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WO2011019222A9 - Composition d'agent de gravure destinée à former des interconnexions de cuivre - Google Patents

Composition d'agent de gravure destinée à former des interconnexions de cuivre Download PDF

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Publication number
WO2011019222A9
WO2011019222A9 PCT/KR2010/005310 KR2010005310W WO2011019222A9 WO 2011019222 A9 WO2011019222 A9 WO 2011019222A9 KR 2010005310 W KR2010005310 W KR 2010005310W WO 2011019222 A9 WO2011019222 A9 WO 2011019222A9
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WO
WIPO (PCT)
Prior art keywords
acid
based metal
metal film
etching
copper
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/KR2010/005310
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English (en)
Korean (ko)
Other versions
WO2011019222A3 (fr
WO2011019222A2 (fr
Inventor
양승재
임민기
권오병
이유진
유인호
박영철
신혜라
이준우
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dongwoo Fine Chem Co Ltd
Original Assignee
Dongwoo Fine Chem Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from KR1020090074828A external-priority patent/KR101805185B1/ko
Priority claimed from KR1020090084866A external-priority patent/KR101805186B1/ko
Priority claimed from KR1020090085436A external-priority patent/KR101745721B1/ko
Application filed by Dongwoo Fine Chem Co Ltd filed Critical Dongwoo Fine Chem Co Ltd
Priority to CN2010800362125A priority Critical patent/CN102471688A/zh
Publication of WO2011019222A2 publication Critical patent/WO2011019222A2/fr
Publication of WO2011019222A9 publication Critical patent/WO2011019222A9/fr
Publication of WO2011019222A3 publication Critical patent/WO2011019222A3/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F1/00—Etching metallic material by chemical means
    • C23F1/10—Etching compositions
    • C23F1/14—Aqueous compositions
    • C23F1/16—Acidic compositions
    • C23F1/26—Acidic compositions for etching refractory metals
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F1/00—Etching metallic material by chemical means
    • C23F1/02—Local etching
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F1/00—Etching metallic material by chemical means
    • C23F1/10—Etching compositions
    • C23F1/14—Aqueous compositions
    • C23F1/16—Acidic compositions
    • C23F1/18—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
    • C23F1/44—Compositions for etching metallic material from a metallic material substrate of different composition
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
    • H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
    • H01L21/321—After treatment
    • H01L21/3213—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer
    • H01L21/32133—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only
    • H01L21/32134—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only by liquid etching only

Definitions

  • the present invention relates to a wet etchant composition for a multilayer including a copper-based metal film and a titanium-based metal film.
  • the process of forming metal wiring on a substrate in a semiconductor device and a flat panel display device is performed by a metal film forming process by sputtering, a photoresist forming process and an etching process for a selective region by photoresist coating, exposure and development. It consists of the steps, and the washing process before and after an individual unit process, etc. are included.
  • the etching process refers to a process of leaving a metal film in a selective region using a photoresist mask, and typically, dry etching using plasma or wet etching using an etching solution is used.
  • chromium Cr resistivity: 12.7 ⁇ 10 -8 ⁇ m
  • molybdenum Mo resistivity: 5 ⁇ 10 -8 ⁇ m
  • aluminum Al resistivity: 2.65 ⁇ 10 -8 ⁇ m
  • alloys thereof are difficult to use as gates and data wirings used in large-sized TFT LCDs.
  • a copper film which is one of the new low resistance metal films.
  • the copper film is known to have an advantage that the resistance is significantly lower than that of the aluminum film or the chromium film and that there is no big problem in the environment.
  • the copper film has many disadvantages in the process of applying and patterning the photoresist, and the disadvantages of poor adhesion to the silicon insulating film have been found.
  • a material which is particularly in the limelight is a copper-titanium film.
  • an etchant for such a copper-titanium film an etchant described in Korean Laid-Open Patent Publication No. 2001-11390 is known. That is, the patent document includes a step of sequentially depositing a copper film and a titanium film on a substrate and simultaneously forming a gate electrode by simultaneously etching a copper film as a first gate metal and a titanium film as a second gate metal according to a predetermined pattern.
  • a method of forming a gate electrode of a thin film transistor and a mixed etchant of HF, HNO 3 and CH 3 COOH used in such an etching process are disclosed.
  • the present invention is to solve the above problems of the prior art, to provide an excellent etching profile for a multi-layer including a copper-based metal film and a titanium-based metal film, and to minimize damage and residue generation to the substrate and the lower insulating film It is an object to provide an etching solution composition.
  • the present invention relates to a copper-based metal film comprising 0.1 to 5% by weight of an inorganic salt oxidizing agent, 0.1 to 5% by weight of a chlorine-containing compound, 0.01 to 2% by weight of a fluorine-containing compound and a balance of water.
  • an etching liquid composition of a multilayer including a titanium-based metal film is provided.
  • the etchant composition of the present invention provides an excellent etching profile during the etching of multiple films including a copper-based metal film and a titanium-based metal film, and the subsequent process can be stably performed by minimizing damage and residues on the substrate and the lower insulating film. To be.
  • the etching liquid composition of the present invention as in the case of chromium or the like, it is possible to manufacture a flat panel display in an environmentally friendly manner by making it possible to replace the substances defined as environmentally harmful substances with copper.
  • 1, 3 and 5 are electron scanning micrographs showing the results of etching the Cu / Ti double layer with the etchant composition of Examples 1, 11 and 19, respectively.
  • the present invention comprises a copper-based metal film and a titanium-based metal film containing 0.1 to 5% by weight of an inorganic salt oxidizing agent, 0.1 to 5% by weight of a chlorine-containing compound, 0.01 to 2% by weight of a fluorine-containing compound and a balance of water
  • the present invention relates to an etching liquid composition of a multilayer.
  • the copper-based metal film means a copper film or a copper alloy film
  • the titanium-based metal film means a titanium film or a titanium alloy film.
  • the multilayer film including the copper-based metal film and the titanium-based metal film may include, for example, a "titanium-based metal film / copper-based metal film" and a titanium-based metal film having a copper-based metal film as a lower film and a titanium-based metal film as an upper film.
  • a double film of "copper metal film / titanium metal film” having a lower film and a copper metal film as an upper film, and further comprising a titanium metal film / copper metal film / titanium metal film or a copper metal film / It also includes the case of multiple films of triplet or more in which copper-based metals and titanium-based metal films are alternately laminated, such as titanium-based metal films / copper-based metal films.
  • Such a multilayer may determine the structure of the multilayer in consideration of a combination of materials constituting the membrane disposed on the upper portion of the membrane or the membrane disposed below, or adhesion to the membranes.
  • the copper film and the titanium film are not limited in thickness to each other, and various combinations are possible. For example, the thickness of the copper film may be formed larger than the thickness of the titanium film, or may be formed small.
  • the etchant composition comprising the inorganic salt oxidizing agent, the chlorine-containing compound, the fluorine-containing compound and the water of the present invention can be prepared by a conventionally known method, and preferably has a purity for semiconductor processing.
  • the inorganic salt oxidizing agent is a main component for etching the copper-based metal film, and is contained in an amount of 0.1 to 5% by weight based on the total weight of the composition, and when it is contained below 0.1% by weight, the etching rate of the copper-based metal film is lowered. There is no advantage, and if it exceeds 5% by weight, overetching may occur and wiring may be lost.
  • Examples of the inorganic salt oxidizing agent include CuCl 2 , Cu (NO 3 ) 2 , CuSO 4 , and the like, and these may be used alone or in combination of two or more.
  • the chlorine-containing compound in the present invention means a compound capable of dissociating chlorine ions, and serves as an auxiliary oxidant for etching the copper-based metal film.
  • the chlorine-containing compound is preferably included in 0.1 to 5% by weight, more preferably in 0.1 to 3% by weight based on the total weight of the composition.
  • the chlorine-containing compound is less than 0.1% by weight, the etching rate of the copper-based metal film is lowered, so that the etching profile is poor.
  • overetching may occur and wiring may be lost.
  • chlorine-containing compound examples include HCl, NaCl, KCl, NH 4 Cl, and the like, which may be used alone or in combination of two or more.
  • NaCl and NH 4 Cl may be more preferably used among them.
  • the fluorine-containing compound serves as a main component for etching the titanium-based metal film, it is contained in 0.01 to 2% by weight relative to the total weight of the composition. If the content is less than 0.01% by weight, the etching rate of the titanium-based metal film may be lowered, and residues may occur. If the content exceeds 2% by weight, the substrate (Glass, etc.) and the insulating film (silicon film, etc.) may be damaged. .
  • the fluorine-containing compound means a compound capable of dissociating fluorine ions or polyatomic fluorine ions.
  • Examples of the fluorine-containing compound include ammonium fluoride, sodium fluoride, potassium fluoride, ammonium bifluoride, sodium bifluoride, potassium bifluoride, and the like. These may be used alone or in combination of two or more.
  • Water used in the present invention means deionized water and is used for the semiconductor process, preferably water of 18 dl / cm or more.
  • the etchant composition of the present invention may further include one or more etching control agents selected from the group consisting of organic and inorganic acids in addition to the above-mentioned components.
  • the etching control agent may be included in 0.1 to 10% by weight based on the total weight of the composition.
  • the organic acid in the etching control agent serves to control the etching rate between the copper and the other metal in the film containing copper by inhibiting the etching of copper.
  • an organic acid is used as an etching control agent, it is preferably included in 0.1 to 10% by weight based on the total weight of the etching liquid composition. If the organic acid is included in less than 0.1% by weight, the etching rate of copper and titanium may be too fast to increase side etching, and a bad profile may be generated, and if it exceeds 10% by weight, the etching rate of copper and titanium may be too high. It can be suppressed and residues can be generated.
  • the organic acid may include citric acid, glycolic acid, glycolic acid, acetic acid, sulfonic acid, oxalic acid, water-soluble compounds having an amino group and a carboxyl group, and the like.
  • the water-soluble compound having an amino group and a carboxyl group not only serves as the above-mentioned etch control agent, but also prevents resorption by chelating copper ions dissociated at the time of etching, thereby increasing the number of processed sheets of the substrate. More preferably.
  • water-soluble compound having an amino group and a carboxyl group examples include alanine, aminobutyric acid, glutamic acid, glycine, glycine, iminodiacetic acid, nitrilotriacetic acid and sarco And sarcosine, and these may be used alone or in combination of two or more.
  • the inorganic acid plays a role opposite to that of the organic acid. That is, the inorganic acid oxidizes and etches the copper-based metal film and serves to oxidize the titanium-based metal film.
  • the inorganic acid is used as an etching control agent, it is preferably contained in 0.1 to 10% by weight based on the total weight of the etching liquid composition.
  • the inorganic acid is contained in less than 0.1% by weight, the etching rate of the copper-based metal film and the titanium-based metal film may be lowered, resulting in poor etching profiles and residues.
  • the inorganic acid exceeds 10% by weight, overetching and photoresist cracks ( This can cause a short circuit due to chemical infiltration.
  • inorganic acid examples include nitric acid, sulfuric acid, phosphoric acid, perchloric acid, and the like. These may be used alone or in combination of two or more.
  • the etchant composition of the present invention may further comprise at least one of a surfactant, a metal ion sequestrant, a corrosion inhibitor and a pH adjusting agent in addition to the above-mentioned components.
  • It provides a method for producing a thin film transistor comprising the step of forming a pattern of metal wiring using the etchant composition.
  • Example 1 CuCl 2 NaCl NH 4 FHF C 6 H 8 O 7 water
  • Example 2 0.3 1.0 0.2 0.5 98.0
  • Example 3 0.3 0.5 0.2 1.0 98.0
  • Example 4 0.5 0.5 0.2 2.0 96.8
  • Example 5 0.5 1.0 0.2 0.5 97.8
  • Example 6 1.0 1.0 0.3 1.0 96.7
  • Example 7 1.0 0.2 0.3 2.0 96.5
  • Test Example 1 Evaluation of etching characteristics of the etching solution composition of Examples 1 to 8 and Comparative Examples 1 to 3
  • a copper / titanium bilayer was deposited on a silicon layer on a glass substrate, and a substrate on which a photoresist was patterned in a uniform form was used as a specimen.
  • Etching liquid prepared in Examples 1 to 8 and Comparative Examples 1 to 3 were put into a spraying etching apparatus (SEMES, model name: ETCHER (TFT)), and the temperature was set to 25 ° C., followed by heating. After reaching 25 ⁇ 0.1 ° C., an etching process was performed. Total etch time was given at 30% based on EPD. Insert the specimen, start spraying, and when the etching is complete, taken out, washed with deionized water, dried using a hot air drying apparatus, and removed the photoresist using a photoresist stripper (PR) stripper.
  • SEMES spraying etching apparatus
  • PR photoresist stripper
  • the etchant composition of Examples 1 to 8 had excellent etching profiles, no damage to the glass substrate and the silicon layer, and showed excellent etching characteristics without residue.
  • Comparative Examples 1 to The etchant composition of 3 was found to be unsuitable for use because of poor etching profiles, unetch of copper and titanium films, and loss of copper patterns were observed (see FIGS. 1 and 2).
  • the etchant composition was prepared to be 180 kg.
  • Example 9 0.3 0.2 0.2 One 98.3 Example 10 0.4 0.3 0.1 0.5 98.7 Example 11 0.5 0.3 0.2 One 98 Example 12 0.5 0.5 0.1 0.5 98.4 Example 13 0.7 0.3 0.2 One 97.8 Example 14 0.7 0.5 0.3 One 97.5 Example 15 One 0.5 0.2 One 97.3 Example 16 2 One 0.3 One 95.7 Example 17 3 One 0.3 One 94.7 Example 18 3 1.2 0.3 One 94.5 Comparative Example 4 0.05 0.01 0.2 One 98.74 Comparative Example 5 One 0.5 0.02 0.5 97.98 Comparative Example 6 7 One 0.2 2 89.8 Comparative Example 7 0.5 0.3 2.5 One 95.7 Comparative Example 8 0.7 0.3 0.2 12 86.8
  • Test Example 3 Evaluation of the etching properties of the etching solution composition of Examples 9 to 18 and Comparative Examples 4 to 8
  • the etchant composition of Examples 9 to 18 showed excellent etching profiles, no damage to the glass substrate and the silicon layer, and showed excellent etching characteristics without residue.
  • Comparative Examples 4 to The etchant composition of 8 was found to be unsuitable for use because of poor etching profiles, unetch of copper and titanium films and loss of copper patterns were observed (see FIGS. 3 and 4).
  • Example 19 0.3 0.1 0.2 0.5 98.9
  • Example 20 0.3 0.5 0.2 0.5 98.5
  • Example 21 0.5 0.2 0.2 1.0 98.1
  • Example 22 0.5 0.5 0.2 0.7 98.1
  • Example 23 1.0 0.3 0.2 0.5 98.0
  • Example 24 1.0 0.5 0.3 1.0 97.2
  • Example 25 3.0 0.2 0.3 2.0 94.5
  • Example 26 3.0 1.0 0.3 2.0 93.7
  • the etchant composition of Examples 19 to 26 exhibited excellent etching characteristics, no damage to the glass substrate and the silicon layer, and excellent etching characteristics without residue.
  • Comparative Examples 9 to The etchant composition of 11 was found to be unsuitable for use because of poor etching profiles, unetch of copper and titanium films and loss of copper patterns were observed (see FIGS. 5 and 6).

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  • Metallurgy (AREA)
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  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
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Abstract

L'invention concerne une composition d'agent de gravure humide destinée à un film multicouches comprenant au moins un film métallique à base de cuivre et un film métallique à base de titane. La composition de l'invention comprend un excellent profil de gravure en cas de gravure du film multicouches, et minimise les dommages d'un substrat de verre et d'une couche d'isolation inférieure et la génération de résidus, permettant ainsi la performance stable d'un traitement ultérieur.
PCT/KR2010/005310 2009-08-13 2010-08-12 Composition d'agent de gravure destinée à former des interconnexions de cuivre Ceased WO2011019222A2 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN2010800362125A CN102471688A (zh) 2009-08-13 2010-08-12 用于形成铜互连的蚀刻组合物

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
KR1020090074828A KR101805185B1 (ko) 2009-08-13 2009-08-13 금속 배선 형성을 위한 식각액 조성물
KR10-2009-0074828 2009-08-13
KR1020090084866A KR101805186B1 (ko) 2009-09-09 2009-09-09 구리 배선의 형성을 위한 식각액 조성물
KR10-2009-0084866 2009-09-09
KR1020090085436A KR101745721B1 (ko) 2009-09-10 2009-09-10 구리 배선의 형성을 위한 식각액 조성물
KR10-2009-0085436 2009-09-10

Publications (3)

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WO2011019222A2 WO2011019222A2 (fr) 2011-02-17
WO2011019222A9 true WO2011019222A9 (fr) 2011-05-19
WO2011019222A3 WO2011019222A3 (fr) 2011-07-07

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CN107043626A (zh) * 2017-06-02 2017-08-15 广州市尤特新材料有限公司 一种蚀刻膏及其制备方法
CN107163947A (zh) * 2017-06-02 2017-09-15 合肥市惠科精密模具有限公司 一种用于液晶面板制造工艺的铜蚀刻液
CN112680732A (zh) * 2020-12-21 2021-04-20 江西遂川光速电子有限公司 一种精细线路刻蚀液
CN118516672A (zh) * 2024-05-24 2024-08-20 宏锐兴(湖北)电子有限责任公司 封装载板专业高精细度线路酸性蚀刻液配方

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WO2011019222A2 (fr) 2011-02-17
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