CN116479425A - Titanium-containing metal film etching liquid composition and etching method using same - Google Patents

Titanium-containing metal film etching liquid composition and etching method using same Download PDF

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Publication number
CN116479425A
CN116479425A CN202310057524.3A CN202310057524A CN116479425A CN 116479425 A CN116479425 A CN 116479425A CN 202310057524 A CN202310057524 A CN 202310057524A CN 116479425 A CN116479425 A CN 116479425A
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titanium
metal film
containing metal
liquid composition
etching liquid
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朴相承
金良姈
李宝研
郑民敬
金世训
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ENF Technology CO Ltd
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ENF Technology 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
    • C23F1/32—Alkaline compositions
    • C23F1/38—Alkaline compositions for etching refractory metals

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  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Weting (AREA)
  • ing And Chemical Polishing (AREA)

Abstract

The present disclosure relates to an etchant composition for a titanium-containing metal film and a method using the same, which can selectively etch a titanium-containing metal film while not affecting other film qualities in a process of manufacturing a semiconductor and a display device, thereby improving productivity and reliability with improved etching characteristics in a semiconductor manufacturing process.

Description

Titanium-containing metal film etching liquid composition and etching method using same
Technical Field
The present disclosure relates to an etchant composition for a titanium-containing metal film and an etching method using the same, and relates to an etchant composition capable of selectively etching a titanium-containing metal film while not affecting other film qualities in a process of manufacturing a semiconductor and a display device, and a method using the same.
Background
The development of IT technology is accelerating the high performance and miniaturization of portable devices such as mobile phones, digital cameras, MP3, USB memories. In addition, the smart phones currently emerging are evolving towards palm top computers. These products require the same capability as a conventional PC (personal computer), and in order to realize them, technical development for a semiconductor device satisfying ultra-high speed, large capacity, low power consumption, excellent performance, reliability, and the like is required.
A general semiconductor device is manufactured in a unit cell of one transistor and one capacitor, and a transistor of such a semiconductor device generally has a MOS structure. A transistor having such a MOS structure includes a source electrode, a gate electrode, and a drain electrode structure, source and drain electrode terminals are fabricated on a silicon substrate, and a current is caused to flow to the terminals. A voltage may be applied to the gate electrode terminal, and Al is mainly used as a metal in the uppermost layer portion, and silicon oxide is generally used as an oxide film under the metal layer. At this time, in order to achieve smooth flow of current between electrodes, a titanium silicide (TiSi) film is generally used as a wiring to connect a source electrode, a gate electrode, and a drain electrode.
The titanium silicide film described above is formed by forming a titanium film over a substrate over which an active electrode, a gate electrode, and a drain electrode are formed, and annealing the formed titanium film. At this time, since the substrate is exposed to the atmosphere during the annealing process, the titanium film reacts with oxygen or water vapor, so that a titanium oxide film may also be formed. The titanium oxide film formed in this way may cause a problem for the formation of the titanium silicide film due to strong bonding force, and thus may cause a short circuit phenomenon. In addition, as the semiconductor process becomes complicated and miniaturized, the problem of reliability degradation according to such defects is also more and more serious.
Therefore, in order to prevent defects of the titanium silicide film, a process of etching the titanium film is necessary after a process of forming the titanium silicide film. As conventional techniques, an etchant composition composed of hydrofluoric acid, periodic acid, and sulfuric acid is disclosed in patent document 1, and an etchant composition composed of hydrogen peroxide, a fluorine-containing compound, a compound containing both an amino group and a carboxyl group, a nitrate compound, a cyclic amine compound, and water is disclosed in patent document 2. However, although these conventional techniques effectively etch titanium films using fluorine, their effects are insufficient, and there is a problem in that metals other than titanium are etched simultaneously to cause damage to other film qualities. In addition, as a composition for selectively etching a titanium film, an etching liquid composition using a buffer or hydrogen peroxide of high concentration is proposed, but there are still problems of damage to other film qualities and overetching of the titanium film.
Prior art literature
Patent literature
Korean patent laid-open publication KR 10-2000-0028870A
Korean patent laid-open publication KR 10-2011-0019604A
Disclosure of Invention
The purpose of the present disclosure is to provide a titanium-containing metal film etching liquid composition that has an anticorrosive effect on other film qualities that are laminated together while etching a titanium-containing metal film at a rapid etching rate.
The present disclosure is directed to providing an etchant composition capable of stably etching a titanium-containing metal film without causing excessive etching problems of the titanium-containing metal film and titanium residues in an etching process.
An object of the present disclosure is to provide an etching method of a titanium-containing metal film and a manufacturing method of a semiconductor device with improved productivity and reliability by excellent etching characteristics for the titanium-containing metal film and corrosion-release effects for other film qualities.
In order to solve the above-described technical problems, the present disclosure may provide a titanium-containing metal film etching liquid composition including a polyvalent phosphonic acid or salt thereof, an inorganic base, a sulfonic acid-based polymer compound, hydrogen peroxide, and the remaining amount of water.
In one implementation of the present disclosure, the sulfonic acid group polymer compound may have a molecular weight of 10000 to 50000g/mol.
In one implementation of the present disclosure, the sulfonic acid-based polymer compound may be included in an amount of 0.001 to 0.1 wt%.
In one implementation of the present disclosure, the multivalent phosphonic acid or salt thereof may be included in an amount of 0.01 to 5 wt%, relative to the total weight of the composition.
In one implementation of the present disclosure, the inorganic base may be included in an amount of 0.1 to 3 wt% relative to the total weight of the composition.
In one implementation of the present disclosure, the sulfonic acid group polymer compound may be represented by the following chemical formula 1.
[ chemical formula 1]
In the chemical formula 1, R 1 To R 3 Each independently hydrogen and selected from the group consisting of C1-C7 linear or branched alkyl and halogen elements, L is a direct bond or C1-C10 alkylene, said alkylene being-CH 2 -may be substituted with C6-C12 aryl, -C (=o) -, -NR '-or a combination thereof, said R' being hydrogen or C1-C7 alkyl, and n being an integer from 30 to 1000.
In one implementation of the present disclosure, the multivalent phosphonic acid or salt thereof may be included in an amount of 0.01 to 3 wt%, an inorganic base in an amount of 0.5 to 3 wt%, a sulfonic acid-based polymer compound in an amount of 0.001 to 0.1 wt%, hydrogen peroxide in an amount of 15 to 25 wt%, and the remaining amount of water, based on the total weight of the etching solution composition.
The etching solution composition according to an embodiment of the present disclosure may further include a phosphate-based compound.
In one implementation of the present disclosure, the phosphate-based compound may be included in an amount of 0.01 to 2 wt% based on the total weight of the etching solution composition.
In one implementation of the present disclosure, the weight ratio of the phosphate-based compound to the inorganic base may be 1:3 to 1:15.
The etchant composition according to an embodiment of the present disclosure may not include a quaternary ammonium salt.
The pH of the etching solution composition according to an embodiment of the present disclosure may be 7 to 11.
In addition, the present disclosure may provide an etching method including a step of contacting the above-described etching liquid composition onto a titanium-containing metal film.
Further, the present disclosure may provide a method of manufacturing a semiconductor device including a step of forming a titanium-containing metal film on a substrate where an active electrode, a gate electrode, and a drain electrode are formed, and a step of etching the metal film with the above-described etchant composition.
The method of manufacturing a semiconductor device according to an embodiment of the present disclosure may further include, after the step of forming the titanium-containing metal film: and forming a single film or a plurality of films of two or more kinds selected from one of a silicon insulating film and a second metal film on a part of the surface of the metal film.
In an implementation of the present disclosure, the second metal film may be a single film or a multi-layered film including one or more metals selected from copper, molybdenum, tungsten, titanium, tantalum, chromium, neodymium, niobium, nickel, indium, and tin.
The method for manufacturing a semiconductor device according to an embodiment of the present disclosure may further include, after the step of etching: and annealing the titanium-containing metal film.
According to the present disclosure, not only a titanium-containing metal film but also an anticorrosive effect for other metal films including a silicon insulating film or a copper-based metal film or the like can be selectively etched rapidly.
According to the present disclosure, the pH variation in the chemical liquid is reduced by the realization of stable etching characteristics, and the bubble generation problem according to the decomposition of hydrogen peroxide can also be solved. Further, quaternary ammonium salts that may cause overetching or residues to the titanium-containing metal film due to reaction with hydrogen peroxide may not be included, so that the titanium-containing metal film may be etched more stably.
According to the present disclosure, by minimizing damage to upper and lower films such as silicon wafers, silicon insulating films, copper-based metal films, etc., a subsequent process can be stably performed.
In particular, according to the present disclosure, a titanium film can be provided that is precisely controlled without damage to the upper and lower films described above. In this regard, defects of the electrical device characteristics, which may be exemplified by short circuits, poor wiring, or a decrease in luminance, which may occur in a subsequent process, may be prevented.
The etchant composition according to the present disclosure can be usefully utilized with an etching process by selective etching of a titanium film and a manufacturing method of a semiconductor device including such an etching process.
Drawings
Fig. 1 shows a Scanning Electron Microscope (SEM) image of a copper film etched by the etching liquid composition of comparative example 1 according to the present disclosure.
Fig. 2 shows a Scanning Electron Microscope (SEM) image of a copper film that has not been etched by the etching liquid composition according to example 1 of the present disclosure.
Detailed Description
Hereinafter, an etching liquid composition for etching a titanium-containing metal film while not affecting the metal film in the process of manufacturing a semiconductor and a display device, an etching method using the same, and a semiconductor device manufacturing method will be described.
At this time, for technical and scientific terms used, if there is no other definition, it has a meaning commonly understood by one of ordinary skill in the art to which the present disclosure belongs, and descriptions of well-known functions and configurations that may unnecessarily obscure the gist of the present disclosure are omitted in the following description and drawings.
As used in this specification, the singular forms may be intended to include the plural forms as well, if the context does not indicate specifically.
Furthermore, units used in the present specification without particular mention are on a weight basis, and as an example,% or ratio units means weight% or weight ratio, unless otherwise defined, weight% means the weight% occupied by any one component in the entire composition within the composition.
Further, numerical ranges used in this specification include lower and upper limits and all values within the range, logically derived increments from the form and width of the defined range, all values defined therebetween, and all possible combinations of upper and lower limits of the numerical ranges defined as different forms from each other. Unless specifically defined otherwise in the description of the present disclosure, values outside the numerical range that may occur due to experimental error or rounding of values are also included within the numerical range that is defined.
In addition, the term "comprising" in this specification is an open-ended description having the meaning equivalent to the expression "comprising," "including," "having," or "characterized by," and does not exclude elements, materials, or processes not otherwise listed.
In addition, the term "substantially not including" in the present specification means that other elements, materials or processes not listed together with a specific element, material or process may not be present in an amount or degree that does not create an unacceptably significant effect on at least one basic and novel technical idea disclosed.
Hereinafter, the present disclosure will be specifically described.
The titanium-containing metal film etching liquid composition according to an embodiment of the present disclosure may include polyvalent phosphonic acid or a salt thereof, an inorganic base, a sulfonic acid-based polymer compound, hydrogen peroxide, and the remaining amount of water.
Hereinafter, in the present specification, polyvalent phosphonic acid may mean polyvalent phosphonic acid and/or polyvalent phosphonate. In particular, the multivalent phosphonate may be an alkali metal, alkaline earth metal or ammonium salt of multivalent phosphonic acid. Specific examples of the alkali metal salt or alkaline earth metal salt may be sodium salt, potassium salt, calcium salt or magnesium salt. In an embodiment of the present disclosure, the multivalent phosphonic acid may comprise a multivalent phosphonic acid sodium salt or a multivalent phosphonic acid potassium salt.
In the titanium film etching liquid composition according to an embodiment of the present disclosure, the polyvalent phosphonic acid may be included in an amount of 0.005 to 5 wt% relative to the total weight of the composition. Specifically, it may be 0.005 to 3 wt%, 0.01 to 2.5 wt%, or 0.01 to 2 wt%. At this time, with inclusion in the content range, the effects of improved etching rate and etching residue cleaning performance of the titanium film can be provided.
In the present disclosure, the polyvalent phosphonic acid may chelate titanium ions to inhibit the mobility of the titanium ions so as to prevent the titanium ions dissolved in the etching liquid at the time of etching from being adsorbed again onto the substrate surface. With the use of polyvalent phosphonic acids, etching phenomena of other metal films that may occur when an excess of organic acid is used for etching can be minimized. The multivalent phosphonic acid may be a bisphosphonic acid, a triphosphonic acid, a tetraphosphonic acid. Specifically, an example of the bisphosphonic acid may be hydroxyethylidene bisphosphonic acid.
In this case, the polyvalent phosphonic acid may comprise an alkali metal salt of a polyvalent phosphonic acid.
In the etching liquid composition according to an embodiment of the present disclosure, the inorganic base may function as a pH adjustor, and as a non-limiting example of the inorganic base, may be selected from sodium hydroxide, potassium hydroxide, sodium carbonate, and the like, and in particular, may be preferably a hydroxide salt.
The inorganic base may be included in an amount of 0.1 to 3.0 wt%, 0.5 to 2.8 wt%, 1.0 to 2.8 wt%, or 1.5 to 2.7 wt% with respect to the total weight of the metal film etching liquid composition. With use in the above range, occurrence of titanium residues is prevented, and an effect of suppressing etching of other metals is excellently exhibited.
Although the amount to be used may be adjusted depending on pH, in the case where the total weight of the comparative composition is added beyond the above range, the etching rate and surface uniformity may be lowered, and thus may be inappropriate.
The sulfonic acid group polymer compound can provide an effect of suppressing etching defects by preventing overetching of a titanium film. The sulfonic acid group-containing polymer compound as a combination of repeating units containing a sulfonic acid group may be a polymer of the same repeating unit or a copolymer of different repeating units. The morphology constituting the copolymerization may include random copolymers, alternating copolymers, block copolymers, graft copolymers, and the like. The random copolymer has, for example, a morphology in which the order of arrangement of the monomers of the first monomer, the second monomer, and the like is unidentified irregular arrangement, the alternating copolymer has a morphology in which the respective monomers are alternately arranged, the block copolymer has a morphology in which the respective monomers form blocks, and the graft copolymer has a morphology in which one monomer has a skeleton chain structure and the other monomer is bonded in a branched form.
The molecular weight of the sulfonic acid group high molecular compound may be 10000 to 80000g/mol, 10000 to 50000g/mol, 15000 to 40000g/mol, or 20000 to 30000g/mol. Here, unless otherwise indicated, the molecular weights are based on the number average molecular weight (Mn). In this case, the polymer compound can be well dissolved in the etching liquid, and overetching can be effectively suppressed to exert uniform etching characteristics. In the case where the molecular weight is less than 10000g/mol, it is difficult to suppress overetching of the titanium film, and in the case where the molecular weight exceeds the above range, the polymer compound is not well dissolved in the etching liquid and is widely adsorbed onto the substrate, and defects due to the occurrence of residues may occur, and thus may be unsuitable.
The sulfonic acid group polymer compound may be contained in an amount of 0.001 to 0.1% by weight, specifically, 0.01 to 0.1% by weight, relative to the total composition weight. In this case, the sulfonic acid functional group chelates titanium ions, thereby suppressing the occurrence of titanium residues, and is advantageous in terms of the protective effect of other metal films. In the case where the sulfonic acid group polymer compound is contained in an amount exceeding 0.1% by weight, the stability of the etching solution may be lowered, and thus it is not appropriate.
The sulfonic acid-based polymer compound according to a preferred embodiment of the present disclosure, as a homopolymer, may be represented by the following chemical formula 1.
[ chemical formula 1]
In the chemical formula 1, R 1 To R 3 Each independently hydrogen and selected from the group consisting of C1-C7 linear or branched alkyl and halogen elements, L is a direct bond or C1-C10 alkylene, said alkylene being-CH 2 Can be substituted by a C6-C12 aryl, -C (=O) -, -NR '-or a combination thereof, said R' being hydrogen or a C1-C7 alkyl,and n is an integer of 30 to 1000.
More specifically, in the chemical formula 1, R 1 To R 3 Each independently is hydrogen, L is a direct bond or C1-C7 alkylene, the alkylene groups being-CH 2 -may be substituted with C6-C12 aryl, -C (=o) -, -NR '-or a combination thereof, said R' being hydrogen and n being an integer from 40 to 600.
The other form of the sulfonic acid-based polymer compound may be, for example, poly (2-acrylamide-2-methyl-1-propanesulfonic acid-co-acrylonitrile) acrylonitrile or poly (4-styrenesulfonic acid-co-maleic acid), but is not limited thereto.
Examples of the form of the preferable homopolymer of the sulfonic acid-based polymer compound may be polystyrene sulfonic acid (poly (4-styrenesulfonic acid), PSS), polyanisole sulfonic acid (poly (anetholesulfonic acid), PAS), polyethylene sulfonic acid (poly (vinylsulfonic acid), PVS), or polyacrylamide-2-methyl-1-propane sulfonic acid (poly (2-acrylamido 2-methyl-1-propanesulfonic acid), PAMPS), but are not limited thereto.
The water contained in the etching liquid composition is not particularly limited, but may specifically be deionized water, and more specifically, as deionized water for semiconductor process, the specific resistance value thereof may be 18mΩ·cm or more.
In the etching solution composition according to an embodiment of the present disclosure, as stable etching characteristics are achieved, the variation in pH of the chemical solution in repeated etching processes may also be small. Specifically, the pH of the titanium film etching liquid composition according to an embodiment of the present disclosure may be 7 to 11, more specifically 8 to 10.
The etchant composition according to an embodiment of the present disclosure may simultaneously satisfy the following content ranges. Specifically, the polyvalent phosphonic acid may be contained in an amount of 0.005 to 3% by weight, an inorganic base in an amount of 0.5 to 3% by weight, a sulfonic acid-based polymer compound in an amount of 0.001 to 0.1% by weight, hydrogen peroxide in an amount of 15 to 25% by weight, and the remaining amount of water, based on the total weight.
More specifically, the etching liquid composition according to the present disclosure may include 0.01 to 2 wt% of polyvalent phosphonic acid, 1.5 to 3 wt% of an inorganic base, 0.01 to 0.1 wt% of a sulfonic acid-based polymer compound, 15 to 23 wt% of hydrogen peroxide, and the remaining amount of water.
The etching solution composition according to an embodiment of the present disclosure may further include a phosphate-based compound. Specifically, the phosphate-based compound may be contained in an amount of 0.01 to 1% by weight or 0.05 to 0.5% by weight based on the whole composition. The phosphate-based compound may comprise a first sodium phosphate (NaH 2 PO 4 ) Second sodium phosphate (Na) 2 HPO 4 ) Sodium third phosphate (Na) 3 PO 4 ) First potassium phosphate (KH) 2 PO 4 ) Second potassium phosphate (K) 2 HPO 4 ) First ammonium phosphate ((NH) 4 )H 2 PO 4 ) Second ammonium phosphate ((NH) 4 ) 2 HPO 4 ) Ammonium phosphate third ((NH) 4 ) 3 PO 4 ) Or a combination of two or more thereof. Preferably, it may be a first potassium phosphate (KH 2 PO 4 ) Second potassium phosphate (K) 2 HPO 4 ) Or a combination thereof. In this case, the etching rate may be adjusted so as to enable uniform etching.
In the etching solution composition according to an embodiment of the present disclosure, the content ratio of the phosphate-based compound and the inorganic base may be specifically 1:3 to 1:15, and more specifically 1:5 to 1:12, on a weight basis.
More specifically, the etching liquid composition according to the present disclosure may include 0.01 to 2 wt% of polyvalent phosphonic acid, 1.5 to 3 wt% of an inorganic base, 0.01 to 0.1 wt% of a sulfonic acid-based polymer compound, 15 to 23 wt% of hydrogen peroxide, 0.1 to 1 wt% of a phosphate-based compound, and the remaining amount of water. In the present disclosure, with the combination of the above-described proper mixing ratios, the excessive etching of the titanium film is not induced while the etching of other metal films is suppressed to the maximum, so that excellent etching selectivity can be provided.
Meanwhile, the etching solution composition according to an embodiment of the present disclosure may substantially not include the quaternary ammonium salt. In the case where the etching liquid composition contains a quaternary ammonium salt, the etching rate for the titanium film is drastically increased, and thus overetching may be caused, which is not preferable. For example, the quaternary ammonium salt may be tetraalkylammonium hydroxide, trialkylarylammonium hydroxide, or the like, and specifically may be tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetrahexylammonium hydroxide, tetraoctylammonium hydroxide, benzyltriethylammonium hydroxide, diethyldimethylammonium hydroxide, or methyltributylammonium hydroxide, but is not limited as long as it has a quaternary ammonium salt form. Here, the alkyl group may be a C1-C8 alkyl group, and the aryl group may be a C6-C12 aryl group.
In the etching solution composition according to an embodiment of the present disclosure, an etching object of the etching solution composition is a pure titanium film. According to the present disclosure, etching or damage is not generated to the upper film or the lower film represented by the silicon insulating film or the copper-based metal film or the like other than the titanium film. Accordingly, defects of the characteristics of the electrical device, which may be exemplified by a short circuit, a poor wiring, or a reduction in luminance, which may occur in a subsequent process, may be effectively prevented.
The silicon insulating film may be one or a combination of two or more selected from a silicon nitride film, a silicon oxide film, and the like.
As an example, the silicon nitride may be a SiNx film, a SiON film, a doped SiNx film (doped SiN layer), or the like.
As an example, the silicon oxide may be a spin-on dielectric (SOD, spin On Dielectric) film, a high density plasma (HDP, high Density Plasma) film, a thermal oxide film (thermal oxide), borophosphosilicate glass (BPSG, borophosphate Silicateglass) film, phosphosilicate glass (PSG, phospho Silicateglass) film, borosilicate glass (BSG, boro Silicateglass) film, polysilazane (PSZ, polysilazane) film, fluorinated silicate glass (FSG, fluorinated Silicateglass) film, low pressure tetraethyl orthosilicate (LP-TEOS, low Pressure Tetra Ethyl Ortho Silicate) film, plasma enhanced tetraethyl orthosilicate (PETEOS, plasma Enhanced Tetra Ethyl Ortho Silicate) film, high temperature oxide (HTO, high Temperature Oxide) film, medium temperature oxide (MTO, medium Temperature Oxide) film, undoped silicate glass (USG, undopped Silicateg)Glass) film, spin On Glass (SOG) film, advanced planarization layer (APL, advanced Planarization Layer) film, atomic layer deposition (ALD, atomic Layer Deposition) film, PE-oxide film (Plasma Enhanced oxide) or O 3 Tetraethyl orthosilicate (O) 3 -TEOS，O 3 Tetra Ethyl Ortho Silicate), etc.
The copper-based metal film may be a single film composed of copper or a copper alloy, or a multilayer film in which two or more of the single films are laminated.
As an example, the copper alloy may be used without limitation as long as it is a metal that can be used for an electrode of a semiconductor device, and as a non-limiting example thereof, one or two or more selected from molybdenum, tungsten, titanium, tantalum, chromium, neodymium, niobium, nickel, indium, tin, and the like may be used.
The present disclosure also describes the use of the titanium-containing metal film etching liquid composition described above.
An aspect of the present disclosure may be a method of etching a titanium-containing metal film comprising the step of contacting the etching liquid composition onto the titanium-containing metal film.
Further, an aspect of the present disclosure may be a method of manufacturing a semiconductor device including a step of forming a titanium-containing metal film on a substrate where an active electrode, a gate electrode, and a drain electrode are formed, and a step of etching the metal film using the above-described etching liquid composition.
According to the present disclosure, when selectively etching a titanium film that is used as a diffusion preventing metal film or the like of a semiconductor device, an upper film or a lower film that may be exemplified as a silicon wafer, a silicon insulating film, a copper-based metal film or the like can be effectively prevented from being etched together, and only the titanium film can be selectively etched. In addition, the re-adsorption of titanium ions which may be generated in the etching process can be prevented, and the titanium residues which may be generated thereby can be effectively removed by being effectively dissolved in the chemical liquid, and thus damage to the upper film or the lower film can be minimized. In this regard, according to the present disclosure, electrical and physical defects that may be generated in an etching process may be minimized, thereby achieving stable device characteristics. In addition, it is commercially advantageous.
The method of manufacturing a semiconductor device according to an embodiment of the present disclosure may further include, after the step of forming the titanium-containing metal film: and forming a single film or a plurality of films of two or more kinds selected from one of a silicon insulating film and a second metal film on a part of the surface of the metal film.
The second metal film may be a copper-based metal film, the copper-based metal film may be a single film composed of copper or a copper alloy or a multilayer film in which two or more of the single films are laminated, and the copper alloy may include one or more selected from molybdenum, tungsten, titanium, tantalum, chromium, neodymium, niobium, nickel, indium, tin, and the like, in addition to copper.
The method of manufacturing a semiconductor device according to an embodiment of the present disclosure may further include, after the step of etching: and annealing the titanium-containing metal film. By the steps, a titanium silicide film can be formed, and the step of etching according to the present disclosure can be performed to prevent cracks that may occur in the step of annealing. That is, according to the present disclosure, a titanium silicide film having further improved performance can be provided.
Hereinafter, the etching liquid composition for titanium-containing metal films according to the present disclosure will be described in more detail by way of examples. However, the following examples are merely references for the detailed description of the present disclosure, which is not limited thereto, and may be implemented in various forms.
Examples 1 to 10 and comparative examples 1 to 5
An etching solution composition (8 kg) was prepared by the components and contents shown in Table 1 below.
TABLE 1
FB225469KR-I
(evaluation method)
1. Etching characteristics
Preparation on silicon waferOn which a titanium film is deposited as a single film, respectively>Silicon oxide film->Copper film->Is a substrate of a substrate (a). A photolithography process of a predetermined pattern was applied thereto, and the patterned glass was cut into 5×5cm with a diamond blade to prepare a test piece.
The etching liquid compositions according to the content combinations described in examples and comparative examples of table 1 were prepared to 8kg. Each of the prepared etchant compositions was placed in an experimental apparatus of a jet etching system, the temperature was set at 32 ℃ and heated, and then an etching process was performed when the temperature was reached. For the total etch time, the overetch was performed at 100% based on end point detection (End Point Detection, EPD). After the etching was completed, after washing with distilled water 3 times, each film thickness change was confirmed by an Ellipsometer (SE-MG-1000), to evaluate etching characteristics.
2. Titanium residue level
The samples obtained by the etching characteristic evaluation method were evaluated for the titanium residue level according to the following criteria.
Reference 1 titanium residue level
-no residue: o (circle)
-the amount of residues is 1-10: and (V)
-the amount of residue exceeds 10 per multiple: x is X
3. Whether or not the metal film (copper film) is etched
The samples obtained by the etching characteristics evaluation method were evaluated for whether or not other metal films (copper films) were etched, according to the following criteria.
Reference 2 etching rate of other metal film (copper film)
-no etching: o (circle)
-Is defined in the following range: and (V)
-exceeding ofⅩ
TABLE 2
TABLE 3
Referring to the table 2, when an example of using an etching solution composition comprising 0.01 to 3 wt% of polyvalent phosphonic acid, 0.5 to 3 wt% of inorganic base, 0.01 to 0.1 wt% of sulfonic acid-based polymer compound, 15 to 25 wt% of hydrogen peroxide, and the remaining amount of water according to the present disclosure was observed, in all cases, even if overetching was performed at 100%, overetching of the titanium film did not occur. Further, no titanium residue was found, and as shown in fig. 2, it was confirmed that the protective effect against other metal films was excellent in terms of not exhibiting etching against the copper film, and the selectivity was excellent.
In contrast, in the case of the etching solution composition of comparative example described in table 3, when overetching was performed at 100%, overetching was caused in all cases except comparative example 4. In comparative example 4, to which no inorganic base was added, etching did not occur. Further, it was confirmed that a plurality of titanium residues remained at the time of etching according to the comparative example, and as also shown in fig. 1, not only the titanium film but also the copper film deposited together therewith was etched, and thus it was not suitable for the protection of other metal films such as the copper film.
As described above, the description has been given in the present disclosure by way of specific matters and the defined examples and comparative examples, but this is provided to facilitate a more comprehensive understanding of the present disclosure, the present disclosure is not limited to the above-described examples, and various modifications and variations can be made by those skilled in the art to which the present disclosure pertains. Therefore, the ideas of the present disclosure should not be limited to the illustrated embodiments, but the appended claims and the modifications equivalent or equivalent to the claims should all fall within the scope of the ideas of the present disclosure.

Claims (17)

1. A titanium-containing metal film etching liquid composition comprising polyvalent phosphonic acid or a salt thereof, an inorganic base, a sulfonic acid-based polymer compound, hydrogen peroxide and the remaining amount of water.
2. The titanium-containing metal film etching liquid composition according to claim 1, wherein the molecular weight of the sulfonic acid group-containing polymer compound is 10000 to 50000g/mol.
3. The titanium-containing metal film etching liquid composition according to claim 1, comprising 0.001 to 0.1% by weight of the sulfonic acid group-containing polymer compound.
4. The titanium-containing metal film etching liquid composition as claimed in claim 1, comprising 0.01 to 5% by weight of the polyvalent phosphonic acid or salt thereof relative to the total weight of the composition.
5. The titanium-containing metal film etching liquid composition as claimed in claim 1, comprising 0.1 to 3% by weight of the inorganic base relative to the total weight of the composition.
6. The titanium-containing metal film etching liquid composition according to claim 1, wherein the sulfonic acid group polymer compound is represented by the following chemical formula 1,
[ chemical formula 1]
In the chemical formula 1, R 1 To R 3 Each independently hydrogen and selected from the group consisting of C1-C7 linear or branched alkyl and halogen elements, L is a direct bond or C1-C10 alkylene, said alkylene being-CH 2 -may be substituted with C6-C12 aryl, -C (=o) -, -NR '-or a combination thereof, said R' being hydrogen or C1-C7 alkyl, and n being an integer from 30 to 1000.
7. The titanium-containing metal film etching liquid composition according to claim 1, comprising 0.01 to 3% by weight of the polyvalent phosphonic acid or salt thereof, 0.5 to 3% by weight of an inorganic base, 0.001 to 0.1% by weight of a sulfonic acid-based polymer compound, 15 to 25% by weight of hydrogen peroxide, and the remaining amount of water, based on the total weight of the etching liquid composition.
8. The titanium-containing metal film etching liquid composition as claimed in claim 1, further comprising a phosphate-based compound.
9. The titanium-containing metal film etching liquid composition according to claim 8, comprising 0.01 to 2% by weight of the phosphate-based compound, based on the total weight of the etching liquid composition.
10. The titanium-containing metal film etching liquid composition as claimed in claim 8, wherein the weight ratio of the phosphate-based compound to the inorganic base is 1:3 to 1:15.
11. The titanium-containing metal film etching liquid composition according to claim 1, which does not contain a quaternary ammonium salt.
12. The titanium-containing metal film etching liquid composition as claimed in claim 1, having a pH of 7 to 11.
13. A method of etching a titanium-containing metal film, comprising:
contacting the etchant composition according to claim 1 onto a titanium-containing metal film.
14. A method of manufacturing a semiconductor device, comprising:
forming a titanium-containing metal film on a substrate on which an active electrode, a gate electrode, and a drain electrode are formed; and
etching the metal film with the etching liquid composition according to claim 1.
15. The method for manufacturing a semiconductor device according to claim 14, further comprising, after the step of forming the titanium-containing metal film:
a single film or a plurality of films of two or more kinds selected from one of a silicon insulating film and a second metal film are formed on a part of the surface of the metal film.
16. The method for manufacturing a semiconductor device according to claim 14, wherein the second metal film is a single film or a multilayer film containing one or more metals selected from copper, molybdenum, tungsten, titanium, tantalum, chromium, neodymium, niobium, nickel, indium, and tin.
17. The method for manufacturing a semiconductor device according to claim 14, further comprising, after the step of etching:
annealing the titanium-containing metal film.
CN202310057524.3A 2022-01-21 2023-01-20 Titanium-containing metal film etching liquid composition and etching method using same Pending CN116479425A (en)

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KR10-2022-0188334 2022-12-29
KR1020220188334A KR20230113150A (en) 2022-01-21 2022-12-29 Etchant composition for titanium-containing metal layer and etching method of titanium-containg metal layer using the same

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