CN108265298A - The manufacturing method of metal film etchant and array substrate for display device - Google Patents

The manufacturing method of metal film etchant and array substrate for display device Download PDF

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Publication number
CN108265298A
CN108265298A CN201711484017.9A CN201711484017A CN108265298A CN 108265298 A CN108265298 A CN 108265298A CN 201711484017 A CN201711484017 A CN 201711484017A CN 108265298 A CN108265298 A CN 108265298A
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metal film
film
weight
mentioned
etchant
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金兑勇
金炼卓
梁圭亨
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Dongwoo Fine Chem Co Ltd
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Dongwoo Fine Chem 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
    • 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
    • C23F1/44—Compositions for etching metallic material from a metallic material substrate of different composition
    • 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
    • C09K13/08—Etching, surface-brightening or pickling compositions containing an inorganic acid containing a fluorine 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
    • C23F1/10—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
    • 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
    • C23F1/30—Acidic compositions for etching other metallic material
    • 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
    • H01L21/30604—Chemical etching
    • 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
    • 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
    • H01L27/1259—Multistep manufacturing methods
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L29/00—Semiconductor devices adapted for rectifying, amplifying, oscillating or switching, or capacitors or resistors with at least one potential-jump barrier or surface barrier, e.g. 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
    • H01L29/68—Types of semiconductor device ; Multistep manufacturing processes therefor controllable by only the electric current supplied, or only the electric potential applied, to an electrode which does not carry the current to be rectified, amplified or switched
    • H01L29/76—Unipolar devices, e.g. field effect transistors
    • H01L29/772—Field effect transistors
    • H01L29/78—Field effect transistors with field effect produced by an insulated gate
    • H01L29/786—Thin film transistors, i.e. transistors with a channel being at least partly a thin film
    • H01L29/78606—Thin film transistors, i.e. transistors with a channel being at least partly a thin film with supplementary region or layer in the thin film or in the insulated bulk substrate supporting it for controlling or increasing the safety of the device
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L29/00—Semiconductor devices adapted for rectifying, amplifying, oscillating or switching, or capacitors or resistors with at least one potential-jump barrier or surface barrier, e.g. 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
    • H01L29/68—Types of semiconductor device ; Multistep manufacturing processes therefor controllable by only the electric current supplied, or only the electric potential applied, to an electrode which does not carry the current to be rectified, amplified or switched
    • H01L29/76—Unipolar devices, e.g. field effect transistors
    • H01L29/772—Field effect transistors
    • H01L29/78—Field effect transistors with field effect produced by an insulated gate
    • H01L29/786—Thin film transistors, i.e. transistors with a channel being at least partly a thin film
    • H01L29/78606—Thin film transistors, i.e. transistors with a channel being at least partly a thin film with supplementary region or layer in the thin film or in the insulated bulk substrate supporting it for controlling or increasing the safety of the device
    • H01L29/78618—Thin film transistors, i.e. transistors with a channel being at least partly a thin film with supplementary region or layer in the thin film or in the insulated bulk substrate supporting it for controlling or increasing the safety of the device characterised by the drain or the source properties, e.g. the doping structure, the composition, the sectional shape or the contact structure

Abstract

The present invention provides the manufacturing method of metal film etchant, array substrate for display device, above-mentioned metal film etchant is characterized in that, include A) hydrogen peroxide, B) fluorochemical, C) four azole compounds, D) there is in a molecule water soluble compound, the E of nitrogen-atoms and carboxyl) sulphate cpd and F) EPE polyol EPE, above-mentioned four azole compounds represent by general formula 1.R1For independently selected from by with the substituted or non-substituted of any one substituent group in halogen atom, cyano, hydroxyl or amido, C1~C12Aliphatic alkyl, R2‑O‑R3、‑NO2、‑COOR4、C6~C12Aromatic hydrocarbyl composition group in substituent group, above-mentioned R2For as (CH2) alkylidene of n and n for 0~6 integer, above-mentioned R3For as C1~C6Aliphatic alkyl substituent group, above-mentioned R4For C1~C6Aliphatic alkyl.General formula 1

Description

The manufacturing method of metal film etchant and array substrate for display device
Technical field
It is used the present invention relates to metal film etchant and using the display device of above-mentioned metal film etchant The manufacturing method of array substrate.
Background technology
In semiconductor device, on substrate formed metal wiring process generally include based on following process the step of：Profit With the metal film formation process of sputtering etc.；It is coated using photoresist, is in exposed and developed selective area photic anti- Lose agent formation process；And etching work procedure, and it is included in cleaning process before and after Individual cells process etc..Such etching work procedure Refer to, using photoresist as mask, the process that metal film is left in selective area is usually used to utilize plasma Deng dry-etching or using metal film etchant Wet-type etching.
In general, liquid crystal display device includes by thin film transistor base plate, filter substrate and is infused in two substrates Between liquid crystal layer formed liquid crystal display panel.
Liquid crystal layer is by being printed on the edge surrounding of two substrates and the sealing agent combination of encirclement liquid crystal layer.Since liquid crystal display panel is Non-luminescent element, therefore back light unit is equipped with behind thin film transistor base plate.The light that backlight is irradiated can be according to liquid crystal point Son ordered state and adjust transit dose.
In order to transmit signal to liquid crystal layer, wiring is formed on thin film transistor base plate.The wiring of thin film transistor base plate Including gate wirings and data wiring.
Here, gate wirings include the gate electrode of gate line and thin film transistor (TFT) for applying grid signal, data wiring packet Containing drain electrode and the source that the data line of data-signal and the data electrode of composition thin film transistor (TFT) are insulated and applied with gate wirings Electrode.
Such wiring can be made of metal single layer or alloy individual layer, but the shortcomings that in order to make up each metal or alloy and Desired physical property is obtained, can also be formed by multilayer.
The multilayer being vaporized on baseplate material is by etching and patterned wiring.For etching, there is dry-etching And Wet-type etching, mostly using being capable of uniform etching and the high Wet-type etching of productivity.
Korean Patent Laid the 10-2003-0082375th discloses a kind of etch combination, but with processing Number, which increases caused etching performance, to be reduced, and there are generation EPD, (End Point Detect (end point determination) are seen by naked eyes Observe etching terminate time), lateral erosion (Side Etch), cone angle (Taper angle) variable quantity increase the phenomenon that, drying (Dry) the problem of the phenomenon that (Pad) portion wiring rectilinear propagation reduces is padded after process.The applicant successfully develops to be handled for solution Number increases the composition of the caused above problem.
Existing technical literature
Patent document
Patent document 1：Korean Patent Laid the 10-2003-0082375th
Invention content
Subject to be solved
The object of the present invention is to provide a kind of metal film etchant, compared with previous etchant, It handles number variable quantity to improve, processing number increases caused EPD, lateral erosion (Side Etch) and cone angle (Taper Angle) variable quantity is small, and drying process back pad portion wiring rectilinear propagation does not reduce.
The method to solve the problem
The present invention is a kind of metal film etchant, which is characterized in that includes A) hydrogen peroxide, B) fluorine-containing chemical combination Object, C) four azole compounds, D) there is in a molecule water soluble compound, the E of nitrogen-atoms and carboxyl) sulphate cpd and F) EPE polyol EPE,
Above-mentioned four azole compounds are represented by the following general formula 1.
[general formula 1]
(R1For independently selected from by with halogen atom, cyano (- CN), hydroxyl (- OH) or amido (- NH2) in any The substituted or non-substituted of a substituent group, C1~C12Aliphatic alkyl ,-R2-O-R3、-NO2、-COOR4And C6~C12Virtue Substituent group in the group of fragrant race's alkyl composition,
Above-mentioned R2For as (CH2) alkylidene of n and n for 0~6 integer,
Above-mentioned R3For as C1~C6Aliphatic alkyl substituent group,
Above-mentioned R4For C1~C6Aliphatic alkyl.)
The present invention provides a kind of manufacturing method of array substrate for display device, which is characterized in that including：A) on substrate The step of forming gate electrode；B) on the substrate comprising above-mentioned gate electrode formed gate insulating layer the step of；C) in above-mentioned grid The step of semiconductor layer is formed on insulating layer；D) on above-mentioned semiconductor layer formed source electrode and drain electrode the step of；And e) shape The step of into the pixel electrode being connect with above-mentioned drain electrode, above-mentioned a) step is included on substrate utilizes metal after formation metal film The step of film etchant etches above-mentioned metal film and forms gate wirings, above-mentioned d) step include being formed profit after metal film The step of etching above-mentioned metal film with metal film etchant and forming source electrode and drain electrode, above-mentioned metal film etching solution Composition includes：A) hydrogen peroxide (H2O2) 15.0~25.0 weight %；B) 0.01~1.0 weight % of fluorochemical；C it is) above-mentioned Four azole compounds, 0.1~1.0 weight % of general formula 1；D) there is the water soluble compound 0.5 of nitrogen-atoms and carboxyl in a molecule ~5.0 weight %；E) 0.05~5.0 weight % of sulphate cpd；F) 1.0~5.0 weight % of EPE polyol EPE； And G) surplus water.
Invention effect
The metal film etchant of the metal film of the present invention can will be golden when manufacturing array substrate for display device Belong to film and thick film etches together, so as to which process is extremely simplified and can maximize process yield.
Further, the metal film etchant of metal film of the invention can will be handled caused by number increase EPD, lateral erosion (Side Etch) and cone angle (Taper angle) variable quantity minimize and effectively manufacture display device array Substrate.
Specific embodiment
Hereinafter, the metal film etchant that the present invention will be described in detail and the manufacturer of array substrate for display device Method.
The present invention relates to a kind of metal film etchants, and it includes A) hydrogen peroxide (H2O2), B) fluorochemical, C) four azole compounds, D) there is in a molecule water soluble compound, the E of nitrogen-atoms and carboxyl) sulphate cpd and F) more First alcohol type surfactant, particularly with the use of the substance with the specific structure represented by general formula 1 as above-mentioned tetrazolium system Object is closed, so as to EDP, lateral erosion (Side Etch) and cone angle (Taper angle) variation that will be handled caused by number increase Measure the effect minimized.
[general formula 1]
(R1For independently selected from by with halogen atom, cyano (- CN), hydroxyl (- OH) or amido (- NH2) in any The substituted or non-substituted of a substituent group, C1~C12Aliphatic alkyl ,-R2-O-R3、-NO2、-COOR4And C6~C12Virtue Substituent group in the group of fragrant race's alkyl composition,
Above-mentioned R2For as (CH2) alkylidene of n and n for 0~6 integer,
Above-mentioned R3For as C1~C6Aliphatic alkyl substituent group,
Above-mentioned R4For C1~C6Aliphatic alkyl.)
Metal film is the metal film that copper is included in the constituent of film in the present invention, thus the concept packet of above-mentioned metal film It includes：The monofilm of copper or copper alloy；Or comprising the film selected from one or more of copper film and tin-copper alloy film and selected from by molybdenum film, molybdenum The multilayer film of the film of one or more of the group of alloy film, titanium film and titanium alloy film composition.
So-called alloy film disclosed in this specification is the concept comprising nitride film or oxidation film.Metal oxide film usually contains Have by AxByCzO (A, B, C=Zn, Cd, Ga, In, Sn, Hf, Zr, Ta；X, y, z >=0) combination and the three component system that forms or Four ingredient system oxides, may be used as pixel electrode.
As the example of above-mentioned multilayer film, can enumerate copper/molybdenum film, copper/molybdenum alloy film, copper alloy/molybdenum alloy film, copper/ The duplicatures such as titanium film or trilamellar membrane.Above-mentioned copper/molybdenum film refers to the film of layers of copper for including molybdenum layer and being formed on above-mentioned molybdenum layer, Above-mentioned copper/molybdenum alloy film refers to comprising Mo alloy and the film of layers of copper being formed on above-mentioned Mo alloy, copper alloy/molybdenum alloy Film refers to that, comprising Mo alloy and the film of copper alloy layer being formed on above-mentioned Mo alloy, above-mentioned copper/titanium film refers to comprising titanium Layer and the film of layers of copper being formed on above-mentioned titanium layer.
In addition, above-mentioned Mo alloy refer to by be selected from by such as titanium (Ti), tantalum (Ta), chromium (Cr), nickel (Ni), neodymium (Nd) and The layer that the alloy of one or more of the groups of compositions such as indium (In) metal and molybdenum is formed.
Particularly, metal film etchant of the invention preferably can be applied to by copper or tin-copper alloy film and molybdenum or molybdenum The multilayer film that alloy film is formed.
Particularly, metal film etchant of the invention preferably can be applied to by copper or tin-copper alloy film and molybdenum or molybdenum The multilayer film that alloy film is formed.
In the present invention, the thickness of copper system metal film is at leastAnd it is reached including thicknessAbove metal film.With Thickness isThe film of degree is different, in thicknessIn the case of above thick film, if using previous etching Liquid (Etchant), then corrosion rate is slow, therefore process time (Process Time) increases.Therefore it needs and previous etching solution Compared to faster corrosion rate (More than), thus previous etching solution cannot be used.In addition, in the characteristic of thick film Cone angle it is big in the case of (60 ° of cone angle or more), when carrying out subsequent handling, it may occur that Step Coverage (Step Coverage) It is bad, it is therefore necessary to reduce cone angle, but in the case of previous etching solution, be difficult to apply due to cone angle is big.
Hereinafter, carry out the composition that the present invention will be described in detail by inscape.
A) hydrogen peroxide (H2O2)
A included in the metal film etchant of the present invention) hydrogen peroxide (H2O2) it is to influence copper system metal film The primary oxidant of etching, the copper system metal film are characterized in that, are comprising molybdenum layer and the copper of layers of copper being formed on above-mentioned molybdenum layer Molybdenum film or the copper-molybdenum alloy film comprising Mo alloy and the layers of copper being formed on above-mentioned Mo alloy.
Relative to composition total weight, above-mentioned A) hydrogen peroxide (H2O2) content for 15.0~25.0 weight %, preferably 18.0~23.0 weight %.If content is less than above range, the possible deficiency of etching power of copper system metal film and molybdenum alloy film And can not realize sufficient etching, in the case where content is more than above range, because of hydrogen peroxide (H2O2) excessive concentration and etch The stability of liquid reduces.
B) fluorochemical
The B that is included of metal film etchant of the present invention) fluorochemical is to refer to dissociate and release in water Put the compound of F ion.Above-mentioned B) fluorochemical be influence molybdenum alloy film etching speed pro-oxidant, adjust molybdenum alloy The etching speed of film.
Relative to composition total weight, above-mentioned B) content of fluorochemical is 0.01~1.0 weight %, preferably 0.05 ~0.5 weight %.If content is less than above range, the etching speed of molybdenum system metal film and metal oxide film is slack-off.Such as Fruit content is more than above range, although then the etching performance of molybdenum alloy film improves, etching speed becomes faster on the whole, therefore can be bright Explict occurrence undercuts the etch damage (Damage) of the Si systems lower layer of (under cut) phenomenon or lower layer.
Above-mentioned B) fluorochemical is not particularly limited as long as substance used in the art.But above-mentioned B) Fluorochemical is preferably selected from by HF, NaF, NH4F、NH4BF4、NH4HF2、KF、KHF2、AlF3And HBF4The group of composition, but from SiO2It damages from the aspect of (Damage), preferably comprising HF2NH4HF2(ABF)。
C) four azole compounds
The above-mentioned C that is included of metal film etchant of the present invention) four azole compounds adjust molybdenum system metal film and The etching speed of copper wiring (data wiring) contacted with metal oxide film.
Above-mentioned C) four azole compounds can represent by the following general formula 1,
[general formula 1]
(R1For independently selected from by with halogen atom, cyano (- CN), hydroxyl (- OH) or amido (- NH2) in any The substituted or non-substituted of a substituent group, C1~C12Aliphatic alkyl ,-R2-O-R3、-NO2、-COOR4And C6~C12Virtue Substituent group in the group of fragrant race's alkyl composition,
Above-mentioned R2For as (CH2) alkylidene of n and n for 0~6 integer,
Above-mentioned R3For as C1~C6Aliphatic alkyl substituent group,
Above-mentioned R4For C1~C6Aliphatic alkyl.)
More specifically, comprising Deng.
Relative to composition total weight, above-mentioned C) contents of four azole compounds is 0.1~1.0 weight %, preferably 0.1 ~0.8 weight %.If content is less than above range, copper wiring etching speed increases and corroding prevents effect from reducing.If More than above range, then the etching speed of molybdenum system metal film and metal oxide film reduces, thus there may be activity time damages It loses.
D) there is the water soluble compound of nitrogen-atoms and carboxyl in a molecule
The D that is included of metal film etchant of the present invention) there is in a molecule water solubility of nitrogen-atoms and carboxyl Compound prevents the selfdecomposition of the aquae hydrogenii dioxidi reaction that may occur in keeping metal film etchant and is etching Prevent etching characteristic from changing during multiple substrates.In general, in the feelings for the metal film etchant for using aquae hydrogenii dioxidi Under condition, keeping when aquae hydrogenii dioxidi occur selfdecomposition and its storage time is not grown, also tool there is a possibility that container explosion it is dangerous because Element.But in the case that there is the water soluble compound of nitrogen-atoms and carboxyl in comprising an above-mentioned molecule, aquae hydrogenii dioxidi Decomposition rate reduces nearly 10 times, it is advantageously ensured that storage time and stability.Particularly, in the case of layers of copper, work as metal film When a large amount of copper ions are remained in etchant, can often occur to form passivation (passivation) film and after aoxidizing blackening Situation about can not be further etched, but in the case where adding above compound, such phenomenon can be prevented.Above-mentioned D) one point The content in son with the water soluble compound of nitrogen-atoms and carboxyl is 0.5~5.0 weight %, particularly preferably 1.0~3.0 weights Measure % ranges.
The content in an above-mentioned molecule with the water soluble compound of nitrogen-atoms and carboxyl is less than above range Under, it can be not easy to obtain sufficient operation allowance when forming passivating film after etching mass substrate (about 500).In addition, upper State D) have in a molecule nitrogen-atoms and carboxyl water soluble compound content be more than above range in the case of, due to molybdenum or The etching speed of molybdenum alloy is slack-off, therefore the residue of molybdenum or molybdenum alloy film can occur in the case of copper-molybdenum film or copper-molybdenum alloy film Problem.
The water soluble compound for having nitrogen-atoms and carboxyl in an above-mentioned molecule can enumerate alanine (alanine), ammonia Base butyric acid (aminobutyric acid), glutamic acid (glutamic acid), glycine (glycine), iminodiacetic acid (iminodiacetic acid), nitrilotriacetic acid (nitrilotriacetic acid) and sarcosine (sarcosine) etc..And And wherein be most preferably iminodiacetic acid (iminodiacetic acid).
E) sulphate cpd
E included in the metal film etchant of the present invention) sulphate cpd is the oxidation for adjusting Cu surfaces Current potential and the increased ingredient of etching speed for making copper film.If above-mentioned E is not present in the metal film etchant of the present invention) Sulphate cpd, then etching speed is very slow and etching outline may be bad.Relative to composition total weight, above-mentioned E) sulfuric acid The content of salt compound is 0.05~5.0 weight %, and particularly preferred content is 0.1~3.0 weight % ranges.In above-mentioned E) sulfuric acid In the case that the content of salt compound is less than above range, etching speed is very slow and may occur that etching outline is bad and process The loss of time.In above-mentioned E) in the case that the content of sulphate cpd is more than above range, the etching speed of copper or tin-copper alloy film It is excessive and easily occur that Step Coverage (Step coverage) is bad, and it is dfficult to apply to thick films to spend fast or cone angle.
Above-mentioned E) sulphate cpd can enumerate ammonium sulfate (Ammonium sulfate), sodium sulphate (Sodium Sulfate), potassium sulfate (Potassium sulfate), magnesium sulfate (Magnesium sulfate), lithium sulfate (Lithium Sulfate) etc..
F) EPE polyol EPE
F included in the metal film etchant of the present invention) EPE polyol EPE performance makes surface Power reduces and improves the effect of etch uniformity.In addition, above-mentioned F) EPE polyol EPE by surrounding etching after The copper ion dissolved out in etching solution so as to inhibit the activity of copper ion, inhibits the decomposition reaction of hydrogen peroxide.If it drops in this way The activity of low copper ion then can steadily carry out process during etching solution is used.
Relative to composition total weight, above-mentioned F) content of EPE polyol EPE is 1.0~5.0 weight %, it is excellent It is selected as 1.5~3.0 weight %.In above-mentioned F) content of EPE polyol EPE less than in the case of above range, may The problem of etch uniformity, which occurs, to be reduced, and the decomposition of hydrogen peroxide is accelerated.If above-mentioned F) EPE polyol EPE contains Amount is more than above range, then there is the shortcomings that generating a large amount of foams.
Above-mentioned F) EPE polyol EPE can enumerate glycerine (glycerol), triethylene glycol (triethylene ) and polyethylene glycol (polyethylene glycol) etc. glycol.And wherein it is preferably triethylene glycol (triethylene glycol)。
In addition, other than mentioned component, common additive can be further added, as additive, from etching (Etch) effect that inclined-plane improves and cone angle is adjusted considers, can enumerate the organic acid for including citric acid, tartaric acid etc., relatively In composition total weight, content is 0.1~5.0 weight %, especially preferably 0.5~3.0 weight %.
The present invention provides a kind of manufacturing method of array substrate for display device, which is characterized in that including：A) on substrate The step of forming gate electrode；B) on the substrate comprising above-mentioned gate electrode formed gate insulating layer the step of；C) in above-mentioned grid The step of semiconductor layer is formed on insulating layer；D) on above-mentioned semiconductor layer formed source electrode and drain electrode the step of；And e) shape The step of into the pixel electrode being connect with above-mentioned drain electrode, above-mentioned a) step is included on substrate utilizes metal after formation metal film The step of film etchant etches above-mentioned metal film and forms gate wirings, above-mentioned d) step include being formed profit after metal film The step of etching above-mentioned metal film with metal film etchant and forming source electrode and drain electrode, above-mentioned metal film etching solution Composition includes：A) hydrogen peroxide (H2O2) 15.0~25.0 weight %；B) 0.01~1.0 weight % of fluorochemical；C it is) above-mentioned Four azole compounds, 0.1~1.0 weight % of general formula 1；D) there is the water soluble compound 0.5 of nitrogen-atoms and carboxyl in a molecule ~5.0 weight %；E) 0.05~5.0 weight % of sulphate cpd；F) 1.0~5.0 weight % of EPE polyol EPE； And G) surplus water.
Each constituent used in the present invention can be manufactured using generally well-known method, metal film of the invention Etchant preferably has the purity for semiconductor process.
Hereinafter, the present invention is described in more detail by embodiment.But following embodiments are used to further illustrate this hair Bright, the scope of the present invention is not limited to following embodiments.Following embodiments can be within the scope of the invention by this field Technical staff suitably change, changes.
Embodiment and comparative example：The manufacture of metal film etchant
According to shown in table 1 below composition manufacture Examples 1 to 6, comparative example 1~5 etchant 6kg.
[table 1]
It distinguishes H2O2 ABF 5-ATAZ IMZ MTA MBTA PATA CETA ATZ IDA AS TEG
Embodiment 1 20.0 0.1 0.3 2.5 1.0 2.0
Embodiment 2 20.0 0.1 0.6 2.5 1.0 2.0
Embodiment 3 20.0 0.1 0.3 2.5 1.0 2.0
Embodiment 4 20.0 0.1 0.2 2.5 1.0 2.0
Embodiment 5 20.0 0.1 0.5 2.5 1.0 2.0
Embodiment 6 20.0 0.1 0.1 2.5 1.0 2.0
Comparative example 1 18.0 0.1 0.1 2.5 0.8 2.0
Comparative example 2 23.0 0.1 0.2 2.5 0.8 2.0
Comparative example 3 18.0 0.1 0.1 2.5 0.5 2.0
Comparative example 4 23.0 0.1 0.3 2.5 0.5 2.0
Comparative example 5 23.0 0.1 0.3
(note) ABF：Ammonium acid fluoride；TEG：Triethylene glycol；MTA：1- methyl-1 H- tetrazolium -5- amine；
MBTA：1- (2- methyl butyls) -1H-TETRAZOLE -5- amine；PATA：1- (3- aminopropyls) -1H-TETRAZOLE -5- amine；
CETA：1- (2- chloroethyls) -1H-TETRAZOLE -5- amine；ATZ：5- Aminotetrazoles；IDA：Iminodiacetic acid；
AS：Ammonium sulfate；5-ATAZ：5- aminotriazole(ATA)s；IMZ：Imidazoles
Experimental example：Etching characteristic confirms experiment
Implement etching work procedure using the etchant of Examples 1 to 6, comparative example 1~5 respectively.It is lost using injecting type Quarter mode experimental facilities (model name：ETCHER (TFT), SEMES companies), during etching work procedure, the temperature of etchant It is set as about 33 DEG C or so.Etching period can be different according to the difference of etch temperature, but in LCD etching work procedures usually with 50~ Degree carries out within 80 seconds.The copper system gold etched using the above-mentioned etching work procedure of SEM (Hitachi, Ltd's product, model name S-4700) detections Belong to the section of outline of film, result is documented in table 2 below.For the copper system metal film used in etching work procedure, Cu/ is used Mo-Ti 5000/Film substrate.
Measure lateral erosion (μm) variable quantity changed with Cu concentration.Cone angle refers to the slope on Cu inclined-planes, after lateral erosion refers to etching The distance between photoresist end and lower metal end for being measured.If side etching quantity changes, when TFT drives Signal transmission speed can be made to change and generate speckle, therefore preferably minimize lateral erosion variable quantity and T/A variable quantities.Originally it comments In valency, when meeting the condition that lateral erosion variable quantity is less than ± 0.1 μm and the condition that cone angle variable quantity is less than ± 10 °, it is determined as Etchant can be continuously employed in etching work procedure and tested.
[table 2]
(note) zero:Well, △：Commonly, ×：It is bad.
As known from Table 2, the etchant of Examples 1 to 6 shows good etching characteristic.Specifically, it utilizes The etching outline and rectilinear propagation that copper system film metal film is etched and obtained by the etchant of embodiment 1 are excellent, also do not have Generate Mo, Ti residue.In addition, show lateral erosion (Side Etch) variable quantity for ± 0.1 μm hereinafter, cone angle (Taper angle) Variable quantity be also very excellent performances as 6 degree.In comparative example 1~5, with the lateral erosion (Side of processing number variation Etch) variable quantity is ± 0.27 μm or more, and variable quantity is big, and the time that composition can be used in etching work procedure shortens, and is bored Angle (Taper angle) variable quantity is 19 ° or more, therefore as what the yield of process into guild's generation subsequent handling reduced asks Topic.

Claims (13)

1. a kind of metal film etchant, which is characterized in that include A) hydrogen peroxide, B) fluorochemical, C) tetrazolium system Compound, D) there is in a molecule water soluble compound, the E of nitrogen-atoms and carboxyl) sulphate cpd and F) polyol type table Face activating agent,
Four azole compounds represent by the following general formula 1,
General formula 1
R1To be taken independently selected from by substituted or non-with any one substituent group in halogen atom, cyano, hydroxyl or amido Generation, C1~C12Aliphatic alkyl ,-R2-O-R3、-NO2、-COOR4、C6~C12Aromatic hydrocarbyl composition group in take Dai Ji,
The R2For as (CH2) alkylidene of n and n for 0~6 integer,
The R3For as C1~C6Aliphatic alkyl substituent group,
The R4For C1~C6Aliphatic alkyl.
2. metal film etchant according to claim 1, which is characterized in that the B) fluorochemical be selected from By HF, NaF, NH4F、NH4BF4、NH4HF2、KF、KHF2、AlF3And HBF4One or more of group of composition.
3. metal film etchant according to claim 1, which is characterized in that the general formula 1 be selected from by One or more of group of composition.
4. metal film etchant according to claim 1, which is characterized in that the D) have in a molecule nitrogen former The water soluble compound of son and carboxyl is selected from by alanine, aminobutyric acid, glutamic acid, glycine, iminodiacetic acid, ammonia three One or more of group of acetic acid and sarcosine composition.
5. metal film etchant according to claim 1, which is characterized in that the E) sulphate cpd for choosing One or more of group that free ammonium sulfate, sodium sulphate, potassium sulfate, magnesium sulfate, lithium sulfate form.
6. metal film etchant according to claim 1, which is characterized in that the F) polyol type surface-active Agent is selected from one or more of group being made of glycerine, triethylene glycol and polyethylene glycol.
7. metal film etchant according to claim 1, which is characterized in that further include additive.
8. metal film etchant according to claim 7, which is characterized in that the additive is includes citric acid With the organic acid of one or more of tartaric acid.
9. metal film etchant according to claim 1, which is characterized in that the metal film etchant Relative to composition total weight, comprising：
A) 15.0~25.0 weight % of hydrogen peroxide；
B) 0.01~1.0 weight % of fluorochemical；
C) four azole compounds, 0.1~1.0 weight % of the general formula 1；
D) there is 0.5~5.0 weight % of water soluble compound of nitrogen-atoms and carboxyl in a molecule；
E) 0.05~5.0 weight % of sulphate cpd；
F) 1.0~5.0 weight % of EPE polyol EPE；With
G) the water of surplus.
10. metal film etchant according to claim 9, which is characterized in that further include additive 0.1~ 5.0 weight %.
11. according to metal film etchant according to any one of claims 1 to 10, which is characterized in that the metal Film is the monofilm of copper or copper alloy or is multilayer film, the multilayer film include in copper film or tin-copper alloy film it is a kind of with On film and film selected from one or more of the group being made of molybdenum film, molybdenum alloy film, titanium film and titanium alloy film.
12. a kind of manufacturing method of array substrate for display device, which is characterized in that including：
A) on substrate formed gate electrode the step of；
B) on the substrate comprising the gate electrode formed gate insulating layer the step of；
C) the step of forming semiconductor layer on the gate insulating layer；
D) on the semiconductor layer formed source electrode and drain electrode the step of；And
E) the step of forming the pixel electrode being connect with the drain electrode,
A) the step be included on substrate formed after metal film etch the metal film using metal film etchant and The step of forming gate wirings,
D) the step includes etching the metal film after forming metal film using metal film etchant and forming source electricity The step of pole and drain electrode,
The metal film etchant includes：A) 15.0~25.0 weight % of hydrogen peroxide；B) fluorochemical 0.01~ 1.0 weight %；C) four azole compounds, 0.1~1.0 weight % of the general formula 1；D) there is nitrogen-atoms and carboxyl in a molecule 0.5~5.0 weight % of water soluble compound；E) 0.05~5.0 weight % of sulphate cpd；F) polyol type surface-active 1.0~5.0 weight % of agent；And G) surplus water.
13. the manufacturing method of array substrate for display device according to claim 12, which is characterized in that the metal film For copper or copper alloy monofilm or be multilayer film, the multilayer film is included selected from one or more of copper film or tin-copper alloy film Film and film selected from one or more of the group being made of molybdenum film, molybdenum alloy film, titanium film and titanium alloy film.
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