WO2020197056A1 - Composition for etching laminate of titanium nitride film and tungsten film, and method for etching semiconductor device by using same - Google Patents

Composition for etching laminate of titanium nitride film and tungsten film, and method for etching semiconductor device by using same Download PDF

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WO2020197056A1
WO2020197056A1 PCT/KR2019/018730 KR2019018730W WO2020197056A1 WO 2020197056 A1 WO2020197056 A1 WO 2020197056A1 KR 2019018730 W KR2019018730 W KR 2019018730W WO 2020197056 A1 WO2020197056 A1 WO 2020197056A1
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etching
acid
composition
titanium nitride
ammonium
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PCT/KR2019/018730
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French (fr)
Korean (ko)
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변지훈
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에스케이머티리얼즈 주식회사
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K13/00—Etching, surface-brightening or pickling compositions
    • C09K13/04—Etching, surface-brightening or pickling compositions containing an inorganic acid
    • C09K13/06—Etching, surface-brightening or pickling compositions containing an inorganic acid with organic 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
    • H01L21/31—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
    • 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
    • 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
    • H01L21/324—Thermal treatment for modifying the properties of semiconductor bodies, e.g. annealing, sintering

Definitions

  • the present invention relates to a composition for etching a titanium nitride layer and a tungsten layer stack, and a method for etching a semiconductor device using the same, and more particularly, a tungsten layer for a titanium nitride layer can be etched at the same etching rate, and even during long-term storage.
  • the present invention relates to a composition for etching a titanium nitride layer and a tungsten layer laminate without lowering the etching rate, and a method for etching a semiconductor device using the same.
  • MOS transistor has a source electrode, a gate electrode, and a drain electrode structure.
  • a semiconductor circuit pattern is manufactured by selectively removing unnecessary portions using a liquid or gas etchant on a wafer.
  • a semiconductor structure is formed by repeating the process of forming a desired circuit pattern on a thin film of several layers constituting a semiconductor.
  • the etching process includes wet etching and dry etching depending on the state of the material causing the etching reaction.
  • Dry etching proceeds phenomenally by a chemical reaction between an element present in the plasma and a surface material, and by promoting a reaction due to the collision of the active species particles present in the plasma.
  • the plasma reaction that occurs during dry etching consists of the generation of active particles in the plasma, movement and adsorption of the active particles to the etching surface, chemical reactions with surface materials, and separation of reaction products.
  • wet etching is a method of etching using a chemical solution that can be dissolved by chemically reacting with the film to be etched.
  • a chemical reaction that occurs at this time will dissociate hydrofluoric acid to be separated into hydrogen ions and fluorine ions, and the separated fluorine ions react with the oxide film to perform etching.
  • a titanium nitride film which is a titanium-based metal together with tungsten or tungsten-based metal, undergoes a patterning process in which unnecessary portions are selectively removed using a gaseous or liquid corrosion solution.
  • the titanium nitride film In the prior art, a mixed solution of phosphoric acid, nitric acid, and acetic acid was used as an etching composition to etch the tungsten and tungsten films at a constant etching rate. When wet etching using the above etching composition, the etching rate is significantly low, which is not preferable in terms of time and economy.
  • the titanium nitride film (TiN) and the tungsten film (W) are kept at a high etching rate, and the etch selectivity is 1, and there is no decrease in the etch rate even during long-term storage, and there is no damage to the insulating film. Development is required.
  • the composition for etching contains sulfuric acid and hydrogen peroxide
  • sulfuric acid and hydrogen peroxide react to form Caro's acid (H 2 SO 5 ).
  • the carboxylic acid formed as described above may cause damage to the insulating layer (Al 2 O 3 ) and also affect storage stability, so that the etching rate of the tungsten and titanium nitride layers decreases during long-term storage.
  • Korean Patent Laid-Open Publication No. 10-2015-0083605 (published date: 2015.07.20.) relates to a method of forming a conductive pattern and a method of manufacturing a semiconductor device using the same, including phosphoric acid, nitric acid, auxiliary It has been described for a wet etching process using an etching composition containing an oxidizing agent and excess water and having the same etching rate for metal nitride and metal.
  • an acid ammonium compound, a halogen acid compound, or a sulfuric acid compound is used as an auxiliary oxidizing agent.
  • Korean Patent Laid-Open No. 10-2015-0050278 discloses (a) 50 to 80% by weight of phosphoric acid, (b) 5 to 20% by weight of nitric acid, (c) 0.01 to 10% by weight of an ammonium compound, and (d) the balance of the solvent.
  • An etching composition for a laminate of a titanium nitride film and a tungsten film is known.
  • Korean Patent Publication No. 10-1695571 relates to a composition for etching a hydrogen peroxide-based metal, and more specifically, a hydrogen peroxide-based composition capable of preventing decomposition of hydrogen peroxide and degeneration of other components in a composition for etching a hydrogen peroxide-based metal. It has been described for a composition for etching metal.
  • the prior art still has the same etch selectivity for the titanium nitride film (TiN) and tungsten film (W), the etch rate is significantly low, which is not desirable in terms of time and economy. There is a problem that the etch rate is lowered.
  • another object of the present invention is to provide a method of etching a titanium nitride layer and a tungsten layer using the etching composition.
  • the present invention provides (a) 20 to 75% by weight of phosphoric acid, (b) 1 to 30% by weight of hydrogen peroxide, (c) 1 to 50% by weight of water, (d) 0 to 5% by weight of ammonium compounds, (e) It provides a composition for simultaneous etching of a titanium nitride film and a tungsten film, comprising 0 to 10% by weight of a chelating agent.
  • the etching composition may be characterized in that 0.01-2wt% of a known additive is further added relative to the total weight of the etching composition.
  • the ammonium compound is ammonium sulfate, ammonium persulfate, ammonium hydroxide, ammonium chloride, ammonium phosphate, ammonium nitrate, ammonium bisulfate It may be any one or more selected from (ammonium bisulfate), preferably ammonium nitrate (Ammonium nitrate).
  • the chelating agents are arginine, histidine, lysine, aspartic acid, glutamic acid, glutamine, serine, threonine, and asparagine.
  • Asparagine Cysteine, Glycine, Proline, Serenocysteine, Alanine, Tyrosine, Valine, Tryptophane, Leucine, Phenylalanine, Methionine, (ethylenedinitrilo)tetraacetic acid (EDTA), butylenediaminetetraacetic acid, (1,2-cyclohexylenedinitrilo-)tetraacetic acid (cyDTA), diethylenetri Amine pentaacetic acid (DETPA), ethylenediaminetetrapropionic acid, (hydroxyether)ethylenediaminetriacetic acid (HEDTA), N,N,N',N'-ethylenediaminetetra(methylenephosphonic) acid (EDTMP), triethylene Tetraminehexaacetic acid (TTHA),
  • the ammonium compound may be contained in an amount of 0.01 to 2% by weight and the chelating agent in an amount of 0.01 to 5% by weight, in which case, the ammonium compound is ammonium nitrate, and the chelating agent is citric acid. acid) and glycine.
  • the present invention provides a method for etching a semiconductor device, characterized in that the etching composition of the present invention is used in the step of simultaneously etching a titanium nitride film and a tungsten film in a semiconductor device including a titanium nitride film and a tungsten film.
  • the etching of the semiconductor device may be performed in a temperature range of 30 to 80°C.
  • the composition for etching a laminate of a titanium nitride film and a tungsten film according to the present invention maintains a high etching rate for the titanium nitride (TiN) film and the tungsten (W) film in the manufacturing process of a semiconductor device, while the etching selectivity of the titanium nitride and tungsten film. Can be made close to 1, there is no decrease in the etching rate even when stored for a long period of time, and has the characteristics of minimizing damage to high-k insulating films such as Al 2 O 3 .
  • TiN titanium nitride
  • W tungsten
  • composition for etching a titanium nitride film and a tungsten film laminate according to the present invention does not have an effect on other film qualities in the vicinity during wet etching, and has an excellent etching rate selectively only for the film to be etched, and has a high dielectric constant such as Al 2 O 3. It has the advantage of minimizing damage to the insulating film.
  • the titanium nitride (TiN, titanium nitride) film and the tungsten (W) film mentioned in the present invention may have a structure in which a single layer or a multi-layer is stacked as a thin film or a thick film through deposition or coating on a semiconductor substrate.
  • the titanium nitride (TiN, titanium nitride) film (or layer) is defined as a titanium nitride film
  • the film (or layer) made of tungsten is defined as a tungsten film.
  • the other film quality mentioned in the specification of the present invention refers to a film made of a material other than the titanium nitride film and the tungsten film present on the pattern during the semiconductor manufacturing process, and may be an insulating film or a protective film, specifically aluminum oxide (hereinafter , Al 2 O 3 ) It may be an insulating film made of a film.
  • the Al 2 O 3 insulating layer has a higher dielectric constant (high-k) than the conventional gate insulating layer of silicon oxide (SiO 2 ), so it can be driven at a low voltage and has a larger band gap than other materials with higher dielectric constants.
  • the properties are also excellent and may be located under or on the side of the titanium nitride and tungsten films.
  • composition for etching by wet etching is selected in consideration of film uniformity maintenance, high etching rate, and excellent selectivity, and has no or minimized influence on other film qualities other than the intended to be etched. Should be.
  • etching composition used in actual wet etching, as a material with high acid or basicity is used, it may attack other adjacent layers or insulating layers, causing damage to the film quality. If hydrogen peroxide is included in the etching composition Side reactions between hydrogen peroxide and other components in the composition may occur, and stability may be degraded, such as hydrogen peroxide decomposition during long-term storage, resulting in poor semiconductor products.
  • the titanium nitride layer and the tungsten layer are etched at a high rate while minimizing the effect on the Al 2 O 3 insulating layer during the etching process, while the etching selectivity, which is the ratio of the etching rates for the titanium nitride layer and the tungsten layer, is almost the same.
  • a composition for etching that can be maintained at preferably 1 is provided.
  • the present invention may optionally further include (d) an ammonium compound and/or (e) a chelating agent in the etching composition comprising (a) phosphoric acid, (b) hydrogen peroxide, and (c) water.
  • additives may be added to the composition for etching to further improve the effect of the invention.
  • the additive includes all of a variety of conventional additives known in the art, such as surfactants, boron compounds, inorganic oxides, polyhydric alcohols, azole compounds, and phosphates, in order to further improve the effects of the invention.
  • the additive may be added in an amount of about 0.01 to 2 wt% based on the total weight of the etching composition.
  • phosphoric acid may act as a main etching component for etching the nitride film in the composition, and hydrogen ions are provided in the composition to accelerate etching.
  • the phosphoric acid may be included in an amount of 20 to 75% by weight, preferably 25 to 75% by weight, more preferably 25 to 70% by weight, and most preferably 30 to 70% by weight, based on the total weight of the etching composition.
  • the etching rate of tungsten in the etching composition is controlled according to the content of hydrogen peroxide, water, and phosphoric acid, and the etching rate increases as the content of hydrogen peroxide and water increases, and the etching rate is suppressed as the content of phosphoric acid increases.
  • hydrogen peroxide is one of the main components that etch the titanium nitride layer and the tungsten layer, and has a strong oxidizing power and may cause an oxidation reaction with other compounds in the composition. Since the hydrogen peroxide can obtain a poor etching profile due to a difference in etching rates between the titanium nitride layer and the tungsten layer, phosphoric acid, water, and additives may be mixed to uniformly maintain the difference in W/TiN etching rate.
  • hydrogen peroxide is a strong oxidizing agent and causes decomposition reactions with other components in the composition during long-term storage, which weakens the long-term stability of the etching composition, so it is important to secure the storage period and stability by using an additive that does not react with hydrogen peroxide.
  • long-term stability of the etching composition including hydrogen peroxide can be secured.
  • the hydrogen peroxide may contain 1 to 30% by weight, preferably 1 to 25% by weight, more preferably 1 to 20% by weight, and most preferably 1 to 15% by weight, based on the total weight of the etching composition.
  • the hydrogen peroxide is contained in an amount of less than 1% by weight, the etching rate is too slow to lengthen the process time, and when it exceeds 30% by weight, the etching rate is generally increased, making it difficult to control the process. Therefore, it is preferable that the titanium nitride layer and the tungsten layer are used within the above range so that the etching rates of the titanium nitride layer and the tungsten layer are the same.
  • the type of water is not particularly limited, but it is preferably distilled water or deionized water (DIW), and more preferably, deionized distilled water for semiconductor processing having a specific resistance value of 18M ⁇ / It is better to be more than cm.
  • DIW deionized water
  • the water is added to reduce the etch rate and prevent the change in the etch selectivity for the oxide layer, and 1 to 50% by weight, preferably 5 to 50% by weight, more preferably 10 to 50% by weight based on the total weight of the etching composition. % By weight, most preferably 20 to 50% by weight may be included.
  • the water content refers to the total amount of water added separately from the outside in addition to the water contained in the diluted phosphoric acid or hydrogen peroxide solution.
  • an ammonium compound and/or (e) a chelating agent may be further included.
  • the ammonium compound added to the etching composition may be included in the etching composition to maximize the oxidizing power of the oxidizing agent, thereby increasing the etching rate during the wet etching process and improving etching non-uniformity.
  • the ammonium compound may contain 0 to 5% by weight, preferably 0 to 4% by weight, more preferably 0 to 3% by weight, most preferably 0.01 to 2% by weight, based on the total weight of the etching composition.
  • the ammonium compound is added in an amount of more than 5% by weight, the etching rate of the titanium nitride layer and the tungsten layer may change, and thus selectivity may be changed.
  • ammonium compounds included in the etching composition of the present invention are specifically ammonium sulfate, ammonium persulfate, ammonium hydroxide, ammonium chloride, ammonium phosphate, It may be any one selected from ammonium nitrate, ammonium bisulfate, or a mixture thereof, preferably ammonium nitrate.
  • the chelating agent forms and deactivates etching by-product ions and chelates generated during etching of the titanium nitride layer and the tungsten layer, thereby preventing readsorption and increasing the uniformity of the etching surface after etching. It plays a role to let.
  • the chelating agent is preferably contained in an amount of 0 to 10% by weight, preferably 0 to 7% by weight, more preferably 0 to 6% by weight, most preferably 0.01 to 5% by weight, based on the total weight of the etching composition. Do. When the weight of the chelating agent exceeds 10% by weight, there is a problem in that the etching rate is reduced due to formation of a chelate with excessive etching by-products, thereby reducing the etching efficiency.
  • the chelating agent is arginine, histidine, lysine, aspartic acid, glutamic acid, glutamine, serine, threonine, and asparagine.
  • Asparagine Cysteine, Glycine, Proline, Serenocysteine, Alanine, Tyrosine, Valine, Tryptophane, Leucine , Phenylalanine, Methionine, ethylenedinitrilo)tetraacetic acid (EDTA), butylenediaminetetraacetic acid, (1,2-cyclohexylenedinitrilo-)tetraacetic acid (cyDTA), diethylenetri Amine pentaacetic acid (DETPA), ethylenediaminetetrapropionic acid, (hydroxyether)ethylenediaminetriacetic acid (HEDTA), N,N,N',N'-ethylenediaminetetra(methylenephosphonic) acid (EDTMP), triethylene Tetraminehexaacetic acid (As
  • a method of simultaneously etching the titanium nitride layer and the tungsten layer in a semiconductor device in which a titanium nitride layer and a tungsten layer are stacked using the etching composition is provided.
  • the etching method includes forming a laminate by sequentially forming the titanium nitride film and a tungsten film on a substrate, and performing etching by adding the etching composition to the laminate. After completing the process, the step of removing the remaining etching composition may be included.
  • the substrate may preferably be a semiconductor wafer, but is not limited thereto, and all commonly used substrates may be used.
  • the titanium nitride film and the tungsten film for the substrate may be formed according to a conventional method of forming a titanium nitride film and a tungsten metal film, and the order of forming the titanium nitride film and the tungsten film is not particularly limited.
  • the temperature may be 30 to 80°C. If the etching temperature is less than 30°C, the etching rate is extremely slow, so that the titanium nitride layer and the tungsten layer cannot be etched. Membrane damage may occur.
  • the method of treating the etching composition for the laminate of the titanium nitride layer and the tungsten layer is not particularly limited, and may be a method such as coating, dipping, spraying or spraying, and a method of dipping (batch type device) or a method of spraying. (Sheet type device) can be preferably used.
  • a removal process using ultrapure water or the like for the etching composition remaining after the etching process is completed, and a drying process for the etched laminate may be performed.
  • phosphoric acid, hydrogen peroxide, water, an ammonium compound, an amino acid, and a chelating agent were mixed in each weight ratio indicated with respect to the total weight of the etching composition, to prepare an etching composition according to the present invention.
  • etching composition [Table 1] and [Table 2] at 60°C for 2 minutes, and then deionized water ), and then dried and evaluated, and the film thickness was measured with a 4-point probe and described in [Table 3].
  • the etch rate is a value calculated by dividing the difference between the thickness of each film before the etch treatment and the film thickness after the etch treatment by the etching time (minutes), and the selectivity is the tungsten film ( W) represents the ratio of the etch rate.
  • a 50 ⁇ (Al 2 O 3 )-thick wafer was prepared in a size of 2 x 2 cm 2 and immersed in the etching composition of [Table 1] or [Table 2] at 60° C. for 20 minutes, and then with deionized water (DIW). After washing, drying was evaluated, and the etch rate was measured by measuring the film thickness by ellipsometry (Nano-view, SEMG-1000: Ellipsometry), and the results are shown in [Table 3].
  • Example 1 43.7 36.8 1.2 0.33
  • Example 2 51.7 39.3 1.32 0.34
  • Example 3 37.7 34.7 1.1 0.34
  • Example 4 41.6 39.4 1.1 0.32
  • Example 5 49.1 41.1 1.2 0.32
  • Example 6 47.7 39.6 1.2 0.31
  • Example 7 46.2 38.5 1.2 0.33
  • Example 8 44.3 40.7 1.1 0.26
  • Example 9 49.2 40.2 1.2 0.32
  • Example 10 43.2 39.8 1.1 0.29
  • Example 11 43.7 39.9 1.1 0.31
  • Example 12 44.2 40.5 1.1 0.32
  • Example 13 38.8 38.8 1.0 0.28
  • Comparative Example 1 9.3 32.6 0.3 0.35 Comparative Example 2 5.5 2.3 2.4 1.91 Comparative Example 3 6.1 2.7 2.3 1.63
  • Comparative Example 1 can be seen that the tungsten etch rate is significantly lower than that of the Example.
  • the etch rate may be increased, or the etch selectivity may be closer to one.
  • the etching compositions of Examples 1 to 13 have improved selectivity and higher tungsten and titanium nitride etching rates than the comparative etching compositions, and have characteristics of minimizing Al 2 O 3 damage.
  • Example 1 After the preparation of the etching composition, the titanium nitride and tungsten wafers were immersed in the etching composition at 60°C after being stored on a weekly basis for 0 to 8 weeks, and the change in the etching rate and selectivity according to the storage time was confirmed. 4].
  • the [Table 4] shows the storage stability evaluation of the etching composition used in Example 1. As shown in [Table 4], there was no decrease in etch rate for the titanium nitride film and the tungsten film even during the storage time (8 weeks), and the etch selectivity was maintained around 1.2. From these results, the composition according to the present invention had no content change and performance degradation due to the reaction, and excellent storage stability of the etching composition was confirmed. The result of observing the change of the etching rate according to the storage time in [Table 4] is shown in FIG. 1.

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Abstract

The present invention relates to a composition for etching, comprising phosphoric acid, hydrogen peroxide, and water and, more specifically, to a composition for etching a laminate of a titanium nitride film and a tungsten film, the composition additionally comprising at least one of an ammonium compound and a chelating agent so as to have excellent stability for long-term storage, while maintaining an etch selectivity of 1 by having the same etch rate when etching the tungsten film against the titanium nitride film.

Description

질화티타늄막 및 텅스텐막 적층체 식각용 조성물 및 이를 이용한 반도체 소자의 식각방법Composition for etching titanium nitride layer and tungsten layer stack, and etching method of semiconductor device using the same
본 발명은 질화티타늄막 및 텅스텐막 적층체 식각용 조성물, 이를 이용한 반도체 소자의 식각방법에 관한 것으로서, 보다 상세하게는 질화티타늄막에 대한 텅스텐막을 동일한 식각속도로 식각할 수 있으며, 장기보관시에도 식각속도의 저하가 없는, 질화티타늄막 및 텅스텐막 적층체 식각용 조성물 및 이를 이용한 반도체 소자의 식각방법에 관한 것이다. The present invention relates to a composition for etching a titanium nitride layer and a tungsten layer stack, and a method for etching a semiconductor device using the same, and more particularly, a tungsten layer for a titanium nitride layer can be etched at the same etching rate, and even during long-term storage. The present invention relates to a composition for etching a titanium nitride layer and a tungsten layer laminate without lowering the etching rate, and a method for etching a semiconductor device using the same.
최근 IT 기술의 발달로 휴대폰, 디지털 카메라, MP3, USB 메모리와 같은 휴대기기의 고성능화, 소형화가 가속화되고 있다. 또한, 현재 대두되고 있는 스마트폰은 휴대용 컴퓨터를 지향하며 발전을 거듭하고 있다. 이러한 제품들은 기존의 컴퓨터(PC)와 동등한 능력을 지녀야 하며, 이를 구현하기 위해서는 초고속, 대용량, 저소비 전력, 우수한 성능을 지닌 반도체에 대한 기술 개발이 요구되고 있다. With the recent development of IT technology, high performance and miniaturization of portable devices such as mobile phones, digital cameras, MP3s, and USB memories are accelerating. In addition, smartphones that are currently emerging are continuing to develop toward a portable computer. These products must have the same capabilities as conventional computers (PCs), and in order to implement them, technology development for semiconductors with ultra-high speed, large capacity, low power consumption, and excellent performance is required.
일반적으로 반도체 직접회로는 하나의 트랜지스터와 하나의 캐패시터(Capacitor)를 단위셀로 하여 제조되고 이러한 반도체 장치의 트랜지스터는 일반적으로 MOS 구조이다. 이러한 MOS 구조의 트랜지스터는 소스(Source) 전극, 게이트(Gate) 전극 및 드레인(Drain) 전극 구조로 이루어진다. In general, semiconductor integrated circuits are manufactured using one transistor and one capacitor as unit cells, and the transistors of such semiconductor devices are generally MOS structures. The MOS transistor has a source electrode, a gate electrode, and a drain electrode structure.
이와 같이, 반도체 직접회로를 가득 채우고 있는 수천만 개 이상의 트랜지스터, 다이오드, 저항, 캐패시터 등의 전자부품들은 서로 정확하게 연결되고 전기 신호를 연산하고 저장하고 있다. 이러한 반도체 직접회로의 제조는 전자부품들과 그 접속 부분들을 모두 미세하고 복잡한 패턴으로 만들어 여러층의 재료 속에 그려 넣는 방식을 사용하고 있으며, 이를 위해서는 식각공정이 매우 중요하다. In this way, more than tens of millions of electronic components, such as transistors, diodes, resistors, and capacitors, that fill the semiconductor integrated circuit are accurately connected to each other and calculate and store electrical signals. In the manufacture of such an integrated semiconductor circuit, all electronic components and their connection parts are made into fine and complex patterns and drawn into multiple layers of material, and an etching process is very important for this.
식각공정은 웨이퍼에 액체 또는 기체의 에천트(etchant)를 이용해 불필요한 부분을 선택적으로 제거해 반도체 회로 패턴을 제조하는 것이다. 반도체를 구성하는 여러 층의 얇은 막에 원하는 회로 패턴을 형성하는 과정을 반복함으로써, 반도체의 구조가 형성된다. In the etching process, a semiconductor circuit pattern is manufactured by selectively removing unnecessary portions using a liquid or gas etchant on a wafer. A semiconductor structure is formed by repeating the process of forming a desired circuit pattern on a thin film of several layers constituting a semiconductor.
이러한 식각공정은 식각 반응을 일으키는 물질의 상태에 따라 습식식각(wet etching)과 건식식각(dry etching)이 있다. The etching process includes wet etching and dry etching depending on the state of the material causing the etching reaction.
건식식각은 현상적으로 볼 때 플라즈마 내에 존재하는 원소와 표면 물질간에 화학반응과 플라즈마 내에 존재하는 활성종 입자의 표면충돌에 기인한 반응촉진에 의해 진행된다. 건식식각 중 일어나는 플라즈마 반응은 플라즈마 내에서 활성입자의 생성, 활성입자의 식각표면으로의 이동 및 흡착, 표면물질과의 화학반응 및 반응생성물의 이탈로 이루어진다. Dry etching proceeds phenomenally by a chemical reaction between an element present in the plasma and a surface material, and by promoting a reaction due to the collision of the active species particles present in the plasma. The plasma reaction that occurs during dry etching consists of the generation of active particles in the plasma, movement and adsorption of the active particles to the etching surface, chemical reactions with surface materials, and separation of reaction products.
한편, 습식식각은 식각하고자 하는 막과 화학적으로 반응하여 용해시킬 수 있는 화학용액을 사용하여 식각하는 방법이다. 가령, 불산을 사용하여 실리콘 산화막을 습식식각하는 경우, 이때 일어나는 화학반응을 살펴보면 불산이 해리되어 수소이온과 불소이온으로 분리되며, 분리된 불소이온이 산화막과 반응하여 식각이 이루어지게 된다.Meanwhile, wet etching is a method of etching using a chemical solution that can be dissolved by chemically reacting with the film to be etched. For example, in the case of wet etching a silicon oxide film using hydrofluoric acid, a chemical reaction that occurs at this time will dissociate hydrofluoric acid to be separated into hydrogen ions and fluorine ions, and the separated fluorine ions react with the oxide film to perform etching.
따라서, 식각이 계속됨에 따라 불소이온은 소모가 되며, 용액자체가 물에 의해 희석되면서 용액내의 수소이온 농도는 증가하게 된다. 이러한 결과는 산화막의 식각속도가 공정이 진행될수록 달라짐을 의미하며, 그 결과는 재현성 있는 공정이 어렵다. 또한 습식식각의 화학반응이 수직 및 수평방향으로 동시에 진행되기 때문에 언더 컷(under cut)현상이 발생하게 된다. 즉, 노광되지 않은 포토 패턴 밑에 식각용액의 침투에 의해 원치않는 언더컷이 발생하게 되면, 패턴의 선폭이 점점 좁아져, 수직한 코어층의 형성을 어렵게 하는 문제점이 발생한다. Accordingly, as etching continues, fluorine ions are consumed, and as the solution itself is diluted with water, the concentration of hydrogen ions in the solution increases. This result means that the etch rate of the oxide layer varies as the process proceeds, and the result is difficult to reproduce the process. In addition, since the chemical reaction of wet etching proceeds simultaneously in the vertical and horizontal directions, an under cut phenomenon occurs. That is, when an unwanted undercut occurs due to penetration of an etching solution under the unexposed photo pattern, the line width of the pattern becomes narrower, making it difficult to form a vertical core layer.
일반적으로, 반도체 집적 회로의 습식식각공정에서 텅스텐 또는 텅스텐계 금속과 함께 티탄계 금속인 티타늄 질화막을 기체 또는 액체의 부식액을 사용하여 불필요한 부분을 선택적으로 제거하는 패터닝 과정을 거치며, 이때, 질화티타늄 막과 텅스텐 막을 일정한 식각속도로 식각하기 위해 종래기술에서는 인산, 질산 및 초산의 혼합용액이 식각 조성물로서 사용되었다. 상기와 같은 식각 조성물을 이용하여 습식식각시 식각속도가 현저히 낮아 시간적, 경제적 측면에서 바람직하지 않다. 또한 높은 공정온도에서 습식식각을 수행할 때 식각 조성물 중 초산과 질산이 증발되어 질화티타늄막 대비 텅스텐막의 선택비를 일정하게 유지 할 수 없다.In general, in a wet etching process of a semiconductor integrated circuit, a titanium nitride film, which is a titanium-based metal together with tungsten or tungsten-based metal, undergoes a patterning process in which unnecessary portions are selectively removed using a gaseous or liquid corrosion solution. In this case, the titanium nitride film In the prior art, a mixed solution of phosphoric acid, nitric acid, and acetic acid was used as an etching composition to etch the tungsten and tungsten films at a constant etching rate. When wet etching using the above etching composition, the etching rate is significantly low, which is not preferable in terms of time and economy. In addition, when wet etching is performed at a high process temperature, acetic acid and nitric acid in the etching composition are evaporated, and the selectivity of the tungsten film compared to the titanium nitride film cannot be maintained constant.
이에 따라 반도체 소자의 제조 공정에서 질화티타늄막(TiN)과 텅스텐막(W)을 높은 식각속도로 식각선택비 1을 유지하고 장기보관시에도 식각속도의 저하가 없는, 절연막에도 damage가 없는 식각 조성물의 개발이 요구된다.Accordingly, in the manufacturing process of a semiconductor device, the titanium nitride film (TiN) and the tungsten film (W) are kept at a high etching rate, and the etch selectivity is 1, and there is no decrease in the etch rate even during long-term storage, and there is no damage to the insulating film. Development is required.
높은 식각속도를 위해 식각용 조성물이 황산과 과산화 수소를 포함할 경우 황산과 과산화수소가 반응하여 카로산(Caro’s acid, H2SO5)가 형성된다. 이와 같이 형성된 카로산은 절연막(Al2O3)에 대한 손상을 일으킬 수 있을 뿐만 아니라 보관안정성에도 영향을 미쳐 장기 보관시 텅스텐과 질화티타늄막의 식각속도가 저하되는 문제점이 있다.For a high etching rate, when the composition for etching contains sulfuric acid and hydrogen peroxide, sulfuric acid and hydrogen peroxide react to form Caro's acid (H 2 SO 5 ). The carboxylic acid formed as described above may cause damage to the insulating layer (Al 2 O 3 ) and also affect storage stability, so that the etching rate of the tungsten and titanium nitride layers decreases during long-term storage.
상기 식각 조성물에 관한 종래기술로서, 한국공개특허 10-2015-0083605호(공개일:2015.07.20.)에서는 도전 패턴의 형성 방법 및 이를 이용한 반도체 장치의 제조 방법에 관한 것으로, 인산, 질산, 보조 산화제 및 여분의 물을 포함하며, 금속 질화물 및 금속에 대해 동일한 식각속도를 갖는 식각용 조성물을 사용한 습식식각 공정에 대해 기재되어 있다. 상기 선행문헌에서는 보조 산화제로 산암모늄 계열 화합물, 할로겐산 화합물 또는 황산 계열 화합물을 사용하고 있다.As a prior art for the etching composition, Korean Patent Laid-Open Publication No. 10-2015-0083605 (published date: 2015.07.20.) relates to a method of forming a conductive pattern and a method of manufacturing a semiconductor device using the same, including phosphoric acid, nitric acid, auxiliary It has been described for a wet etching process using an etching composition containing an oxidizing agent and excess water and having the same etching rate for metal nitride and metal. In the prior literature, an acid ammonium compound, a halogen acid compound, or a sulfuric acid compound is used as an auxiliary oxidizing agent.
또한 한국공개특허 10-2015-0050278호에는 (a) 인산 50 내지 80중량%, (b) 질산 5 내지 20중량%, (c) 암모늄계 화합물 0.01 내지 10중량% 및 (d) 잔부량의 용매를 포함하는, 질화티타늄막 및 텅스텐막의 적층체용 식각 조성물이 공지되어 있다.In addition, Korean Patent Laid-Open No. 10-2015-0050278 discloses (a) 50 to 80% by weight of phosphoric acid, (b) 5 to 20% by weight of nitric acid, (c) 0.01 to 10% by weight of an ammonium compound, and (d) the balance of the solvent. An etching composition for a laminate of a titanium nitride film and a tungsten film is known.
또 다른 종래기술로서, 한국등록특허공보 10-1695571호에서는 과산화수소계 금속 식각용 조성물에 관한 것으로, 보다 구체적으로 과산화수소계 금속 식각용 조성물 내 과산화수소의 분해 및 다른 성분들의 변성을 방지할 수 있는 과산화수소계 금속 식각용 조성물에 대해 기재되어 있다. As another prior art, Korean Patent Publication No. 10-1695571 relates to a composition for etching a hydrogen peroxide-based metal, and more specifically, a hydrogen peroxide-based composition capable of preventing decomposition of hydrogen peroxide and degeneration of other components in a composition for etching a hydrogen peroxide-based metal. It has been described for a composition for etching metal.
그러나, 아직 선행기술들은 질화티타늄막(TiN)과 텅스텐막(W)에 대하여 동일한 식각선택비를 가질 경우는 식각속도가 현저히 낮아 시간적 경제적 측면에서 바람직하지 않으며, 저장안정성에도 영향을 미쳐 장기 보관시 식각속도가 저하되는 문제점이 있다. However, the prior art still has the same etch selectivity for the titanium nitride film (TiN) and tungsten film (W), the etch rate is significantly low, which is not desirable in terms of time and economy. There is a problem that the etch rate is lowered.
본 발명의 목적은 반도체소자의 제조공정에서 질화티타늄막(TiN)과 텅스텐막(W)의 높은 식각속도로 거의 동일한 식각선택비를 만족하고 장기보관시에도 식각용 조성물의 저장 안정성이 우수하며, Al2O3 high-k 절연막에 대한 손상을 최소화하는, 질화티타늄막 및 텅스텐막의 식각용 조성물을 제공하는데 있다.It is an object of the present invention to satisfy almost the same etch selectivity at a high etching rate of a titanium nitride film (TiN) and a tungsten film (W) in a semiconductor device manufacturing process, and excellent storage stability of the etching composition even during long-term storage, It is to provide a composition for etching a titanium nitride film and a tungsten film that minimizes damage to the Al 2 O 3 high-k insulating film.
또한 본 발명의 다른 목적은 상기 식각 조성물을 이용하는 질화티타늄막 및 텅스텐막을 식각하는 방법을 제공하는 것이다. In addition, another object of the present invention is to provide a method of etching a titanium nitride layer and a tungsten layer using the etching composition.
상기 과제를 해결하기 위하여 본원 발명은 (a) 인산 20 내지 75중량%, (b) 과산화수소 1 내지 30중량%, (c) 물 1 내지 50중량%, (d) 암모늄화합물 0 내지 5 중량%, (e) 킬레이트제 0 내지 10 중량% 로 이루어지는 것을 특징으로 하는 질화티타늄막 및 텅스텐막의 동시 식각용 조성물을 제공한다. In order to solve the above problems, the present invention provides (a) 20 to 75% by weight of phosphoric acid, (b) 1 to 30% by weight of hydrogen peroxide, (c) 1 to 50% by weight of water, (d) 0 to 5% by weight of ammonium compounds, (e) It provides a composition for simultaneous etching of a titanium nitride film and a tungsten film, comprising 0 to 10% by weight of a chelating agent.
본 발명의 일실시예 있어서, 상기 식각용 조성물은 식각용 조성물 전체 중량 대비 0.01~ 2wt%의 공지된 첨가제가 더 부가된 것을 특징으로 할 수 있다. In one embodiment of the present invention, the etching composition may be characterized in that 0.01-2wt% of a known additive is further added relative to the total weight of the etching composition.
상기 암모늄화합물은 암모늄설페이트(ammonium sulfate), 암모늄퍼설페이트(ammonium persulfate), 수산화암모늄(ammonium hydroxide), 염화암모늄(ammonium chloride), 인산암모늄(ammonium phosphate), 질산암모늄(ammonium nitrate), 암모늄 바이설페이트(ammonium bisulfate) 중에서 선택되는 어느 하나 이상일 수 있으며, 바람직하게는 질산암모늄(Ammonium nitrate)이다.The ammonium compound is ammonium sulfate, ammonium persulfate, ammonium hydroxide, ammonium chloride, ammonium phosphate, ammonium nitrate, ammonium bisulfate It may be any one or more selected from (ammonium bisulfate), preferably ammonium nitrate (Ammonium nitrate).
또한 상기 킬레이트제는 아르기닌(Arginine), 히스티딘(Histidine), 리신(Lysine), 아스파르트산(Aspartic acid), 글루타민산(Glutamic acid), 글루타민(Glutamine), 세린(Serine), 트레오닌(Threonine), 아스파라긴(Asparagine), 시스테인(Cysteine), 글리신(Glycine), 프롤린(Proline), 세레노시스테인(Serenocysteine), 알라닌(Alanine), 티로신(Tyrosine), 발린(Valine), 트립토판(Tryptophane), 류신(Leucine), 페닐알라닌(Phenylalanine), 메티오닌(Methionine), (에틸렌디니트릴로)테트라아세트산(EDTA), 부틸렌디아민테트라아세트산, (1,2-사이클로헥실렌디니트릴로-)테트라아세트산(cyDTA), 디에틸렌트리아민펜타아세트산(DETPA), 에틸렌디아민테트라프로피온산, (하이드록시에텔)에틸렌디아민트리아세트산(HEDTA), N,N,N’,N’-에틸렌디아민테트라(메틸렌포스폰)산 (EDTMP), 트리에틸렌테트라민헥사아세트산 (TTHA), 1,3-디아미노-2-하이드록시프로판-N,N,N’,N’-테트라아세트산 (DHPTA), 시트르산(Citric acid), 살리실산(Salicylic acid), 타르타르산(Tartaric acid), 글루콘산(Gluconic acid), 옥살산(Oxalic acid), 말론산(Malonic acid), 말산(Malic acid), 설파믹산(Sulfamic acid), 석신산(Succinic acid) 중에서 선택되는 어느 하나 이상일 수 있으며, 바람직하게는 시트르산(Citric acid), 글리신(Glycine) 중 적어도 하나 이상이다. In addition, the chelating agents are arginine, histidine, lysine, aspartic acid, glutamic acid, glutamine, serine, threonine, and asparagine. Asparagine), Cysteine, Glycine, Proline, Serenocysteine, Alanine, Tyrosine, Valine, Tryptophane, Leucine, Phenylalanine, Methionine, (ethylenedinitrilo)tetraacetic acid (EDTA), butylenediaminetetraacetic acid, (1,2-cyclohexylenedinitrilo-)tetraacetic acid (cyDTA), diethylenetri Amine pentaacetic acid (DETPA), ethylenediaminetetrapropionic acid, (hydroxyether)ethylenediaminetriacetic acid (HEDTA), N,N,N',N'-ethylenediaminetetra(methylenephosphonic) acid (EDTMP), triethylene Tetraminehexaacetic acid (TTHA), 1,3-diamino-2-hydroxypropane-N,N,N',N'-tetraacetic acid (DHPTA), citric acid, salicylic acid, tartaric acid (Tartaric acid), gluconic acid (Gluconic acid), oxalic acid (Oxalic acid), malonic acid (Malonic acid), malic acid (Malic acid), sulfamic acid (Sulfamic acid), any one or more selected from succinic acid (Succinic acid) It may be, and preferably at least one of citric acid and glycine.
또한, 본원 발명에서 상기 암모늄화합물은 0.01 내지 2 중량%, 상기 킬레이트제는 0.01 내지 5 중량% 로 포함될 수 있으며, 이때, 상기 암모늄화합물은 질산 암모늄(ammonium nitrate)이고, 상기 킬레이트제는 시트르산(Citric acid) 및 글리신(Glycine)일 수 있다.In addition, in the present invention, the ammonium compound may be contained in an amount of 0.01 to 2% by weight and the chelating agent in an amount of 0.01 to 5% by weight, in which case, the ammonium compound is ammonium nitrate, and the chelating agent is citric acid. acid) and glycine.
또한 본원 발명은 질화티타늄막 및 텅스텐막을 포함하는 반도체 소자에서 질화티타늄막과 텅스텐막을 동시에 식각하는 단계에서 상기 본원 발명의 식각용 조성물을 이용하는 것을 특징으로 하는 반도체 소자의 식각 방법을 제공한다. In addition, the present invention provides a method for etching a semiconductor device, characterized in that the etching composition of the present invention is used in the step of simultaneously etching a titanium nitride film and a tungsten film in a semiconductor device including a titanium nitride film and a tungsten film.
상기 반도체 소자의 식각은 30 내지 80℃의 온도 범위에서 실시될 수 있다.The etching of the semiconductor device may be performed in a temperature range of 30 to 80°C.
본 발명에 따른 질화티타늄막 및 텅스텐막의 적층체 식각용 조성물은 반도체소자의 제조공정에서 질화티타늄(TiN)막과 텅스텐(W)막에 대하여 높은 식각 속도를 유지하면서도 질화티타늄과 텅스텐막의 식각 선택비를 1에 근접하도록 할 수 있으며, 장기간 보관시에도 식각속도의 저하가 없고, Al2O3와 같은 high-k 절연막에 대한 손상을 최소화하는 특성을 갖는다. The composition for etching a laminate of a titanium nitride film and a tungsten film according to the present invention maintains a high etching rate for the titanium nitride (TiN) film and the tungsten (W) film in the manufacturing process of a semiconductor device, while the etching selectivity of the titanium nitride and tungsten film. Can be made close to 1, there is no decrease in the etching rate even when stored for a long period of time, and has the characteristics of minimizing damage to high-k insulating films such as Al 2 O 3 .
도 1은 본 발명의 식각용 조성물의 보관기간에 따른 질화티타늄(TiN)막 및 텅스텐(W)막 식각속도의 변화를 관찰한 그래프이다. 1 is a graph illustrating changes in etching rates of a titanium nitride (TiN) layer and a tungsten (W) layer according to the storage period of the etching composition of the present invention.
다른 식으로 정의하지 않는 한, 본 명세서에서 사용된 모든 기술적 및 과학적 용어들은 본 발명이 속하는 기술분야에서 숙련된 전문가에 의해서 통상적으로 이해되는 것과 동일한 의미를 가진다. 일반적으로, 본 명세서에서 사용된 명명법은 본 기술분야에서 잘 알려져 있고 통상적으로 사용되는 것이다.Unless otherwise defined, all technical and scientific terms used in this specification have the same meaning as commonly understood by an expert skilled in the art to which the present invention belongs. In general, the nomenclature used in this specification is well known and commonly used in the art.
본원 명세서 전체에서, 어떤 부분이 어떤 구성 요소를 “포함”한다고 할 때, 이는 특별히 반대되는 기재가 없는 한 다른 구성 요소를 제외하는 것이 아니라 다른 구성 요소를 더 포함할 수 있는 것을 의미한다.In the entire specification of the present application, when a certain part “includes” a certain constituent element, it means that other constituent elements may be further included rather than excluding other constituent elements unless otherwise indicated.
본 발명에 따른 질화티타늄막 및 텅스텐막 적층체 식각용 조성물은 습식식각 시 주위의 다른 막질에 대한 영향은 없으면서, 식각하고자 하는 막에 대해서만 선택적으로 우수한 식각 속도를 가지며 Al2O3와 같은 고유전율 절연막에 대한 손상을 최소화하는 장점을 가진다. The composition for etching a titanium nitride film and a tungsten film laminate according to the present invention does not have an effect on other film qualities in the vicinity during wet etching, and has an excellent etching rate selectively only for the film to be etched, and has a high dielectric constant such as Al 2 O 3. It has the advantage of minimizing damage to the insulating film.
본 발명에서 언급되는 티타늄 나이트라이드(TiN, 질화티타늄)막 및 텅스텐(W)막은 반도체 기판 상에 증착 또는 코팅을 통해 박막 또는 후막으로 단층 또는 다층으로 적층되는 구조 일 수 있다. The titanium nitride (TiN, titanium nitride) film and the tungsten (W) film mentioned in the present invention may have a structure in which a single layer or a multi-layer is stacked as a thin film or a thick film through deposition or coating on a semiconductor substrate.
이 때 티타늄 나이트라이드(TiN, 질화티타늄)막(또는 층)은 질화티타늄막으로 정의하며, 텅스텐으로 이루어진 막(또는 층)은 텅스텐막으로 정의한다. In this case, the titanium nitride (TiN, titanium nitride) film (or layer) is defined as a titanium nitride film, and the film (or layer) made of tungsten is defined as a tungsten film.
또한 본 발명의 명세서에서 언급되는 다른 막질은 반도체 제조 공정 중 패턴 상에 존재하는 질화티타늄막 및 텅스텐막 이외의 다른 재질의 막을 의미하며, 일례로 절연막, 보호막일 수 있으며, 구체적으로 산화알루미늄(이하, Al2O3)막으로 이루어진 절연막일 수 있다. 상기 Al2O3 절연막은 기존의 게이트 절연막인 실리콘 옥사이드 (SiO2)보다 높은 유전율 (high-k)을 가지고 있어 저전압 구동이 가능하고 다른 높은 유전율을 가지는 물질 보다 밴드 갭 (band gap)이 커서 절연 특성 또한 우수하며 상기 질화티타늄막 및 텅스텐막의 하부 또는 측면에 위치할 수 있다.In addition, the other film quality mentioned in the specification of the present invention refers to a film made of a material other than the titanium nitride film and the tungsten film present on the pattern during the semiconductor manufacturing process, and may be an insulating film or a protective film, specifically aluminum oxide (hereinafter , Al 2 O 3 ) It may be an insulating film made of a film. The Al 2 O 3 insulating layer has a higher dielectric constant (high-k) than the conventional gate insulating layer of silicon oxide (SiO 2 ), so it can be driven at a low voltage and has a larger band gap than other materials with higher dielectric constants. The properties are also excellent and may be located under or on the side of the titanium nitride and tungsten films.
습식 식각의 식각용 조성물은 막 균일도(Uniformity) 유지, 높은 식각 속도(Etch Rate), 우수한 선택비(Selectivity) 등을 고려하여 선정되며, 식각을 수행하고자 하는 이외의 다른 막질에 대한 영향이 없거나 최소화되어야 한다. The composition for etching by wet etching is selected in consideration of film uniformity maintenance, high etching rate, and excellent selectivity, and has no or minimized influence on other film qualities other than the intended to be etched. Should be.
그러나 실제 습식 식각에 사용하는 식각용 조성물의 경우 산 또는 염기도가 높은 재질이 사용됨에 따라 인접한 다른 막이나 절연막을 공격(attack)하여 막질에 대한 손상을 유발할 수 있으며, 식각용 조성물에 과산화수소가 포함될 경우 조성물 내 과산화수소와 기타 성분들 간의 부반응이 일어날 수도 있고, 장기간 보관시 과산화수소가 분해되는 등 안정성이 떨어져 결과적으로 반도체 제품의 불량을 야기할 수 있다. However, in the case of an etching composition used in actual wet etching, as a material with high acid or basicity is used, it may attack other adjacent layers or insulating layers, causing damage to the film quality.If hydrogen peroxide is included in the etching composition Side reactions between hydrogen peroxide and other components in the composition may occur, and stability may be degraded, such as hydrogen peroxide decomposition during long-term storage, resulting in poor semiconductor products.
이에 본 발명에서는 식각공정시, Al2O3 절연막에 대한 영향을 최소화하면서도 질화티타늄막 및 텅스텐막을 높은 속도로 식각하면서도 상기 질화티타늄막 및 텅스텐막 각각에 대한 식각속도의 비인 식각선택비를 거의 동일하게, 바람직하게는 1로 유지할 수 있는 식각용 조성물을 제시한다. Accordingly, in the present invention, the titanium nitride layer and the tungsten layer are etched at a high rate while minimizing the effect on the Al 2 O 3 insulating layer during the etching process, while the etching selectivity, which is the ratio of the etching rates for the titanium nitride layer and the tungsten layer, is almost the same. For example, a composition for etching that can be maintained at preferably 1 is provided.
본 발명은 (a) 인산, (b) 과산화수소, (c) 물을 포함하는 식각용 조성물에 있어서 선택적으로 (d) 암모늄화합물 및/또는 (e) 킬레이트제를 더 포함할 수 있다. The present invention may optionally further include (d) an ammonium compound and/or (e) a chelating agent in the etching composition comprising (a) phosphoric acid, (b) hydrogen peroxide, and (c) water.
이외에도 상기 식각용 조성물은 발명의 효과를 더욱 양호하게 하기 위한 다양한 종류의 각종 첨가제를 첨가할 수 있다. 예로서, 상기 첨가제는 계면활성제, 붕소계 화합물, 무기산화물, 다가알코올, 아졸계화합물, 인산염 등 발명의 효과를 더욱 양호하게 하기 위하여, 이 분야에 공지되어 있는 통상의 여러 첨가제들을 모두 포함한다. 상기 첨가제는 식각용조성물 전체중량 대비 약 0.01~ 2wt%를 첨가할 수 있다. In addition, various kinds of additives may be added to the composition for etching to further improve the effect of the invention. As an example, the additive includes all of a variety of conventional additives known in the art, such as surfactants, boron compounds, inorganic oxides, polyhydric alcohols, azole compounds, and phosphates, in order to further improve the effects of the invention. The additive may be added in an amount of about 0.01 to 2 wt% based on the total weight of the etching composition.
상기 식각용 조성물에서 (a) 인산은 조성물 내에서 질화막 식각을 위한 주 식각 성분으로 작용할 수 있으며, 조성물 내에 수소 이온을 제공하여 식각을 촉진시킨다. In the etching composition, (a) phosphoric acid may act as a main etching component for etching the nitride film in the composition, and hydrogen ions are provided in the composition to accelerate etching.
상기 인산은 식각용 조성물 총 중량에 대하여 20 내지 75중량%, 바람직하게는 25 내지 75 중량%, 더욱 바람직하게는 25 내지 70 중량%, 가장 바람직하게는 30 내지 70 중량%로 포함될 수 있다. 상기 식각용 조성물에서 텅스텐의 식각은 과산화수소, 물 및 인산의 함량에 따라서 식각속도가 조절되며 과산화수소와 물의 함량이 증가할수록 식각속도가 높아지고, 인산의 함량이 증가할수록 식각속도가 억제된다. 따라서, 인산의 함량이 20 중량% 미만인 경우, 상대적으로 과산화수소와 물의 함량이 높아져 과식각이 발생할 수 있으며, 인산의 함량이 75 중량%를 초과하는 경우, 과산화수소와 물의 함량이 낮아져 텅스텐의 식각속도가 줄어들 우려가 있다. The phosphoric acid may be included in an amount of 20 to 75% by weight, preferably 25 to 75% by weight, more preferably 25 to 70% by weight, and most preferably 30 to 70% by weight, based on the total weight of the etching composition. The etching rate of tungsten in the etching composition is controlled according to the content of hydrogen peroxide, water, and phosphoric acid, and the etching rate increases as the content of hydrogen peroxide and water increases, and the etching rate is suppressed as the content of phosphoric acid increases. Therefore, when the content of phosphoric acid is less than 20% by weight, the content of hydrogen peroxide and water is relatively high, so overetching may occur, and when the content of phosphoric acid exceeds 75% by weight, the content of hydrogen peroxide and water is lowered, so that the etching rate of tungsten is lowered. There is a fear of reduction.
또한, 상기 식각용 조성물에서 (b)과산화수소는 질화티타늄막 및 텅스텐막을 식각하는 주성분의 하나로서, 강한 산화력을 가지며 조성물 내 다른 화합물과 산화 반응을 일으킬 수 있다. 상기 과산화수소는 질화티타늄막과 텅스텐막의 식각속도 차이로 인해 불량한 식각 프로파일을 얻을 수 있기 때문에, 인산, 물 및 첨가제를 혼합하여 W/TiN 식각속도 차이를 균일하게 유지시킬 수 있다. 또한, 과산화수소는 강력한 산화제로서 장기보관시 조성 내 다른 성분들과 분해반응을 일으켜 식각용 조성물의 장기 안정성을 약화시키므로 과산화수소와 반응하지 않는 첨가제를 사용하여 보관기간 및 안정성을 확보하는 것이 중요하다. 특히, 질산 또는 황산을 포함하지 않음으로 인하여 과산화수소를 포함한 식각 조성물의 장기 안정성을 확보할 수 있다.In addition, in the etching composition, (b) hydrogen peroxide is one of the main components that etch the titanium nitride layer and the tungsten layer, and has a strong oxidizing power and may cause an oxidation reaction with other compounds in the composition. Since the hydrogen peroxide can obtain a poor etching profile due to a difference in etching rates between the titanium nitride layer and the tungsten layer, phosphoric acid, water, and additives may be mixed to uniformly maintain the difference in W/TiN etching rate. In addition, hydrogen peroxide is a strong oxidizing agent and causes decomposition reactions with other components in the composition during long-term storage, which weakens the long-term stability of the etching composition, so it is important to secure the storage period and stability by using an additive that does not react with hydrogen peroxide. In particular, since it does not contain nitric acid or sulfuric acid, long-term stability of the etching composition including hydrogen peroxide can be secured.
상기 과산화수소는 식각용 조성물 총 중량에 대하여 1 내지 30 중량%, 바람직하게는 1 내지 25 중량%, 더욱 바람직하게는 1 내지 20 중량%, 가장 바람직하게는 1 내지 15 중량%가 포함될 수 있다. 과산화수소가 1중량% 미만으로 포함될 경우, 식각속도가 너무 느려 공정 시간이 길어지고, 30중량%가 초과할 경우에는 식각속도가 전체적으로 빨라지기 때문에 공정상 컨트롤하는 것이 어려워진다. 따라서, 질화티타늄막 및 텅스텐막의 식각 속도가 동일해질 수 있도록, 상기의 범위 내에서 사용되는 것이 바람직하다. The hydrogen peroxide may contain 1 to 30% by weight, preferably 1 to 25% by weight, more preferably 1 to 20% by weight, and most preferably 1 to 15% by weight, based on the total weight of the etching composition. When hydrogen peroxide is contained in an amount of less than 1% by weight, the etching rate is too slow to lengthen the process time, and when it exceeds 30% by weight, the etching rate is generally increased, making it difficult to control the process. Therefore, it is preferable that the titanium nitride layer and the tungsten layer are used within the above range so that the etching rates of the titanium nitride layer and the tungsten layer are the same.
한편, 상기 식각용 조성물에서 (c) 물의 종류는 특별히 한정되지 않으나, 증류수 또는 탈이온수(deionized water: DIW)인 것이 바람직하고, 보다 바람직하게는 반도체 공정용 탈이온 증류수로서 비저항값이 18㏁/㎝ 이상인 것이 좋다.On the other hand, in the etching composition (c) the type of water is not particularly limited, but it is preferably distilled water or deionized water (DIW), and more preferably, deionized distilled water for semiconductor processing having a specific resistance value of 18㏁/ It is better to be more than cm.
상기 물은 식각율 감소 및 산화막에 대한 식각 선택성의 변화를 방지하기 위해 첨가되며, 식각용 조성물 총 중량에 대하여 1 내지 50 중량%, 바람직하게는 5 내지 50 중량%, 더욱 바람직하게는 10 내지 50 중량%, 가장 바람직하게는 20 내지 50 중량%가 포함될 수 있다. 상기 물의 함량은 희석된 인산이나, 과산화수소수에 포함된 물에 더하여 외부에서 따로 더 첨가하는 물의 총량을 의미한다.The water is added to reduce the etch rate and prevent the change in the etch selectivity for the oxide layer, and 1 to 50% by weight, preferably 5 to 50% by weight, more preferably 10 to 50% by weight based on the total weight of the etching composition. % By weight, most preferably 20 to 50% by weight may be included. The water content refers to the total amount of water added separately from the outside in addition to the water contained in the diluted phosphoric acid or hydrogen peroxide solution.
상기 식각용 조성물에 있어서 (d) 암모늄화합물 및/또는 (e) 킬레이트제 를 더 포함할 수 있다. In the etching composition, (d) an ammonium compound and/or (e) a chelating agent may be further included.
이때, 상기 식각용 조성물에 추가하는 암모늄화합물은 식각용 조성물에 포함되어 산화제의 산화력을 극대화하여 습식식각 공정시 식각속도를 증가시키는 동시에 식각 불균일을 개선시키는 역할을 할 수 있다. At this time, the ammonium compound added to the etching composition may be included in the etching composition to maximize the oxidizing power of the oxidizing agent, thereby increasing the etching rate during the wet etching process and improving etching non-uniformity.
상기 암모늄화합물은 식각용 조성물 총 중량에 대하여 0 내지 5 중량%, 바람직하게는 0 내지 4 중량%, 더욱 바람직하게는 0 내지 3 중량%, 가장 바람직하게는 0.01 내지 2 중량%가 포함될 수 있다. 상기 암모늄 화합물을 5 중량% 초과로 첨가되는 경우 질화티타늄막 및 텅스텐막의 식각 속도가 변화하게 되어 선택도가 변하게 될 수 있다. The ammonium compound may contain 0 to 5% by weight, preferably 0 to 4% by weight, more preferably 0 to 3% by weight, most preferably 0.01 to 2% by weight, based on the total weight of the etching composition. When the ammonium compound is added in an amount of more than 5% by weight, the etching rate of the titanium nitride layer and the tungsten layer may change, and thus selectivity may be changed.
본 발명의 식각용 조성물에 포함되는 암모늄화합물은 구체적으로 암모늄설페이트(ammonium sulfate), 암모늄퍼설페이트(ammonium persulfate), 수산화암모늄(ammonium hydroxide), 염화암모늄(ammonium chloride), 인산암모늄(ammonium phosphate), 질산암모늄(ammonium nitrate), 암모늄 바이설페이트(ammonium bisulfate) 중에서 선택되는 어느 하나 또는 이들의 혼합물일 수 있으며 바람직하게는 질산암모늄(Ammonium nitrate)일 수 있다. The ammonium compounds included in the etching composition of the present invention are specifically ammonium sulfate, ammonium persulfate, ammonium hydroxide, ammonium chloride, ammonium phosphate, It may be any one selected from ammonium nitrate, ammonium bisulfate, or a mixture thereof, preferably ammonium nitrate.
또한, 본 발명의 상기 식각용 조성물에서 킬레이트제는 질화티티늄막 및 텅스텐막의 식각이 진행되는 동안 발생하는 식각부산물 이온들과 킬레이트를 형성하여 비활성화 시킴으로써, 재흡착 방지 및 식각 후 식각면의 균일도를 증가시키는 역할을 한다.In addition, in the etching composition of the present invention, the chelating agent forms and deactivates etching by-product ions and chelates generated during etching of the titanium nitride layer and the tungsten layer, thereby preventing readsorption and increasing the uniformity of the etching surface after etching. It plays a role to let.
상기 킬레이트제는 식각용 조성물 총 중량에 대하여 0 내지 10 중량%, 바람직하게는 0 내지 7 중량%, 더욱 바람직하게는 0 내지 6 중량%, 가장 바람직하게는 0.01 내지 5 중량%로 포함되는 것이 바람직하다. 상기 킬레이트제의 중량이 10 중량%를 초과하는 경우 과도한 식각부산물과의 킬레이트 형성으로 식각속도가 감소되어 식각효율이 떨어지는 문제가 있다. The chelating agent is preferably contained in an amount of 0 to 10% by weight, preferably 0 to 7% by weight, more preferably 0 to 6% by weight, most preferably 0.01 to 5% by weight, based on the total weight of the etching composition. Do. When the weight of the chelating agent exceeds 10% by weight, there is a problem in that the etching rate is reduced due to formation of a chelate with excessive etching by-products, thereby reducing the etching efficiency.
상기 킬레이트제는 구체적으로 아르기닌(Arginine), 히스티딘(Histidine), 리신(Lysine), 아스파르트산(Aspartic acid), 글루타민산(Glutamic acid), 글루타민(Glutamine), 세린(Serine), 트레오닌(Threonine), 아스파라긴(Asparagine), 시스테인(Cysteine), 글리신(Glycine), 프롤린(Proline), 세레노시스테인(Serenocysteine), 알라닌(Alanine), 티로신(Tyrosine), 발린(Valine), 트립토판(Tryptophane), 류신(Leucine), 페닐알라닌(Phenylalanine), 메티오닌(Methionine), 에틸렌디니트릴로)테트라아세트산(EDTA), 부틸렌디아민테트라아세트산, (1,2-사이클로헥실렌디니트릴로-)테트라아세트산(cyDTA), 디에틸렌트리아민펜타아세트산(DETPA), 에틸렌디아민테트라프로피온산, (하이드록시에텔)에틸렌디아민트리아세트산(HEDTA), N,N,N’,N’-에틸렌디아민테트라(메틸렌포스폰)산 (EDTMP), 트리에틸렌테트라민헥사아세트산 (TTHA), 1,3-디아미노-2-하이드록시프로판-N,N,N’,N’-테트라아세트산 (DHPTA), 시트르산(Citric acid), 살리실산(Salicylic acid), 타르타르산(Tartaric acid), 글루콘산(Gluconic acid), 옥살산(Oxalic acid), 말론산(Malonic acid), 말산(Malic acid), 설파믹산(Sulfamic acid), 석신산(Succinic acid) 중에서 선택되는 어느 하나 또는 이들의 혼합물일 수 있고, 글리신(Glycine) 및/또는 시트르산(Citric acid)를 사용하는 것이 바람직하다. Specifically, the chelating agent is arginine, histidine, lysine, aspartic acid, glutamic acid, glutamine, serine, threonine, and asparagine. (Asparagine), Cysteine, Glycine, Proline, Serenocysteine, Alanine, Tyrosine, Valine, Tryptophane, Leucine , Phenylalanine, Methionine, ethylenedinitrilo)tetraacetic acid (EDTA), butylenediaminetetraacetic acid, (1,2-cyclohexylenedinitrilo-)tetraacetic acid (cyDTA), diethylenetri Amine pentaacetic acid (DETPA), ethylenediaminetetrapropionic acid, (hydroxyether)ethylenediaminetriacetic acid (HEDTA), N,N,N',N'-ethylenediaminetetra(methylenephosphonic) acid (EDTMP), triethylene Tetraminehexaacetic acid (TTHA), 1,3-diamino-2-hydroxypropane-N,N,N',N'-tetraacetic acid (DHPTA), citric acid, salicylic acid, tartaric acid (Tartaric acid), gluconic acid (Gluconic acid), oxalic acid (Oxalic acid), malonic acid (Malonic acid), malic acid (Malic acid), sulfamic acid (Sulfamic acid), any one selected from succinic acid (Succinic acid) or It may be a mixture of these, and it is preferable to use glycine and/or citric acid.
본 발명의 또 다른 일 실시예에 따르면, 상기 식각용 조성물을 이용하여질화티타늄막 및 텅스텐막이 적층된 반도체 소자에서 상기 질화티타늄막과 텅스텐막을 동시에 식각하는 방법을 제공한다. According to another exemplary embodiment of the present invention, a method of simultaneously etching the titanium nitride layer and the tungsten layer in a semiconductor device in which a titanium nitride layer and a tungsten layer are stacked using the etching composition is provided.
보다 상세하게는, 상기 식각방법은 상기 질화티타늄막 및 텅스텐막을 기판 위에 순차적으로 형성하여 적층체를 제조하는 단계, 상기 식각조성물을 상기 적층체에 가하여 식각을 실시하는 단계를 포함하여, 상기 식각공정을 완료한 후 잔류하는 식각용 조성물을 제거하는 단계가 포함될 수 있다. More specifically, the etching method includes forming a laminate by sequentially forming the titanium nitride film and a tungsten film on a substrate, and performing etching by adding the etching composition to the laminate. After completing the process, the step of removing the remaining etching composition may be included.
상기 기판은 바람직하게는 반도체 웨이퍼일 수 있으나, 이에 한정되는 것은 아니며 통상적으로 사용되는 기판은 모두 사용이 가능할 수 있다. The substrate may preferably be a semiconductor wafer, but is not limited thereto, and all commonly used substrates may be used.
또한, 상기 기판에 대한 질화티타늄막과 텅스텐막은 통상의 질화티타늄막 및 텅스텐 금속막의 형성 방법에 따라 형성될 수 있으며, 질화티타늄막과 텅스텐막의 형성 순서는 특별히 제한되지 않는다. Further, the titanium nitride film and the tungsten film for the substrate may be formed according to a conventional method of forming a titanium nitride film and a tungsten metal film, and the order of forming the titanium nitride film and the tungsten film is not particularly limited.
상기 식각 조성물을 이용하여 식각공정시 온도는 30 내지 80℃일 수 있으며, 상기 식각 온도가 30℃ 미만이면 식각속도가 지니치게 느려 질화티타늄막과 텅스텐막을 식각할 수 없고, 80℃를 초과하면 추가적으로 막손상이 발생할 수 있다. When the etching process is performed using the etching composition, the temperature may be 30 to 80°C. If the etching temperature is less than 30°C, the etching rate is extremely slow, so that the titanium nitride layer and the tungsten layer cannot be etched. Membrane damage may occur.
그러나, 이러한 조건은 엄밀하게 적용되지는 않으며, 당업자에 의해 용이하거나 적합한 조건으로 선택될 수 있다.However, these conditions are not strictly applied and may be easily or appropriately selected by those skilled in the art.
상기 질화티타늄막과 텅스텐막의 적층체에 대한 식각 조성물의 처리 방법은 특별히 한정되지 않으며, 가령, 도포, 침적, 분무 또는 분사 등의 방법일 수 있고, 침적하는 방법(배치식 장치) 또는 분사하는 방법(매엽식 장치)을 바람직하게 이용할 수 있다.The method of treating the etching composition for the laminate of the titanium nitride layer and the tungsten layer is not particularly limited, and may be a method such as coating, dipping, spraying or spraying, and a method of dipping (batch type device) or a method of spraying. (Sheet type device) can be preferably used.
또한, 상기 식각공정을 완료한 후에 잔류하는 상기 식각용 조성물에 대해 초순수 등을 이용한 제거 공정 및 식각이 완료된 적층체에 대한 건조 공정이 실시될 수 있다. In addition, a removal process using ultrapure water or the like for the etching composition remaining after the etching process is completed, and a drying process for the etched laminate may be performed.
이하, 실시예, 비교예 및 실험예를 통하여 본 발명 과정의 세부사항을 설명하고자 한다. 이는 본 발명에 관련된 대표적 예시로서, 이것만으로 본 발명의 적용 범위를 결코 제한할 수 없음을 밝히는 바이다. Hereinafter, details of the process of the present invention will be described through Examples, Comparative Examples and Experimental Examples. This is a representative example related to the present invention, and this alone reveals that the scope of application of the present invention cannot be limited.
실시예 1 내지 실시예 13Examples 1 to 13
하기 표 1에 나타낸 것과 같이 인산, 과산화수소, 물, 암모늄화합물, 아미노산 및 킬레이트제를 식각용 조성물 총 중량에 대하여 표시된 각 중량비로 혼합하여, 본 발명에 따른 식각용 조성물을 제조하였다. As shown in Table 1 below, phosphoric acid, hydrogen peroxide, water, an ammonium compound, an amino acid, and a chelating agent were mixed in each weight ratio indicated with respect to the total weight of the etching composition, to prepare an etching composition according to the present invention.
구분division 식각용 조성물의 조성 (중량%)Composition of etching composition (% by weight)
인산Phosphoric acid 과산화수소Hydrogen peroxide 물water 암모늄화합물Ammonium compounds 킬레이트제Chelating agent
성분ingredient 함량content 성분ingredient 함량content
실시예1Example 1 67.1567.15 1.51.5 31.3531.35
실시예2Example 2 64.6064.60 3.03.0 32.4032.40
실시예3Example 3 67.1167.11 1.51.5 31.3431.34 A-1A-1 0.050.05
실시예4Example 4 67.1167.11 1.51.5 31.3431.34 A-2A-2 0.050.05
실시예5Example 5 67.1167.11 1.51.5 31.3431.34 A-3A-3 0.050.05
실시예6Example 6 67.1167.11 1.51.5 31.3431.34 B-1B-1 0.050.05
실시예7Example 7 67.1167.11 1.51.5 31.3431.34 B-2B-2 0.050.05
실시예8Example 8 67.1167.11 1.51.5 31.3431.34 B-3B-3 0.050.05
실시예9Example 9 63.7563.75 1.51.5 30.7530.75 B-1B-1 4.04.0
실시예10Example 10 67.1167.11 1.51.5 31.3431.34 B-4B-4 0.050.05
실시예11Example 11 67.1167.11 1.51.5 31.3431.34 B-5B-5 0.050.05
실시예12Example 12 67.1167.11 1.51.5 31.3431.34 B-6B-6 0.050.05
실시예13Example 13 64.0964.09 3.03.0 32.3132.31 A-2A-2 0.20.2 B-1B-1 0.20.2
B-4B-4 0.20.2
A-1: Ammonium persulfate; A-2: Ammonium nitrate; A-3: Ammonium acetateB-1: Citric acid; B-2: Oxalic acid; B-3: Succinic acid; B-4: Glycine; B-5: Valine; B-6: Aspartic acidA-1: Ammonium persulfate; A-2: Ammonium nitrate; A-3: Ammonium acetate B-1: Citric acid; B-2: Oxalic acid; B-3: Succinic acid; B-4: Glycine; B-5: Valine; B-6: Aspartic acid
비교예 1 내지 3Comparative Examples 1 to 3
하기 표 2에서 나타낸 바와 같이, 인산, 과산화수소, 물, 질산, APS(Ammonium persulfate) 및 초산을 혼합하여 비교예의 식각용 조성물을 제조하였다. 인산은 85%의 수용액을, 과산화수소는 30% 및 질산은 75% 수용액을 사용하였다. As shown in Table 2 below, phosphoric acid, hydrogen peroxide, water, nitric acid, APS (Ammonium persulfate), and acetic acid were mixed to prepare a composition for etching of Comparative Example. An aqueous solution of 85% silver phosphoric acid, 30% hydrogen peroxide, and 75% silver nitrate was used.
구분division 식각용 조성물의 조성 (중량%)Composition of etching composition (% by weight)
인산Phosphoric acid 과산화수소Hydrogen peroxide 질산nitric acid 물water APSAPS 초산Acetic acid
비교예 1Comparative Example 1 80.7580.75 1.51.5 17.7517.75
비교예 2Comparative Example 2 71.471.4 1.41.4 13.213.2 1414
비교예 3Comparative Example 3 71.471.4 10.510.5 17.117.1 1One
실험예 1 (질화티타늄(TiN) 및 텅스텐(W)의 식각속도 평가)Experimental Example 1 (Evaluation of the etching rate of titanium nitride (TiN) and tungsten (W))
300Å(TiN) 및 400Å(W) 두께의 웨이퍼를 2 x 2㎠ 크기로 시편을 제조하여 60℃의 [표 1], [표 2]의 식각용 조성물에 2 분간 침지시킨 후, 탈이온수(DIW)로 세정 후 건조하여 평가하였으며, 4-Point probe로 막 두께를 측정하여 [표 3]에 기재하였다. 이때, 식각속도는 각 막의 식각처리 전의 막 두께와 식각 처리 후의 막 두께의 차이를 식각 시간(분)으로 나누어 산출한 수치이며, 선택비는 질화티타늄막(TiN)의 식각속도에 대한 텅스텐막(W)의 식각 속도의 비를 나타낸다. Samples of 300Å(TiN) and 400Å(W) thick wafers were prepared in a size of 2×2㎠ and immersed in the etching composition of [Table 1] and [Table 2] at 60℃ for 2 minutes, and then deionized water ), and then dried and evaluated, and the film thickness was measured with a 4-point probe and described in [Table 3]. At this time, the etch rate is a value calculated by dividing the difference between the thickness of each film before the etch treatment and the film thickness after the etch treatment by the etching time (minutes), and the selectivity is the tungsten film ( W) represents the ratio of the etch rate.
실험예 2 ( high-k 손상 여부 평가)Experimental Example 2 (evaluation of high-k damage)
50Å(Al2O3) 두께의 웨이퍼를 2 x 2㎠ 크기로 시편을 제조하여 60℃의 [표 1] 또는 [표 2]의 식각용 조성물에 20분간 침지시킨 후, 탈이온수(DIW)로 세정 후 건조하여 평가하였으며, 식각속도는 엘립소미트리 (Nano-view, SEMG-1000 : Ellipsometry)로 막 두께를 측정하여 그 결과를 [표 3]에 기재하였다.A 50Å(Al 2 O 3 )-thick wafer was prepared in a size of 2 x 2 cm 2 and immersed in the etching composition of [Table 1] or [Table 2] at 60° C. for 20 minutes, and then with deionized water (DIW). After washing, drying was evaluated, and the etch rate was measured by measuring the film thickness by ellipsometry (Nano-view, SEMG-1000: Ellipsometry), and the results are shown in [Table 3].
구분division W 식각속도(Å/min)W Etching speed (Å/min) TiN 식각속도(Å/min)TiN etching rate (Å/min) 선택비(W/TiN)Selection ratio (W/TiN) Al2O3 식각속도(Å/min)Al 2 O 3 etching speed (Å/min)
실시예1Example 1 43.743.7 36.836.8 1.21.2 0.330.33
실시예2Example 2 51.751.7 39.339.3 1.321.32 0.340.34
실시예3Example 3 37.737.7 34.734.7 1.11.1 0.340.34
실시예4Example 4 41.641.6 39.439.4 1.11.1 0.320.32
실시예5Example 5 49.149.1 41.141.1 1.21.2 0.320.32
실시예6Example 6 47.747.7 39.639.6 1.21.2 0.310.31
실시예7Example 7 46.246.2 38.538.5 1.21.2 0.330.33
실시예8Example 8 44.344.3 40.740.7 1.11.1 0.260.26
실시예9Example 9 49.249.2 40.240.2 1.21.2 0.320.32
실시예10Example 10 43.243.2 39.839.8 1.11.1 0.290.29
실시예11Example 11 43.743.7 39.939.9 1.11.1 0.310.31
실시예12Example 12 44.244.2 40.540.5 1.11.1 0.320.32
실시예13Example 13 38.838.8 38.838.8 1.01.0 0.280.28
비교예1Comparative Example 1 9.39.3 32.632.6 0.30.3 0.350.35
비교예2Comparative Example 2 5.55.5 2.32.3 2.42.4 1.911.91
비교예3Comparative Example 3 6.16.1 2.72.7 2.32.3 1.631.63
상기 [표 3]에 나타난 바와 같이 실시예 1 내지 13의 식각조성물을 사용할 경우, 텅스텐 및 질화티타늄 식각속도는 비교예 2 내지 3에 비해 6배 이상의 식각속도와 균일한 식각 선택비를 확인할 수 있으며, Al2O3 식각속도도 비교예 2내지 3에 비해 현저히 낮은 식각속도 특성을 확인할 수 있다. As shown in [Table 3], when the etching compositions of Examples 1 to 13 are used, the etching rates of tungsten and titanium nitride are 6 times higher than those of Comparative Examples 2 to 3, and a uniform etching selectivity can be confirmed. , Al 2 O 3 etching rate was also significantly lower than Comparative Examples 2 to 3 can be confirmed the etching rate characteristics.
또한, 본원 발명의 적정 함량을 벗어난 비교예1은 실시예보다 텅스텐 식각속도가 현저히 낮은 것을 확인할 수 있다In addition, outside the appropriate content of the present invention Comparative Example 1 can be seen that the tungsten etch rate is significantly lower than that of the Example.
실시예 3~13에서와 같이 첨가제를 추가하므로서 식각선택비를 유지하면서도 식각속도를 증진시키거나, 식각 선택비를 1에 더욱 가까워지도록 하는 효과를 볼 수 있다.As in Examples 3 to 13, by adding an additive, while maintaining the etch selectivity, the etch rate may be increased, or the etch selectivity may be closer to one.
이와 같은 결과로부터 실시예 1 내지 13의 식각조성물이 비교예 식각조성물보다 개선된 선택비와 높은 텅스텐 및 질화티타늄 식각속도를 가지며, Al2O3 손상을 최소화하는 특성을 가짐을 확인 할 수 있다.From these results, it can be seen that the etching compositions of Examples 1 to 13 have improved selectivity and higher tungsten and titanium nitride etching rates than the comparative etching compositions, and have characteristics of minimizing Al 2 O 3 damage.
실험예 3 ( 보관시간에 따른 성능 변화 평가)Experimental Example 3 (Evaluation of performance change according to storage time)
실시예1 식각 조성물 제조후 0 ~ 8주까지 주단위로 보관 후 질화티타늄 및 텅스텐 웨이퍼를 60℃에서 식각조성물에 침지하여 보관시간에 따른 식각속도 및 선택비 변화를 확인하였으며, 그결과를 [표 4]에 기재하였다.Example 1 After the preparation of the etching composition, the titanium nitride and tungsten wafers were immersed in the etching composition at 60°C after being stored on a weekly basis for 0 to 8 weeks, and the change in the etching rate and selectivity according to the storage time was confirmed. 4].
보관시간Storage time 식각조성물Etching composition W 식각속도(Å/min)W Etching speed (Å/min) TiN 식각속도(Å/min)TiN etching rate (Å/min) 선택비(W/TiN)Selection ratio (W/TiN)
0일0 days 실시예1Example 1 45.945.9 36.936.9 1.21.2
1일1 day 42.142.1 35.335.3 1.21.2
1주1 week 43.743.7 36.836.8 1.21.2
2주2 weeks 46.646.6 38.838.8 1.21.2
3주3 weeks 46.246.2 39.239.2 1.21.2
4주4 weeks 45.345.3 37.337.3 1.21.2
6주6 weeks 43.843.8 37.637.6 1.21.2
8주8 weeks 44.444.4 35.635.6 1.21.2
또한, 상기 [표 4]는 실시예 1에서 사용된 식각조성물의 보관안정성 평가를 나타낸 것이다. [표 4]에 나타난 바와 같이 보관시간(8주)에도 질화티타늄막 및 텅스텐막에 대한 식각속도의 저하가 발생하지 않았으며, 식각선택비도 1.2내외를 유지하였다. 이와 같은 결과로부터 본 발명에 따른 조성물은 반응으로 인한 함량변화 및 성능저하가 없으며 식각조성물의 우수한 보관안정성을 확인할 수 있었다. 상기 [표 4]의 보관시간에 따른 식각속도의 변화를 관찰한 결과를 도 1에 나타내었다.In addition, the [Table 4] shows the storage stability evaluation of the etching composition used in Example 1. As shown in [Table 4], there was no decrease in etch rate for the titanium nitride film and the tungsten film even during the storage time (8 weeks), and the etch selectivity was maintained around 1.2. From these results, the composition according to the present invention had no content change and performance degradation due to the reaction, and excellent storage stability of the etching composition was confirmed. The result of observing the change of the etching rate according to the storage time in [Table 4] is shown in FIG. 1.
이상으로 본 발명 내용의 특정한 부분을 상세히 기술하였는 바, 당업계의 통상의 지식을 가진 자에게 있어서 이러한 구체적 기술은 단지 바람직한 실시양태일 뿐이며, 이에 의해 본 발명의 범위가 제한되는 것이 아닌 점은 명백할 것이다. 따라서, 본 발명의 실질적은 범위는 첨부된 청구항들과 그것들의 등가물에 의하여 정의된다고 할 것이다.As the specific parts of the present invention have been described in detail above, it will be apparent to those of ordinary skill in the art that these specific descriptions are only preferred embodiments, and the scope of the present invention is not limited thereby. will be. Accordingly, it will be said that the substantial scope of the present invention is defined by the appended claims and their equivalents.

Claims (10)

  1. 질화티타늄막 및 텅스텐막을 동시에 식각하는 식각용 조성물에 있어서,In the etching composition for simultaneously etching a titanium nitride film and a tungsten film,
    (a) 인산 20 내지 75중량%, (b) 과산화수소 1 내지 30중량%, (c)물 1내지 50중량%, (d) 암모늄화합물 0 내지 5 중량%, (e) 킬레이트제 0 내지 10 중량% 로 이루어지는 것을 특징으로 하는 질화티타늄막 및 텅스텐막의 동시 식각용 조성물. (a) 20 to 75% by weight of phosphoric acid, (b) 1 to 30% by weight of hydrogen peroxide, (c) 1 to 50% by weight of water, (d) 0 to 5% by weight of ammonium compounds, (e) 0 to 10% by weight of chelating agent A composition for simultaneous etching of a titanium nitride film and a tungsten film, characterized in that consisting of %.
  2. 제1항에 있어서, The method of claim 1,
    상기 식각용 조성물 전체 중량 대비 0.01 ~ 2wt%의 공지된 첨가제가 더 부가된 것임을 특징으로 하는 질화티타늄막 및 텅스텐막의 동시 식각용 조성물. A composition for simultaneous etching of a titanium nitride film and a tungsten film, characterized in that 0.01 to 2 wt% of a known additive is further added to the total weight of the etching composition.
  3. 제1항에 있어서, The method of claim 1,
    상기 암모늄화합물은 암모늄설페이트(ammonium sulfate), 암모늄퍼설페이트(ammonium persulfate), 수산화암모늄(ammonium hydroxide), 염화암모늄(ammonium chloride), 인산암모늄(ammonium phosphate), 질산암모늄(ammonium nitrate), 암모늄 바이설페이트(ammonium bisulfate) 중에서 선택되는 어느 하나 이상인 것을 특징으로 하는 질화티타늄막 및 텅스텐막의 동시 식각용 조성물. The ammonium compound is ammonium sulfate, ammonium persulfate, ammonium hydroxide, ammonium chloride, ammonium phosphate, ammonium nitrate, ammonium bisulfate A composition for simultaneous etching of a titanium nitride film and a tungsten film, characterized in that at least one selected from (ammonium bisulfate).
  4. 제3항에 있어서,The method of claim 3,
    상기 암모늄화합물은 질산암모늄(Ammonium nitrate)인 것을 특징으로 하는 질화티타늄막 및 텅스텐막의 동시 식각용 조성물. The ammonium compound is a composition for simultaneous etching of a titanium nitride layer and a tungsten layer, characterized in that the ammonium nitrate (Ammonium nitrate).
  5. 제1항에 있어서,The method of claim 1,
    상기 킬레이트제는 아르기닌(Arginine), 히스티딘(Histidine), 리신(Lysine), 아스파르트산(Aspartic acid), 글루타민산(Glutamic acid), 글루타민(Glutamine), 세린(Serine), 트레오닌(Threonine), 아스파라긴(Asparagine), 시스테인(Cysteine), 글리신(Glycine), 프롤린(Proline), 세레노시스테인(Serenocysteine), 알라닌(Alanine), 티로신(Tyrosine), 발린(Valine), 트립토판(Tryptophane), 류신(Leucine), 페닐알라닌(Phenylalanine), 메티오닌(Methionine), (에틸렌디니트릴로)테트라아세트산(EDTA), 부틸렌디아민테트라아세트산, (1,2-사이클로헥실렌디니트릴로-)테트라아세트산(cyDTA), 디에틸렌트리아민펜타아세트산(DETPA), 에틸렌디아민테트라프로피온산, (하이드록시에텔)에틸렌디아민트리아세트산(HEDTA), N,N,N’,N’-에틸렌디아민테트라(메틸렌포스폰)산 (EDTMP), 트리에틸렌테트라민헥사아세트산 (TTHA), 1,3-디아미노-2-하이드록시프로판-N,N,N’,N’-테트라아세트산 (DHPTA), 시트르산(Citric acid), 살리실산(Salicylic acid), 타르타르산(Tartaric acid), 글루콘산(Gluconic acid), 옥살산(Oxalic acid), 말론산(Malonic acid), 말산(Malic acid), 설파믹산(Sulfamic acid), 석신산(Succinic acid) 중에서 선택되는 어느 하나 이상인 것을 특징으로 하는 질화티타늄막 및 텅스텐막의 동시 식각용 조성물. The chelating agents are arginine, histidine, lysine, aspartic acid, glutamic acid, glutamine, serine, threonine, and asparagine. ), Cysteine, Glycine, Proline, Serenocysteine, Alanine, Tyrosine, Valine, Tryptophane, Leucine, Phenylalanine (Phenylalanine), Methionine, (ethylenedinitrilo)tetraacetic acid (EDTA), butylenediaminetetraacetic acid, (1,2-cyclohexylenedinitrilo-)tetraacetic acid (cyDTA), diethylenetriamine Pentaacetic acid (DETPA), ethylenediaminetetrapropionic acid, (hydroxyether)ethylenediaminetriacetic acid (HEDTA), N,N,N',N'-ethylenediaminetetra(methylenephosphonic) acid (EDTMP), triethylenetetra Minhexaacetic acid (TTHA), 1,3-diamino-2-hydroxypropane-N,N,N',N'-tetraacetic acid (DHPTA), citric acid, salicylic acid, tartaric acid ( Tartaric acid), gluconic acid, oxalic acid, malonic acid, malic acid, sulfamic acid, succinic acid A composition for simultaneous etching of a titanium nitride layer and a tungsten layer, characterized by
  6. 제5항에 있어서,The method of claim 5,
    상기 킬레이트제는 시트르산(Citric acid), 글리신(Glycine) 중 적어도 하나 이상인 것을 특징으로 질화티타늄막 및 텅스텐막의 동시 식각용 조성물. The composition for simultaneous etching of a titanium nitride film and a tungsten film, wherein the chelating agent is at least one of citric acid and glycine.
  7. 제1항에 있어서, The method of claim 1,
    상기 암모늄화합물은 0.01 내지 2 중량%, 상기 킬레이트제는 0.01 내지 5 중량% 로 포함하는 것을 특징으로 하는 질화티타늄막 및 텅스텐막의 동시 식각용 조성물. The composition for simultaneous etching of a titanium nitride film and a tungsten film, characterized in that the ammonium compound is contained in an amount of 0.01 to 2% by weight and the chelating agent in an amount of 0.01 to 5% by weight.
  8. 제7항에 있어서, 상기 암모늄화합물은 질산 암모늄(Ammonium nitrate)이고, 상기 킬레이트제는 시트르산(Citric acid) 및 글리신(Glycine)인 것을 특징으로 하는 질화티타늄막 및 텅스텐막의 동시 식각용 조성물.[8] The composition of claim 7, wherein the ammonium compound is ammonium nitrate, and the chelating agent is citric acid and glycine.
  9. 제1항 내지 제8항 중 어느 한 항에 기재된 식각용 조성물을 이용하여 질화티타늄막 및 텅스텐막을 포함하는 반도체 소자에서 질화티타늄막과 텅스텐막을 동시에 식각하는 단계를 포함하는 반도체 소자의 식각 방법. A method of etching a semiconductor device comprising the step of simultaneously etching a titanium nitride film and a tungsten film in a semiconductor device including a titanium nitride film and a tungsten film using the etching composition according to any one of claims 1 to 8.
  10. 제9항에 있어서, 상기 식각 단계는 30 내지 80℃의 온도 범위에서 실시되는 것을 특징으로 하는 반도체 소자의 식각 방법. The method of claim 9, wherein the etching step is performed at a temperature range of 30 to 80°C.
PCT/KR2019/018730 2019-03-25 2019-12-30 Composition for etching laminate of titanium nitride film and tungsten film, and method for etching semiconductor device by using same WO2020197056A1 (en)

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