WO2008098593A1 - Composition d'un décapant du titane - Google Patents

Composition d'un décapant du titane Download PDF

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Publication number
WO2008098593A1
WO2008098593A1 PCT/EP2007/001324 EP2007001324W WO2008098593A1 WO 2008098593 A1 WO2008098593 A1 WO 2008098593A1 EP 2007001324 W EP2007001324 W EP 2007001324W WO 2008098593 A1 WO2008098593 A1 WO 2008098593A1
Authority
WO
WIPO (PCT)
Prior art keywords
titanium
etchant composition
titanium etchant
aluminum
corrosion inhibitor
Prior art date
Application number
PCT/EP2007/001324
Other languages
English (en)
Inventor
John Yan
Original Assignee
Basf Se
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
Application filed by Basf Se filed Critical Basf Se
Priority to PCT/EP2007/001324 priority Critical patent/WO2008098593A1/fr
Publication of WO2008098593A1 publication Critical patent/WO2008098593A1/fr

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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
    • 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
    • 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 metal etchant. More particularly, the present invention relates to a titanium etchant composition.
  • Titanium one of the conductor materials, has been widely used in various fields, including integrated circuits, optoelectric communication, and even in the micro-electro-mechanical (MEM) field.
  • MEM micro-electro-mechanical
  • titanium in a semiconductor fabricating process, titanium can be used as a wetting layer for an aluminum wire, so as to improve the step coverage ability of aluminum atoms. Titanium also can be used as a contact metal to reduce the contact resistance generated due to contact between the metal and silicon. Additionally, titanium can also be used as a barrier layer, an anti-reflective layer, and the like.
  • the optoelectric field gate electrodes, source electrodes, drain electrodes, scan lines, storage capacitor electrodes, signal lines, pixel lines, and the like may all utilize titanium or relevant alloy material.
  • a step of etching titanium is unavoidable, so it is especially important how to select a titanium etchant composition having a high etch rate to titanium, meanwhile without causing any corrosion to other films.
  • a conductor bump is directly connected to a chip, and a titanium film is required to be formed during the process of fabricating the bump.
  • FIG 1 it is a schematic sectional diagram of a bump in a flip chip bonding technique.
  • a chip 100 has an aluminum pad 110 formed thereon, and the aluminum pad 110 has a passivation layer 120 formed thereon, for protecting the chip 100.
  • the protective layer 120 is generally made of silicon dioxide or silicon nitride.
  • An opening of the aluminum pad 110 is covered by a under ball metallurgy layer 130 as an interface of the aluminum pad 110 and the bump 140.
  • the under ball metallurgy layer 130 is generally formed by an adhesion layer 130a, a barrier layer 130b, and a wetting layer 130c from bottom to top.
  • the material of the adhesion layer 130a is, for example, titanium
  • the material of the barrier layer 130b is, for example, chromium
  • the material of the wetting layer 130c is, for example, copper.
  • the used titanium etchant causes corrosion to the materials, such as chromium, copper, aluminum, silicon dioxide, and silicon nitride, so that the patterns of other films will be unavoidably deformed, and each film lost its function, and even the electric property of the device is deteriorated.
  • the present invention is directed to a titanium etchant composition, applicable for reducing the corrosion on aluminum and a dielectric material by the etchant, so as to ensure the integrity of patterns for other films.
  • the present invention provides a titanium etchant composition, which at least includes hydrogen fluoride (HF), corrosion inhibitor, and water.
  • HF hydrogen fluoride
  • the content of HF in the titanium etchant composition is, for example, 0.05 to 49 % by weight; and the content of the corrosion inhibitor is, for example, 0.1 to 99.9 % by weight.
  • the corrosion inhibitor is, for example, sodium silicate, azoles, organic acid, alcohols, ethers, or a mixture thereof.
  • the azoles is, for example, benzotriazole (BTA), 2,3,5-triphenyl-2H-tetraazolium chloride (TTC), or a mixture thereof.
  • the organic acid is, for example, glycine, histidine (HS), glutamic acid, propylene glycol monomethyl acetate, amino tris (methylenephosphonic acid) (ATMP), l-hydroxyethylidene-l,l-diphosphonic acid (HEDP), or a mixture thereof.
  • the alcohols is, for example, ethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, glycerol, butanol, pentanol, or a mixture thereof.
  • the ethers is, for example, butyl carbitol, diisopropyl ether, triisopropyl alcohol diether, propylene glycol dimethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol dimethyl ether, or a mixture thereof.
  • the corrosion inhibitor is, for example, used to inhibit the corrosion of aluminum, chromium, copper, or a combination thereof.
  • the corrosion inhibitor can also used to inhibit the corrosion of a dielectric material, and the dielectric material is, for example, silicon oxide or silicon nitride.
  • the etch rate of the titanium etchant composition to aluminum, chromium, copper, or a combination thereof is, for example, less than 50 A/min; the etch rate of the titanium etchant composition to silicon oxide or silicon nitride is, for example, less than 10 A/min; and the etch rate of the titanium etchant composition to titanium is, for example, greater than 300 A/min.
  • the etch selectivity of titanium to aluminum with the titanium etchant composition is greater than 6, and the etch selectivity of titanium to aluminum with the titanium etchant composition can also be greater than 15.
  • the titanium etchant composition is applicable for a flat panel display, an integrated circuit, a flip chip package, a printed circuit board, a color filter, a micro-electro-mechanical process, or another process comprising etching titanium.
  • the corrosion inhibitor is utilized as an ingredient for the titanium ethcant composition in the present invention, the corrosion caused by the titanium etchant to aluminum and other dielectric materials can be effectively inhibited, so that the integrity of patterns of other films, except the titanium film, can be ensured, and the over etching and the deterioration of the electrical property of the device can be avoided.
  • FIG 1 is a schematic sectional diagram of a bump in a flip chip bonding technique.
  • the present invention provides a titanium etchant composition, which includes HF, corrosion inhibitor, and water.
  • the content of HF is, for example, 0.05 to 49 % by weight, and the content of the corrosion inhibitor is 0.1 to 99.9 t% by weight.
  • the corrosion inhibitor is, for example, sodium silicate, azoles, organic acid, alcohols, ethers, or a mixture thereof.
  • Water can be ultra purified water or deionized water.
  • the azoles is, for example, benzotriazole (BTA) or 2,3,5-triphenyl-2H-tetraazolium chloride (TTC).
  • BTA benzotriazole
  • TTC 2,3,5-triphenyl-2H-tetraazolium chloride
  • an azole alone or a mixture of two of the above azoles can be used.
  • the organic acid is, for example, glycine, histidine (HS), glutamic acid, propylene glycol monomethyl acetate, amino tris (methylenephosphonic acid) (ATMP), or l-hydroxyethylidene-l,l-diphosphonic acid (HEDP).
  • an organic acid alone or a combination of the above organic acids can be used.
  • the alcohols is, for example, ethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, glycerol, butanol, or pentanol.
  • the molecular weight of polyethylene glycol and polypropylene glycol is, for example, 200, 400, 600, 800, 1000, 2000, 4000, and 8000, and preferably, it is for example, 2000.
  • an alcohol alone or a combination of the above alcohols can be used.
  • the ethers is, for example, butyl carbitol, diisopropyl ether, triisopropyl alcohol diether, propylene glycol dimethyl ether, dipropylene glycol monomethyl ether, or dipropylene glycol dimethyl ether.
  • an ether alone or a combination of the above ethers can be used.
  • the corrosion inhibitor can be merely sodium silicate or one of the above organic compounds, or can be any combination of more than two compounds selected from the sodium silicate and the above organic compounds, which is added with HF and water to form a titanium etchant.
  • the corrosion inhibitor is, for example, used to inhibit the corrosion of the titanium etchant to aluminum, chromium, copper, or a combination thereof, and also used to inhibit the corrosion of the etchant to the dielectric material.
  • the dielectric material is, for example, silicon oxide, silicon dioxide, silicon nitride, silicon oxynitride, borophospho silicate glass (BPSG), or phosphosilicate glass (PSG).
  • the etch rate of the titanium etchant of the present invention to aluminum, chromium, copper, or a combination thereof is, for example, less than 50 A/min; the etch rate of silicon oxide or silicon nitride is, for example, less than 10 A/min; and the etch rate of titanium is, for example, greater than 300 A/min.
  • the etch selectivity of titanium to aluminum with the titanium etchant composition is, for example, greater than 6.
  • the etch selectivity of titanium to aluminum with the titanium etchant composition can further be greater than 15.
  • the corrosion inhibitor can be absorbed on the surface of the aluminum film
  • the titanium etchant of the present invention can inhibit the corrosion of the titanium etchant to aluminum and the dielectric material when etching titanium, so that the integrity of patterns of the aluminum film and other dielectric layers can be ensured.
  • the experimental results obtained by etching the test sheet with the titanium etchant composition of the present invention and that obtained by only using HF as an etchant to perform the etching are illustrated below. [0030] [Experiment Procedures]
  • test sheet is fabricated by taking a chip generally used in a semiconductor process as a substrate, and forming a layer of thin film on the substrate.
  • a plurality of sets of test sheets can be fabricated, each set includes 6 test sheets, and each test sheet has a different film formed thereon individually, which includes titanium film test sheet, aluminum film test sheet, chromium film test sheet, copper film test sheet, silicon dioxide film test sheet, and silicon nitride film test sheet respectively.
  • titanium etchant of an experimental example and an etchant of a comparative example the titanium etchant of the experimental example is formed by uniformly mixing 0.5 % by weight of HF, 10-30 % by weight of corrosion inhibitor, and 69.5-89.5 % by weight of water.
  • the proportion of each ingredient for the titanium etchant in each experimental example is listed in Table 1.
  • the etchant of the comparative example is formed by uniformly mixing 0.5 % by weight of HF and
  • a photoresist layer is coated on the film layer of the test sheet, and then, a step of exposing and developing is performed, so as to pattern the photoresist layer on the test sheet, and thus forming a region to be etched on the film.
  • Etch rate of aluminum 1401 (A/min)
  • Etch selectivity of titanium to aluminum 0.9
  • Etch rate of copper 0
  • Etch rate of silicon dioxide 35 (A/min)
  • Etch rate of silicon nitride 15 (A/min)
  • the corrosion inhibitor used in the present invention can indeed achieve the effect of inhibiting the corrosion of aluminum.
  • HF used in the present invention will not etch chromium and copper, and moreover, the corrosion on the dielectric material, such as silicon dioxide and silicon nitride, can be alleviated by adding the corrosion inhibitor.
  • the titanium etchant composition of the present invention can effectively increase the etch selectivity of the titanium to aluminum, chromium, copper, and dielectric materials, so that the technicians in this field can have a preferred control ability for the etching process on titanium, so as to improve the process window.
  • the titanium etchant composition of the present invention can be applied in the various fields, such as a flat panel display (TFT LCD, LTPS, TN, STN, PDP, FED, SED, ELD, and VFD), an integrated circuit, a flip chip package, a printed circuit board, a color filter, a micro-electro-mechanical process, or another process comprising etching titanium.
  • the titanium etchant composition of the present invention can greatly increase the etch selectivity of the titanium to the aluminum, chromium, copper, and dielectric materials, so as to ensure that each film containing aluminum, chromium, copper, and dielectric materials will not be etched by the etchant.
  • the pattern of each film can be arranged according to the original design, and the integrity of the pattern is ensured, so that the device will have desirable electric properties, and thus further enhancing the reliability and stability of the product.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Metallurgy (AREA)
  • Mechanical Engineering (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Internal Circuitry In Semiconductor Integrated Circuit Devices (AREA)
  • Weting (AREA)

Abstract

L'invention porte sur un décapant du titane comportant du HF,un inhibiteur de corrosion et l'eau. La teneur en HF est de 0,05-49 % en poids et celle de l'inhibiteur de corrosion de 0,1-99,9 % en poids. L'inhibiteur de corrosion peut être du silicate de sodium, un azole, un acide organique, des alcools, des éthers, ou leur mélange. Le décapant du titane empêche la surgravure de l'aluminium, du chrome, des matériaux cuivreux et des diélectriques, et conserve les propriétés électriques des dispositifs.
PCT/EP2007/001324 2007-02-15 2007-02-15 Composition d'un décapant du titane WO2008098593A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/EP2007/001324 WO2008098593A1 (fr) 2007-02-15 2007-02-15 Composition d'un décapant du titane

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/EP2007/001324 WO2008098593A1 (fr) 2007-02-15 2007-02-15 Composition d'un décapant du titane

Publications (1)

Publication Number Publication Date
WO2008098593A1 true WO2008098593A1 (fr) 2008-08-21

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8801958B2 (en) 2010-03-30 2014-08-12 Samsung Electronics Co., Ltd. Titanium etchant composition and method of forming a semiconductor device using the same
US9831088B2 (en) 2010-10-06 2017-11-28 Entegris, Inc. Composition and process for selectively etching metal nitrides
CN114855170A (zh) * 2022-04-20 2022-08-05 辽宁轻工职业学院 Ta10钛合金锻件高温淬火组织金相腐蚀剂及配制和使用方法

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2974021A (en) * 1957-02-08 1961-03-07 Borowik Albert Process and composition for chemically treating titanium and its alloys
US3960741A (en) * 1974-08-28 1976-06-01 General Electric Company Etchant for removing metals from glass substrates
US3992235A (en) * 1975-05-21 1976-11-16 Bell Telephone Laboratories, Incorporated Etching of thin layers of reactive metals
US5376236A (en) * 1993-10-29 1994-12-27 At&T Corp. Process for etching titanium at a controllable rate
US5462640A (en) * 1991-04-24 1995-10-31 Kernforschungszentrum Karlsruhe Gmbh Etching solution
US5830280A (en) * 1996-03-15 1998-11-03 Tokyo Electron Limited Washing liquid for post-polishing and polishing-cleaning method in semiconductor process
FR2816528A1 (fr) * 2000-11-14 2002-05-17 Lionel Girardie Procede de gravure selective du cuivre et de nettoyage par face et de la circonference d'un substrat
US20030124851A1 (en) * 2001-12-31 2003-07-03 Lg.Philips Lcd Co., Ltd. Etching solution for etching Cu and Cu/Ti metal layer of liquid crystal display device and method of fabricating the same

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2974021A (en) * 1957-02-08 1961-03-07 Borowik Albert Process and composition for chemically treating titanium and its alloys
US3960741A (en) * 1974-08-28 1976-06-01 General Electric Company Etchant for removing metals from glass substrates
US3992235A (en) * 1975-05-21 1976-11-16 Bell Telephone Laboratories, Incorporated Etching of thin layers of reactive metals
US5462640A (en) * 1991-04-24 1995-10-31 Kernforschungszentrum Karlsruhe Gmbh Etching solution
US5376236A (en) * 1993-10-29 1994-12-27 At&T Corp. Process for etching titanium at a controllable rate
US5830280A (en) * 1996-03-15 1998-11-03 Tokyo Electron Limited Washing liquid for post-polishing and polishing-cleaning method in semiconductor process
FR2816528A1 (fr) * 2000-11-14 2002-05-17 Lionel Girardie Procede de gravure selective du cuivre et de nettoyage par face et de la circonference d'un substrat
US20030124851A1 (en) * 2001-12-31 2003-07-03 Lg.Philips Lcd Co., Ltd. Etching solution for etching Cu and Cu/Ti metal layer of liquid crystal display device and method of fabricating the same

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8801958B2 (en) 2010-03-30 2014-08-12 Samsung Electronics Co., Ltd. Titanium etchant composition and method of forming a semiconductor device using the same
US9831088B2 (en) 2010-10-06 2017-11-28 Entegris, Inc. Composition and process for selectively etching metal nitrides
CN114855170A (zh) * 2022-04-20 2022-08-05 辽宁轻工职业学院 Ta10钛合金锻件高温淬火组织金相腐蚀剂及配制和使用方法

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