CN103635608A - Metal wiring etching solution and method for manufacturing liquid crystal display device using same - Google Patents
Metal wiring etching solution and method for manufacturing liquid crystal display device using same Download PDFInfo
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- CN103635608A CN103635608A CN201280030638.9A CN201280030638A CN103635608A CN 103635608 A CN103635608 A CN 103635608A CN 201280030638 A CN201280030638 A CN 201280030638A CN 103635608 A CN103635608 A CN 103635608A
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- 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 at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System 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
-
- 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
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K13/00—Etching, surface-brightening or pickling compositions
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K13/00—Etching, surface-brightening or pickling compositions
- C09K13/04—Etching, surface-brightening or pickling compositions containing an inorganic acid
- C09K13/10—Etching, surface-brightening or pickling compositions containing an inorganic acid containing a boron compound
-
- 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
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- 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 at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System 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
- H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
- H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
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- 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 at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System 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
- H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
- H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
- H01L21/308—Chemical or electrical treatment, e.g. electrolytic etching using masks
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
- H01L27/02—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having at least one potential-jump barrier or surface barrier; including integrated passive circuit elements with at least one potential-jump barrier or surface barrier
- H01L27/12—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having at least one potential-jump barrier or surface barrier; including integrated passive circuit elements with at least one potential-jump barrier or surface barrier the substrate being other than a semiconductor body, e.g. an insulating body
- H01L27/1214—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having at least one potential-jump barrier or surface barrier; including integrated passive circuit elements with at least one potential-jump barrier or surface barrier the substrate being other than a semiconductor body, e.g. an insulating body comprising a plurality of TFTs formed on a non-semiconducting substrate, e.g. driving circuits for AMLCDs
- H01L27/124—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having at least one potential-jump barrier or surface barrier; including integrated passive circuit elements with at least one potential-jump barrier or surface barrier the substrate being other than a semiconductor body, e.g. an insulating body comprising a plurality of TFTs formed on a non-semiconducting substrate, e.g. driving circuits for AMLCDs with a particular composition, shape or layout of the wiring layers specially adapted to the circuit arrangement, e.g. scanning lines in LCD pixel circuits
Abstract
The invention discloses a copper-containing metal film etchant composition for a semiconductor device and an etching method using the same. The metal film etching solution composition of the present invention comprises fluoroboric acid or fluoroboric acid and at least one fluorine-containing compound. The etching method of a metal film containing copper using the etchant composition according to the present invention can etch a copper-containing multilayer metal film together without damaging a lower glass substrate during etching, thereby improving the production yield of a semiconductor device. The etchant composition and the etching method using the same according to the present invention can prevent Open circuit (Data Open) defects due to delamination and erosion without using sulfate, and can solve the problem of deposition with metal salts and can achieve a fine pattern by etching without using an organic acid.
Description
Technical field
The present invention relates to for etching comprise copper that the semiconductor device of liquid crystal indicator uses etc. metal wiring etchant and utilize its engraving method.
Background technology
In semiconductor device, the process that forms metal wiring on substrate conventionally by the metallic membrane by sputter etc. form operation, the photoresist material at selective area that is coated with, exposes and developed by photoresist material forms operation and etching work procedure forms.In semiconductor device, the resistance of metal wiring is the principal element of bringing out capacitance-resistance (RC) signal delay.Be used for arranging the etching work procedure of circuit layout (circuit line), liquid-crystal display (liquid crystal display to the display unit as being attracted attention recently, LCD) install and widely used TFT-LCD (Thin Film Transistor Liquid Crystal Display, Thin Film Transistor-LCD) manufacture, demonstrates accurate, distinct image extremely important.In the situation of TFT-LCD, increase panel size and realize the main direction that high resolving power is becoming technological development.
In operation for the manufacture of the conventional art of TFT-LCD substrate, grid and source/drain electrode wiring material as TFT, often used aluminum or aluminum alloy layer, and particularly, aluminium-molybdenum alloy is used morely., for the maximization of TFT-LCD, must reduce RC signal delay, for this reason, have the copper as low resistive metal is used to form to attempting of distribution.But, with regard to utilize the operation of copper film in order to form distribution for, at coating photoresist material and carry out there are many difficulties in the operation of patterning, the problem that exists the clinging power with silicon insulating film to decline.
In order to make up this shortcoming of copper film, use metallized multilayer film, typically, used the metallized multilayer film of copper and titanium, copper and molybdenum.With regard to copper film/titanium film, due to the chemical property of titanium, cannot etched shortcoming thereby there is if there is no fluorion.But, if comprise fluorion in etching solution, the fluorion particularly occurring in the etching solution that comprises hydrofluoric acid (HF), glass substrate and various silicon layer (passivation layer being comprised of with silicon nitride film semiconductor layer) are etched together with also, thereby exist, in manufacturing process, bad worry may occur.On the other hand, with regard to copper film/molybdenum film, if regulate well the thickness of copper and molybdenum film, can make the film with or better character similar with copper film/titanium film, favourable from this aspect that does not need to comprise fluorion etching solution.On the other hand, in order to eliminate the problem of copper film/titanium film and copper film/molybdenum film, also there is the situation as metal wiring by copper film/titanium-molybdenum film.In this case, owing to being difficult to avoid the etching speed of each metal to occur difference, thus in the angle of Working Procedure Controlling, important is not only optionally etch copper or copper alloy layer, but can realize the etching in the lump of real multilayer film.
In addition, with regard to the etching solution of the metallic membrane that comprises copper, etch copper or copper and other metal are inadequate merely, also will have etching face necessity smoothly, make not occur electric short circuit.Owing to being placed with many thin film layers on TFT substrate, thereby if prevent from occurring undesirable electric short circuit between them, the shape of blocking side of preferred etched metal level,, etching section (profile) tilts equably, and below is wider than top, be taper (taper) shape of releiving.This is because if etching section is the conical in shape of releiving, and the staggered floor between the multi-layer thin rete forming reduces.In fact, in inhomogeneous, the inexact situation of the etched pattern of grid metal film, the resolving power that TFT-LCD image occurs declines, true problem is off color.And, after etching, the surface of etched copper or other metallic membrane should not have the small embossment that is called as resistates (residue), its surface should be smooth.
Summary of the invention
Technical problem
One of technical problem of the present invention is to provide a kind ofly can not damage glass substrate, in the lump the copper-containing metal film etchant of etching copper-containing metal multilayer film.
Another technical problem of the present invention is to provide a kind of engraving method that utilizes this etchant.
The technical scheme of dealing with problems
In one aspect of the invention, provide a kind of etchant of copper-containing metal film, take composition all wts as benchmark, comprise: hydrogen peroxide 5.0 to 30 % by weight; Phosphoric acid 0.1 to 7.0 % by weight; Oxidation promoter 0.1 to 3.0 % by weight that comprises potassium ion; Azole compounds 0.1 to 3.0 % by weight; Fluoroboric acid (HBF
4) separately or composition 0.11 to 2.0 % by weight of fluoroboric acid and at least one other fluorochemicals; And the water of surplus.
In another aspect of the present invention, a kind of copper-containing metal film engraving method is provided, comprising: the step that forms copper-containing metal film on substrate; On above-mentioned copper-containing metal film, form the step of photoetching agent pattern; And by the step of the above-mentioned copper-containing metal film of above-mentioned etchant etching.
Beneficial effect
According to the etchant of one aspect of the invention, can not damage glass substrate, etching comprises the multilayer film of the various metals of copper in the lump, thereby can make glass substrate recycling.And with regard to regard to the etchant of one aspect of the invention, lower film is in the situation of molybdenum or molybdenum alloy, when etching owing to not staying molybdenum resistates, thereby form the outstanding etching face of taper.And then, according to the etchant of one aspect of the invention, can prevent that critical size (critical dimension, CD) from reducing when side etching (side etch), thereby the distribution that can also be used in fine pattern forms.In addition, if use the engraving method etching copper-containing metal film according to one aspect of the invention, can increase the accumulated process sheet number of same etch liquid, thereby increase the production yield of semiconductor device.
Accompanying drawing explanation
Fig. 1 shows according to one embodiment of the present invention, the metal multilayer film consisting of is carried out to the schematic diagram of etched operation the single film of copper and the single film of titanium-molybdenum alloy.
Fig. 2 is about according to the electron scanning micrograph of the thin film transistor of the etching work procedure of embodiment 1 and Production Example 1.
Fig. 3 is about according to the electron scanning micrograph of the thin film transistor of the etching work procedure of embodiment 2 and Production Example 2.
Fig. 4 is about according to the electron scanning micrograph of the thin film transistor of the etching work procedure of embodiment 3 and Production Example 3.
Fig. 5 is about according to the electron scanning micrograph of the thin film transistor of the etching work procedure of embodiment 4 and Production Example 4.
Fig. 6 is about according to the electron scanning micrograph of the thin film transistor of the etching work procedure of comparative example 1 and Production Example 5.
Fig. 7 is about according to the electron scanning micrograph of the thin film transistor of the etching work procedure of comparative example 2 and Production Example 6.
Preferred forms
Below to etchant of the present invention and utilize its engraving method to be elaborated.
In one aspect of the invention, provide a kind of etchant for etching copper-containing metal film.In embodiment more specifically of the present invention, this copper-containing metal film is used to form the circuit layout of liquid crystal indicator.
Wherein, so-called copper-containing metal film is metal single layer film or the two-layer above multilayer film that contains copper.For example, this copper-containing metal film can be the unitary film being comprised of copper or copper alloy that comprises copper.On the other hand, this copper-containing metal film can be following multilayer film,, except the layer being comprised of copper or copper alloy, also further comprises the layer that for example contains other metallic membrane of any one above metal in molybdenum and titanium.
Although be not particularly limited, in one embodiment of the present invention of etching multilayer film, above-mentioned copper film or tin-copper alloy film WU are upper membrane, other metallic membrane, and for example, molybdenum film is lower film.In another embodiment of the invention, other metallic membrane is upper membrane, and copper or tin-copper alloy film WU are lower film.In addition, in another kind of embodiment of the present invention, comprise the multilayer film of a kind of above film in alternately configured copper film and molybdenum and titanium.Now, can consider the structure that the material category of the film that is disposed at bottom or top or connectivity etc. decide multilayer film.In addition, in copper film and molybdenum and titanium, the thickness of a kind of above film can be the indefinite various combination in ground, but preferably copper film thickness forms thicklyer than the thickness of a kind of above film in molybdenum and titanium.On the other hand, form in the embodiment of a film at molybdenum together with titanium, these two kinds of metals can exist with alloy morphology.
Etchant of the present invention is to contain hydrogen peroxide, phosphoric acid (H
3pO
4), the oxidation promoter, azole compounds and the fluoroboric acid (HBF that comprise potassium ion
4) or the aqueous solution of other fluorochemicals of fluoroboric acid and non-fluoroboric acid.
In one embodiment of the invention, this etchant be take composition all wts as benchmark, comprises: hydrogen peroxide 5.0 to 30 % by weight, phosphoric acid 0.1 to 7.0 % by weight, oxidation promoter 0.1 to 3.0 % by weight that comprises potassium ion, azole compounds 0.1 to 3.0 % by weight, fluoroboric acid are separately or composition 0.11 to 2.0 % by weight of fluoroboric acid and at least one fluorochemicals and the water of surplus.
Hydrogen peroxide, the phosphoric acid of etchant, the oxidation promoter that comprises potassium ion, the azole compounds of being contained in of the present invention, can be manufactured by generally well-known method, preferably has the purity that semiconductor process is used.In addition, with regard to water, the deionized water that can use semiconductor process to use.In addition, with regard to fluoroboric acid, can buy and there is semiconductor process and use by the commercial articles of the aqueous solution state of purity, or directly manufacture and use.
The hydrogen peroxide that is contained in etchant of the present invention is the oxygenant as copper or tin-copper alloy film WU and other metallic membrane, is the main composition of etching metal film.In the specific embodiment of the present invention, preferably, can use metallic impurity for the hydrogen peroxide of ppb semiconductor process use purity below horizontal.
In a kind of embodiment of etchant of the present invention, it is benchmark that the content of hydrogen peroxide be take whole etchant weight, accounts for 5.0 to 30 % by weight.In embodiment more specifically of the present invention, the content of hydrogen peroxide accounts for 10 to 25 % by weight.If the content of hydrogen peroxide, within the scope of this, can reach the stability of etchant and etching rapidly and smoothly simultaneously.If the content of hydrogen peroxide surpasses 30 % by weight, in etching solution, have in the situation of metal ion, due to its catalyst action, there is the danger of blasting, if lower than 5.0 % by weight, metallic membrane cannot be by etching swimmingly, thereby metallic membrane is remaining as resistates, or the etching speed of copper metallic membrane significantly declines, be therefore difficult to etching solution to be applied to operation.
In etchant of the present invention, phosphoric acid, as the main composition of other metallic membranes such as etching together with hydrogen peroxide and molybdenum film, preferably, can be used to make to have the purity that semiconductor process is used, and metallic impurity are that ppb is below horizontal.
In etchant of the present invention, it is benchmark that phosphoric acid be take whole etchant weight, uses 0.1 to 7.0 % by weight.In concrete a kind of embodiment of the present invention, the content of phosphoric acid is 2 to 5 % by weight.Phosphoric acid regulates the pH of etching solution, makes the metallic membrane that can etching comprises copper.
If use phosphoric acid with aforementioned range, can maintain swimmingly the etching of copper film on one side, Yi Bian prevent from forming the resistates of copper film and copper-containing metal film.If the scope with above-mentioned content is used phosphoric acid, can be 1.5 to 2.5 the pH regulator of etching solution.In this pH scope, the etching speed of copper film is smooth and easy, thereby control etching work procedure, becomes easy.In addition, if use phosphoric acid, phosphate ion is combined with oxidized cupric ion and is formed phosphoric acid salt, thereby increases the solvability to water, thereby after etching, eliminates the resistates of copper-containing metal film.But, if higher than aforesaid higher limit, may there is the over etching of copper-containing metal film because of phosphoric acid in the content of phosphoric acid, if the content of phosphoric acid lower than aforesaid lower value, the etching speed of copper-containing metal film may decline.
In etchant of the present invention, the oxidation promoter that comprises potassium ion is born the effect that helps hydrogen peroxide to improve etching speed.In concrete a kind of embodiment of the present invention, the above-mentioned oxidation promoter that comprises potassium ion is saltpetre.In above-mentioned concrete embodiment, the effect that saltpetre is carried out is to become potassium ion (K at etching solution internal disintegration
+) and nitrate ion (NO
3 -), thereby with the electronics that speed is accepted metal multilayer film surface rapidly, reduce, therefore make etching reaction enliven and carry out.
In the present invention, the content of the oxidation promoter that comprises potassium ion, take whole composition weights as benchmark, accounts for 0.1 to 3.0 % by weight.In the situation that the content of the above-mentioned oxidation promoter that comprises potassium ion is within the scope of this, not only improve etching speed, and the composition of stabilization etching solution, thereby can carry out long etching with the etching solution of batch, therefore there is the effect of the treatment capacity (throughput) that increases the unit time.In addition, in above-mentioned scope, the amount that can add and subtract oxidation promoter regulates etching speed and etching section, thereby is used from the effect of etched another adjusting parameter in the lump of the metallized multilayer film being comprised of copper and other metal.
In etchant of the present invention, azole compounds suppresses the etching of copper, thereby reduces to carry out the etched deviation between copper or tin-copper alloy film WU and other metallic membrane, makes it possible to carry out in the lump etching.In addition, above-mentioned azole compounds is also born the effect that reduces the key size loss (CD loss) of copper-containing metal film figure and improve the nargin (margin) in operation.In this manual, so-called azole compounds, refers to the five-membered ring that contains nitrogen element, has the first son of at least more than one non-carbon in ring.On the other hand, exceptionally, pyrroles is also considered as being contained in above-mentioned azole compounds.In the present invention, azole compounds can be used various kinds, do not limited especially, for example, have benzo tetrazolium, amino tetrazole, pentazole, triazole, imidazoles, indoles, pyrazoles etc. to there are 2 above heteroatomic compounds and there is the pyrroles of 1 nitrogen.In the present invention, as azole compounds, also comprise using above-claimed cpd as parent the compound being replaced by C1～C6 alkyl or C5～C12 aryl therein.In a concrete embodiment of the present invention, azole compounds is amino tetrazole.
In one embodiment of the invention, the content of above-mentioned azole compounds, take etchant all wts as benchmark, accounts for 0.1 to 3.0 % by weight.If the content of above-mentioned azole compounds is within the scope of this, copper and the etching in the lump of other metallic membrane, contributes to and reduces CD loss, guarantees the rectilinear propagation of distribution.
In etchant of the present invention, fluoroboric acid is used separately, or is used in combination with the fluorochemicals of at least one.Above-mentioned fluorochemicals is as fluorine source, and can use is variedly not the material of fluoroboric acid and hydrofluoric acid (HF), but preferably, can select free MgF
2, H
2siF
6, NaF, NaHF
2, NH
4f, NH
4hF
2, NH
4bF
4, KF, KHF
2, AlF
3and H
2tiF
6in the group forming more than a kind.In a concrete embodiment of the present invention, use the constituent of fluoroboric acid and Potassium monofluoride (KF).
The fluoroboric acid using in etchant of the present invention makes to be commonly used for the molybdenum film of lower film or the etching of molybdenum-titanium film becomes smooth and easy, particularly to bad the playing an important role of distribution that prevents from being caused by resistates and residual film in grid and source-drain electrode distribution.Fluoroboric acid also, with together with hydrogen peroxide and phosphoric acid in etchant, plays the vital role of the etching power that maintains composition.
The common fluoride ion source that contains such as hydrofluoric acid of fluoroboric acid technology different from the past, makes not damage glass substrate or contains silicon substrate, in the lump etching copper-containing metal film.The etchant of the present invention that uses the composition of fluoroboric acid or fluoroboric acid and fluorochemicals, does not corrode glass substrate, thereby in manufacturing process, in the bad situation of substrate deposition, has advantages of and can recycle glass substrate.
In addition, fluoroboric acid plays the regulating effect that makes not occur notch cuttype taper profile when other metallic membrane of etching.In other metallic membrane, for example, during etching molybdenum film, due to the characteristic of molybdenum, often there is the situation of the resistates of small-particle form.In molybdenum film, if leave resistates, finally on corresponding circuit substrate, cause electric short circuit, or the in the situation that of liquid crystal indicator, reduce brightness, therefore, resistates becomes important undesirable element.Fluoroboric acid plays a part to prevent this molybdenum resistates.In addition, in other metallic membrane, comprise in the situation of titanium, must be such as the fluorine source of fluoroboric acid when etching.
And if use the composition of fluoroboric acid or fluoroboric acid and at least one fluorochemicals,, in etching work procedure, sheet is counted processing power and is improved.In liquid crystal indicator volume production operation, preferably use identical etchant, process most substrates.Yet, take that there is no the etchant in the past of fluoroboric acid be example, in the situation that the metallized multilayer film of etch copper and molybdenum, the copper and the molybdenum ion that due to the effect because of etching solution, generate react with etching solution again, thereby change rapidly the composition of etchant.Due to the cause of this reacting phenomenon again, with the etching solution of conventional art, to process after a certain amount of substrate, the etching characteristic of this etching solution changes.But, if use the etchant of the present invention comprise fluoroboric acid, can postpone this of considerable part and react again, thereby maintain to greatest extent under the etching characteristic of etching solution, can carry out stably etching.Therefore,, if use the etchant that contains fluoroboric acid of the present invention, the substrate number that can process with identical etchant increases.
In the present invention, do not use sulfuric acid and the vitriol in the past using.Sulfuric acid and sulfuric acid based compound are categorized as strong acid.If use this sulfuric acid or sulfuric acid based compound, the erosion action that may occur to be caused by it, that is, etching reagent infiltrates and to engage weak position, the effect at the undesirable position of etching between photoresist material and metal.Erosion action causes the perforation (data open) of data wiring of pin hole (pinhole) shape bad in copper film, this becomes the staggered floor being caused by galvanic couple (galvanic) the bad factor that reduces the TFT characteristic of using metal wiring film bad and that caused by the line of distribution self, in actual volume production, become fatal undesirable element.At etchant of the present invention and utilizing in its engraving method, do not use sulfuric acid and sulfuric acid based compound, thereby can prevent the data wiring of this copper film to connect bad.
In one embodiment of the invention, in above-mentioned etchant, can further comprise the additive conventionally comprising, for example tensio-active agent.But advantage of the present invention is, even without this additive, also can obtain outstanding etching performance.Therefore,, in the preferred embodiment of the present invention, provide the etchant that does not comprise this additive.The problem that the etchant that does not use additive is separated out on etched substrate owing to can fundamentally preventing organic acid and metal ion to form infusible precipitate, thereby preferably.
In another aspect of the present invention, provide a kind of method of utilizing aforesaid etchant etching copper-containing metal film.Wherein, so-called copper-containing metal film, as front above-mentioned, is metal single layer film or the two-layer above multilayer film that contains copper.
The engraving method of copper-containing metal film of the present invention comprises: the step that forms copper-containing metal film on substrate; On above-mentioned copper-containing metal film, form the step of photoetching agent pattern; And by the step of the above-mentioned copper-containing metal film of above-mentioned etchant etching.With regard to the formation of above-mentioned copper-containing metal film, such as waiting known various metal laminated method in known technology to realize by deposition.
Fig. 1 roughly shows according to one embodiment of the present invention, the figure of the method for the duplicature of etching and titanium-molybdenum alloy film.Below with reference to Fig. 1, be described more specifically the engraving method according to this embodiment.
Upper at glass substrate (10), according to chemical vapour deposition, the alloy film of successive sedimentation molybdenum and titanium (12) and copper film or tin-copper alloy film WU (14).The thickness of each film by molybdenum-titanium alloy film (12) approximately
copper film (14) approximately
form that (Fig. 1 a).Between glass substrate (10) and molybdenum-titanium alloy film (12), can add structure for display unit (not shown).Display unit refers to structure, on the conductive layer of the semiconductor films such as the various oxide films such as silicon oxide film, silicon nitride film or non-crystalline silicon, polysilicon or the amorphous polysilicon being doped, various metallic membranes etc., form pattern, thereby above-mentioned layer is with 1 layer of structure overlapping to form above.In addition, upper at substrate (10), copper film (14) upper, molybdenum-titanium alloy film (12) is first-class, carries out common washing procedure.
Then, in order to form copper or copper alloy/molybdenum-titanium duplicature at position optionally, coating photoresist material (16) (Fig. 1 b), utilizes mask optionally to expose, and by developing solution, partly removes photoresist material (16) (Fig. 1 c).In this case, photoresist material (16) can be negativity or positivity reactive material, and wherein, in the situation of positive photoresist, the part of exposure is developed, and in the situation of negative photoresist, on the point that the branch not exposing is developed, there are differences.In addition, in this operation, can add the operation that ashing (ashing), thermal treatment etc. are carried out conventionally.
Then, utilize above-mentioned etchant, carry out copper/molybdenum-titanium duplicature etching work procedure.Fig. 1 d illustrates the etched situation of copper film (14).Continue by identical etching solution etching molybdenum-titanium film (12) (Fig. 1 e).Fig. 1 e illustrates the figure of film thickness etc. turgidly compared with reality.The etching work procedure of this copper/molybdenum-titanium duplicature can be carried out according to the known method in this field, has dipping, spraying method etc.During etching work procedure, the temperature of etching solution can be approximately 30 to approximately 33 ℃, and etching period is carried out approximately 50 seconds to approximately 100 second time conventionally.Finally, from whole, remove photoresist material, formation shape as shown in Figure 1 f.
As mentioned above, a kind of embodiment of having lifted the duplicature that etching comprises copper film and three kinds of metals of titanium-molybdenum has illustrated engraving method of the present invention, but aforesaid principle in the situation that more than 3 layers multilayer film or formed or the single film of copper and copper alloy by two kinds of metals of copper and molybdenum or copper and titanium also can similarly apply.
With above-mentioned engraving method, can manufacture liquid crystal indicator and semiconductor device etc.In this case, between substrate and copper-containing metal film, can be formed with semiconductor structure bodies.Above-mentioned semiconductor structure bodies is for comprising the display unit semiconductor structure bodies such as LCD, PDP, comprise more than one the film in the semiconductor films such as silicon fiml of insulating film by methods such as chemical vapour depositions, conductive film, amorphous or polycrystalline etc. by methods such as sputters, refer to the structure of manufacturing with photo-mask process, etching work procedure etc.
With regard to the structure of the TFT of liquid crystal indicator, comprising: the step that forms gate electrode on substrate; Comprising the step that forms gate insulation layer on the substrate of above-mentioned gate electrode; On above-mentioned gate insulation layer, form the step of semiconductor layer; The step of formation source and drain electrode on above-mentioned semiconductor layer; And the step that forms the pixel electrode that is connected in above-mentioned drain electrode; The method that forms gate electrode, source and drain electrode, pixel electrode can be undertaken by above-mentioned engraving method.That is, above-mentioned copper-containing metal film can, by etching, form the gate wirings of TFT-LCD and source/drain electrode distribution of composition data line.TFT-LCD source/drain electrode distribution is the distribution that its resistance becomes problem, thereby use copper-containing metal film, particularly use copper/molybdenum-titanium, titanium, molybdenum multilayer film, and easily carry out etching with etchant of the present invention, thereby can carry out the maximization of TFT-LCD.
In still another aspect of the invention, provide a kind of use liquid crystal indicator that aforesaid engraving method manufacture obtains.
In one side more of the present invention, provide a kind of use semiconductor device that aforesaid method manufacture obtains.
Embodiment
Lift Production Example and experimental example below, illustrate in greater detail the present invention.No matter under any circumstance following examples are for describing the present invention in detail by example, and, and all non-is intention for limiting the scope of the invention.
< Production Example 1 is to Production Example 6>
For the engraving method of engraving method more of the present invention and conventional art, manufactured the Production Example composition that comprises the composition of content shown in following table 1 and the water of surplus.It is to take the weight percent unit that whole composition weights are benchmark that all compositions of table 1 form.
Table 1
| ? | H 2O 2 | Phosphoric acid | KNO 3 | Amino tetrazole | HBF 4 | KF | HF |
| Production Example 1 | 15% | 2.5% | 0.5% | 0.6% | 0.1% | 0.1% | 0% |
| Production Example 2 | 25% | 2.5% | 0.5% | 0.6% | 0.1% | 0.1% | 0% |
| Production Example 3 | 10% | 2.5% | 0.5% | 0.6% | 0.1% | 0.1% | 0% |
| Production Example 4 | 5% | 2.5% | 0.1% | 0.6% | 0.1% | 0.1% | 0% |
| Production Example 5 | 15% | 2.5% | 0.5% | 0.6% | 0% | 0% | 0.4% |
| Production Example 6 | 15% | 2.5% | 3.0% | 0.6% | 0% | 0.5% | 0% |
embodiment 1
On glass substrate, by chemical vapour deposition, the alloy film of successive sedimentation molybdenum and titanium (50:50) and copper film.With regard to the thickness of each film, molybdenum-titanium alloy film is for approximately
copper film is for approximately
Then, in order to form the duplicature of copper film/molybdenum-titanium film at position optionally, coating photoresist material, utilizes mask optionally to expose, and by developing solution, partly removes photoresist material.Then, utilize the etchant obtaining in above-mentioned Production Example 1, carry out the duplicature etching work procedure of copper film/molybdenum-titanium film.Aspect execution, etching mode carries out with spraying method, and the temperature of etching solution is 30 ℃ during etching work procedure, and etching period is approximately 70 seconds.With the etching end point (End Point Detection (EPD)) of eyes perception metal, obtain according to the etching speed of time (etching rage).After etching work procedure, through rinsing after operation and drying process, finally from whole, remove photoresist material.
Use cross section scanning electronic microscope (SEM) (HIT's product, model is S-4200), check by the section of the etched copper film/molybdenum-titanium film of above-mentioned operation.
embodiment 2
The etchant obtaining in using above-mentioned Production Example 2, use the method identical with above-described embodiment 1 to carry out etching work procedure, the duplicature section that obtains etching speed and observe with section S EM.
embodiment 3
The etchant obtaining in using above-mentioned Production Example 3, use the method identical with above-described embodiment 1 to carry out etching work procedure, the duplicature section that obtains etching speed and observe with section S EM.
embodiment 4
The etchant obtaining in using above-mentioned Production Example 4, use the method identical with above-described embodiment 1 to carry out etching work procedure, the duplicature section that obtains etching speed and observe with section S EM.
comparative example 1
The etchant obtaining in using above-mentioned Production Example 5, use the method identical with above-described embodiment 1 to carry out etching work procedure, the duplicature section that obtains etching speed and observe with section S EM.
comparative example 2
The etchant obtaining in using above-mentioned Production Example 6, use the method identical with above-described embodiment 1 to carry out etching work procedure, the duplicature section that obtains etching speed and observe with section S EM.
To be presented in following table 2 according to the etching speed in the etching work procedure of above-described embodiment and comparative example, CD loss assessment, cone angle evaluation, the long evaluation result of tail.
Table 2
estimation of stability along with the etching solution of etching period process: accumulated process sheet number is measured
If etching is copper-containing metal film in fact,, along with the process of time, in etching solution, the concentration of cupric ion increases, thereby occurs declining according to the pollution of described lower glass substrate or etching section characteristic.That is, along with etched, carry out, in etching solution, the copper metal concentration of cupric ion or copper metal particle etc. increases, if this concentration surpasses a certain boundary, etching section characteristic is transformed to bad section from good taper profile.To so can produce maximum value (being threshold value) in the etching solution of the etched copper metal ingredient of good taper and be used as the yardstick of accumulated process sheet number, evaluate the etching stability along with time process of etching solution.Etching solution to above-mentioned Production Example 1 to 6, the evaluation of carrying out etching stability is as follows.In the composition obtaining in above-mentioned Production Example 1, add after copper powder 1000ppm, dissolve 4 hours, obtain copper and add etching solution.Use this copper to add etching solution, use the method identical with above-described embodiment 1, the identical copper film/molybdenum-substrate titanium film with using in experiment shown in table 2 (5 * 5cm size) is carried out after etching, with FE-SEM, analyze etching section.Under the etching section of analysis like this is good taper profile situation, add again again copper powder 1000ppm, repeatedly said process.Repeatedly implement said process, until copper powder addition reaches 6000ppm～8000ppm.The evaluation of etching section forms in the following manner: centered by how many copper components and concentrations can be maintained until good etching section, observe the electron micrograph of etched substrate.For the quality evaluation of etching section, considered that CD-loss, cone angle, substrate bottom have or not residual film, whether bad undercutting (undercut) is, whether bad staggered floor is, corrode whether bad etc.
Calculate, compare with initial stage etching section (reference) (not adding the situation of copper powder), along with dustiness increases the copper powder content that the time point of profile change drops into, substitution is according to the copper film thickness of the area of substrate size and lamination, the contrary accumulated process sheet number of calculating.Calculating in process of accumulated process sheet number, size of substrate is not what fix, thereby by carry out contrary accumulated process sheet number of calculating the etching solution of above-described embodiment 1 according to the analytical results of the dustiness of copper powder, its result is presented in following table 3.
Table 3
| The etch combination using | Accumulated process sheet number (ppm) |
| Production Example 1 | 6500 |
| Production Example 2 | 6500 |
| Production Example 3 | 6500 |
| Production Example 4 | 6500 |
| Production Example 5 | 2000 |
| Production Example 6 | 3000 |
In order to observe the etching section of the copper-containing metal film of the etch combination according to the present invention, with the etched copper-containing metal film of electron microscope observation.Fig. 2 to Fig. 7 be as etch combination, use separately Production Example 1 to 6 etching solution (, be followed successively by embodiment 1 to 4 and comparative example 1,2), the FE-SEM photo of etched copper-containing metal film under the copper concentration in threshold value (accumulated process sheet the is counted ppm value) scope of above-mentioned table 3.As shown in Figures 2 to 5, known when using etchant of the present invention, the damage of glass substrate does not have completely, and multilayer film is etched in the lump.In addition, as shown in Table 2 above, known when using etchant of the present invention, accumulated process sheet number increases.
On the contrary, in the situation of comparative example, observe the damage of glass substrate, can confirm that the undercutting of the etched staggered floor of glass substrate as shown in Figure 6 and lower film is as shown in Figure 7 bad, as shown in table 2, can confirm that accumulated process sheet number reduces.
That is, with regard to replace the comparative example 1 of fluoroboric acid with hydrofluoric acid with regard to, known, as shown in Figure 6, the damage of glass substrate (Glass Attack) is serious, as shown in table 2, and accumulated process sheet number also significantly reduces.In addition, as shown in comparative example 2, although the composition levels of at least one fluorochemicals is in the scope of the present invention's regulation, do not have in the situation of fluoroboric acid, although etching speed is fast, accumulated process sheet digital display work reduces.Moreover, if etching speed is greater than
etching control difficulty, opens circuit bad and as shown in Figure 7, according to the fraction defective of the undercutting of lower film, increases, and reduces on the contrary and produces yield.
Therefore, as shown in table 2 and accompanying drawing, etchant according to the present invention, due to the fluoroboric acid that comprises certain content scope, is therefore compared with conventional art, there is no the damage of glass substrate, and accumulated process sheet number is large, and this is directly connected to production yield.
Most preferred embodiment of the present invention described above is disclosed.Wherein used specific term, but this just describes object of the present invention in detail for the technician for to affiliated technology and use, be not intended to limit the scope of the present invention of recording in meaning or restriction claims.
The industrial possibility of utilizing
According to etchant of the present invention with utilize its engraving method can be for comprising the manufacture of the semiconductor device of liquid crystal indicator.
Claims (10)
1. an etchant for copper-containing metal film, is characterized in that, take composition all wts as benchmark, comprises:
Hydrogen peroxide 5.0 to 30 % by weight;
Phosphoric acid 0.1 to 7.0 % by weight;
Oxidation promoter 0.1 to 3.0 % by weight that comprises potassium ion;
Azole compounds 0.1 to 3.0 % by weight;
Fluoroboric acid (HBF
4) separately or composition 0.11 to 2.0 % by weight of fluoroboric acid and at least one other fluorochemicals; And
The water of surplus.
2. etchant according to claim 1, is characterized in that, described in comprise potassium ion oxidation promoter be saltpetre.
3. etchant according to claim 1, is characterized in that, described fluorochemicals selects free MgF
2, H
2siF
6, NaF, NaHF
2, NH
4f, NH
4hF
2, NH
4bF
4, KF, KHF
2, AlF
3and H
2tiF
6in the group forming more than a kind.
4. etchant according to claim 3, is characterized in that, the composition of described fluoroboric acid and at least one other fluorochemicals consist of fluoroboric acid 0.01 to 1 % by weight and fluorochemicals 0.1 to 1 % by weight.
5. etchant according to claim 4, is characterized in that, described other fluorochemicals is Potassium monofluoride.
6. etchant according to claim 1, it is characterized in that, described copper-containing metal film is the single film being comprised of copper or copper alloy, or is multilayer film, and described multilayer film for further having the film that contains any one above metal in molybdenum and titanium except the film of copper or copper alloy.
7. a copper-containing metal film engraving method, is characterized in that, comprising:
On substrate, deposit the step of copper-containing metal film;
On described copper-containing metal film, form the step of photoetching agent pattern; And
Step with copper-containing metal film described in the etchant etching described in any one in claim 1 to 6.
8. engraving method according to claim 7, is characterized in that, with impregnation method or spraying method, carries out described etched step.
9. a liquid crystal indicator, is manufactured by method claimed in claim 7.
10. a semiconductor device, is manufactured by method claimed in claim 7.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR10-2011-0060238 | 2011-06-21 | ||
| KR1020110060238A KR101770754B1 (en) | 2011-06-21 | 2011-06-21 | Etchant for Metal Interconnects and Method for Preparing Liquid Crystal Display Devices Using the same |
| PCT/KR2012/004717 WO2012177017A2 (en) | 2011-06-21 | 2012-06-15 | Metal wire etchant liquid and method for manufacturing a liquid crystal display using the etchant |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103635608A true CN103635608A (en) | 2014-03-12 |
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|---|---|---|---|
| CN201280030638.9A Pending CN103635608A (en) | 2011-06-21 | 2012-06-15 | Metal wiring etching solution and method for manufacturing liquid crystal display device using same |
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| Country | Link |
|---|---|
| KR (1) | KR101770754B1 (en) |
| CN (1) | CN103635608A (en) |
| TW (1) | TW201313879A (en) |
| WO (1) | WO2012177017A2 (en) |
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| CN114774922A (en) * | 2022-04-01 | 2022-07-22 | 肇庆微纳芯材料科技有限公司 | Metal etching solution and preparation method and etching method thereof |
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| KR102092350B1 (en) * | 2013-10-18 | 2020-03-24 | 동우 화인켐 주식회사 | Manufacturing method of an array substrate for liquid crystal display |
| KR102160286B1 (en) * | 2013-11-04 | 2020-09-28 | 동우 화인켐 주식회사 | Manufacturing method of an array substrate for liquid crystal display |
| KR102178949B1 (en) | 2013-11-21 | 2020-11-16 | 삼성디스플레이 주식회사 | Echtant and method for manufacturing display device using the same |
| CN103668209B (en) * | 2013-12-07 | 2016-01-20 | 江阴江化微电子材料股份有限公司 | Titanium-aluminium-titanium metal stacked film etchant |
| KR102368376B1 (en) * | 2015-09-22 | 2022-02-28 | 동우 화인켐 주식회사 | Etchant composition for metal layer and preparing method of an array substrate for liquid crystal display using same |
| KR102479444B1 (en) * | 2015-12-30 | 2022-12-21 | 삼영순화(주) | Etchant and manufacturing method for semiconductor device using the same |
| KR102007428B1 (en) | 2017-03-09 | 2019-08-05 | 코닝 인코포레이티드 | Method of fabricating a metal thin film supported by a glass support |
| WO2018164535A1 (en) * | 2017-03-09 | 2018-09-13 | 코닝 인코포레이티드 | Method for manufacturing metal thin film supported by glass support |
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| KR100505328B1 (en) * | 2002-12-12 | 2005-07-29 | 엘지.필립스 엘시디 주식회사 | ETCHING SOLUTIONS AND METHOD TO REMOVE MOLYBDENUM RESIDUE FOR Cu MOLYBDENUM MULTILAYERS |
| WO2004101222A2 (en) * | 2003-05-12 | 2004-11-25 | Advanced Technology Materials, Inc. | Chemical mechanical polishing compositions for step-ii copper liner and other associated materials and method of using same |
| KR101347499B1 (en) * | 2006-11-21 | 2014-01-07 | 동우 화인켐 주식회사 | Method of producing tft array substrate for liquid crystal display |
| KR101619380B1 (en) * | 2009-05-14 | 2016-05-11 | 삼성디스플레이 주식회사 | Etchant and method of array substrate using the same |
| KR101582946B1 (en) * | 2009-12-04 | 2016-01-08 | 삼성디스플레이 주식회사 | Thin film transistor substrate and the method therrof |
-
2011
- 2011-06-21 KR KR1020110060238A patent/KR101770754B1/en active IP Right Grant
-
2012
- 2012-06-15 WO PCT/KR2012/004717 patent/WO2012177017A2/en active Application Filing
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Cited By (2)
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|---|---|---|---|---|
| CN114774922A (en) * | 2022-04-01 | 2022-07-22 | 肇庆微纳芯材料科技有限公司 | Metal etching solution and preparation method and etching method thereof |
| CN114774922B (en) * | 2022-04-01 | 2022-11-15 | 肇庆微纳芯材料科技有限公司 | Molybdenum-aluminum metal etching solution and preparation method and etching method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2012177017A3 (en) | 2013-02-28 |
| KR20120140481A (en) | 2012-12-31 |
| WO2012177017A2 (en) | 2012-12-27 |
| TW201313879A (en) | 2013-04-01 |
| KR101770754B1 (en) | 2017-08-24 |
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