultrapure water.After using the photo-resist stripper to remove photo-resist, use scanning electronic microscope (SEM; NOVA-200 Phillips) estimates cone angle, critical size (CD) loss, etch residue etc.In addition, in order to study the stability of etching agent, when increasing copper ion concentration, measure in the stable copper max ionic concn of etching agent maintenance.
Table 2
Figure GDA00003446980400081
For copper/molybdenum-titanium alloy (
Figure GDA00003446980400082
Thickness) double-deck substrate, table 2 will be according to the etching performance of the composition for etching of the present invention and the existing composition that is used for etching relatively, and composition according to the present invention comprises oxygenant, etching control agent, sequestrant, sapping inhibitor, copper etching inhibitor, residue remover and water.Reveal approximately 4 although be used for the existing compositions table of etching, the copper max ionic concn of 000ppm, compositions table of the present invention reveal the copper max ionic concn that surpasses 6,000ppm, do not observe foreign matter or deposition in etching device.That is to say that compare with existing etching agent, compositions table of the present invention reveals the stability of improvement.And when comparing with existing etching agent, it shows similar CD loss, cone angle and resistates.
Table 3
Table 3 show for copper/molybdenum-titanium alloy ( Thickness) double-deck substrate further comprises the etching performance according to etching agent composition of the present invention of evaporation suppressor.It shows the copper max ionic concn that surpasses 6,000ppm, does not observe foreign matter or deposition in etching device.When the result with the comparative example 1-2 shown in the table 2 compares, because cone angle is low at least 5 °, therefore can more easily carry out thin film deposition and the Patternized technique of back.
Table 4
Figure GDA00003446980400093
Table 4 shows the etching performance of the alloy layer thickness that depends on copper/molybdenum-titanium alloy duplicature.Generally speaking, because different electron transfer rate in the multilayer film, so the variation in thickness of copper layer and following alloy layer causes the performance of etching control agent deterioration, causes residue problems thus in alloy layer.Yet the compositions table for etching according to the present invention reveals good etching form, does not have resistates or projection in alloy layer.Therefore, will be big advantage for the technology robustness, even because it also shows good etching form when layer thickness changes.
Claims (according to the modification of the 19th of treaty)
1. composition that is used for the etching metallic membrane, it comprises:
The oxygenant of 7-30wt%;
The etching control agent of 0.1-5wt%;
The sequestrant of 0.1-5wt%;
The sapping inhibitor of 0.01-3wt%;
The copper etching inhibitor of 0.01-5wt%;
The residue remover of 0.01-5wt%;
The evaporation suppressor of 0.1-7wt%; With
The water of q.s is to the gross weight of 100wt%.
2. according to the composition that is used for the etching metallic membrane of claim 1, wherein oxygenant is hydrogen peroxide.
3. according to the composition that is used for the etching metallic membrane of claim 1, wherein the etching control agent is to be selected from following one or more: acetic acid, citric acid, oxalic acid, toxilic acid, oxyacetic acid, Succinic Acid, tartrate, fumaric acid, Whitfield's ointment, oxysuccinic acid and trimethylacetic acid.
4. according to the composition that is used for the etching metallic membrane of claim 1, wherein sequestrant is to be selected from following one or more: complexon I, iminodiethanoic acid, methyliminodiacetic acid, the hydroxyethyl iminodiethanoic acid, diethylene triaminepentaacetic acid(DTPA), ethylenediamine tetraacetic acid (EDTA), N-hydroxyethyl ethylenediamine tetraacetic acid (EDTA), methylethylenediaminetetraacetic acid, triethylenetetraaminehexaacetic acid, ethylenediamine tetramethylene phosphonic acid, diethylenetriamine pentamethylenophosphonic acid(DTPP), 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid, Amino Trimethylene Phosphonic Acid, glycerine, arginine, L-glutamic acid, L-Ala, halfcystine, glutamine, glyphosate and Padil.
5. according to the composition that is used for the etching metallic membrane of claim 1, wherein the sapping inhibitor is one or more the inorganic phosphate that is selected from ammonium phosphate, ammonium hydrogen phosphate, primary ammonium phosphate, sodium phosphate, sodium hydrogen phosphate and SODIUM PHOSPHATE, MONOBASIC, and one or more the organic acid ammonium salt that is selected from ammonium acetate and ammonium citrate.
6. according to the composition that is used for the etching metallic membrane of claim 5, wherein the weight ratio of inorganic phosphate and organic acid ammonium salt is 1:0.25-2.
7. according to the composition that is used for the etching metallic membrane of claim 1, wherein copper etching inhibitor is amino tetrazole, imidazoles, indoles, purine, pyrazoles, pyridine, pyrimidine, pyrroles, tetramethyleneimine, tetramethyleneimine, benzotriazole or their mixture.
8. according to the composition that is used for the etching metallic membrane of claim 1, wherein residue remover is to be selected from following one or more: Neutral ammonium fluoride, ammonium bifluoride, Sodium Fluoride, Potassium monofluoride, ammonium bifluoride, sodium bifluoride and potassium hydrogen fluoride.
9. according to the composition that is used for the etching metallic membrane of claim 1, wherein evaporation suppressor is ethylene glycol, propylene glycol, polyoxyethylene glycol or their mixture.
10. according to each the composition that is used for the etching metallic membrane of claim 1-9, wherein metallic membrane is to comprise one or more the single or multiple lift that is selected from copper, molybdenum, titanium and molybdenum-titanium alloy.

Claims (11)

1. composition that is used for the etching metallic membrane, it comprises:
The oxygenant of 7-30wt%;
The etching control agent of 0.1-5wt%;
The sequestrant of 0.1-5wt%;
The sapping inhibitor of 0.01-3wt%;
The copper etching inhibitor of 0.01-5wt%;
The residue remover of 0.01-5wt%; With
The water of q.s is to the gross weight of 100wt%.
2. according to the composition that is used for the etching metallic membrane of claim 1, wherein oxygenant is hydrogen peroxide.
3. according to the composition that is used for the etching metallic membrane of claim 1, wherein the etching control agent is to be selected from following one or more: acetic acid, citric acid, oxalic acid, toxilic acid, oxyacetic acid, Succinic Acid, tartrate, fumaric acid, Whitfield's ointment, oxysuccinic acid and trimethylacetic acid.
4. according to the composition that is used for the etching metallic membrane of claim 1, wherein sequestrant is to be selected from following one or more: complexon I, iminodiethanoic acid, methyliminodiacetic acid, the hydroxyethyl iminodiethanoic acid, diethylene triaminepentaacetic acid(DTPA), ethylenediamine tetraacetic acid (EDTA), N-hydroxyethyl ethylenediamine tetraacetic acid (EDTA), methylethylenediaminetetraacetic acid, triethylenetetraaminehexaacetic acid, ethylenediamine tetramethylene phosphonic acid, diethylenetriamine pentamethylenophosphonic acid(DTPP), 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid, Amino Trimethylene Phosphonic Acid, glycerine, arginine, L-glutamic acid, L-Ala, halfcystine, glutamine, glyphosate and Padil.
5. according to the composition that is used for the etching metallic membrane of claim 1, wherein the sapping inhibitor is one or more inorganic phosphates that are selected from ammonium phosphate, ammonium hydrogen phosphate, primary ammonium phosphate, sodium phosphate, sodium hydrogen phosphate and SODIUM PHOSPHATE, MONOBASIC, and one or more organic acid ammonium salts that are selected from ammonium acetate, halogenated acetic acids ammonium and ammonium citrate.
6. according to the composition that is used for the etching metallic membrane of claim 5, wherein the weight ratio of inorganic phosphate and organic acid ammonium salt is 1:0.25-2.
7. according to the composition that is used for the etching metallic membrane of claim 1, wherein copper etching inhibitor is amino tetrazole, imidazoles, indoles, purine, pyrazoles, pyridine, pyrimidine, pyrroles, tetramethyleneimine, tetramethyleneimine, benzotriazole or their mixture.
8. according to the composition that is used for the etching metallic membrane of claim 1, wherein residue remover is to be selected from following one or more: Neutral ammonium fluoride, ammonium bifluoride, Sodium Fluoride, Potassium monofluoride, ammonium bifluoride, sodium bifluoride and potassium hydrogen fluoride.
9. according to the composition that is used for the etching metallic membrane of claim 1, it further comprises the evaporation suppressor of 0.1-7wt%.
10. according to the composition that is used for the etching metallic membrane of claim 9, wherein evaporation suppressor is ethylene glycol, propylene glycol, polyoxyethylene glycol or their mixture.
11. according to each the composition that is used for the etching metallic membrane of claim 1-10, wherein metallic membrane is to comprise one or more the single or multiple lift that is selected from copper, molybdenum, titanium and molybdenum-titanium alloy.
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