WO2018180256A9 - 洗浄液組成物 - Google Patents
洗浄液組成物 Download PDFInfo
- Publication number
- WO2018180256A9 WO2018180256A9 PCT/JP2018/008378 JP2018008378W WO2018180256A9 WO 2018180256 A9 WO2018180256 A9 WO 2018180256A9 JP 2018008378 W JP2018008378 W JP 2018008378W WO 2018180256 A9 WO2018180256 A9 WO 2018180256A9
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- Prior art keywords
- cleaning
- solution composition
- cleaning solution
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- wafer
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- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
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- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
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- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
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- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
- C11D2111/10—Objects to be cleaned
- C11D2111/14—Hard surfaces
- C11D2111/18—Glass; Plastics
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
- C11D2111/10—Objects to be cleaned
- C11D2111/14—Hard surfaces
- C11D2111/22—Electronic devices, e.g. PCBs or semiconductors
Definitions
- the present invention relates to a cleaning solution composition, a stock solution composition for the cleaning solution composition, and a method of manufacturing an electronic device using the cleaning composition.
- CMP chemical mechanical polishing
- a groove is provided in advance on the surface of the substrate, and an insulating film is formed by CVD or the like so as to fill the groove. Thereafter, the insulating film surface is planarized by CMP to form an element isolation region.
- the substrate surface after CMP is contaminated with particles typified by alumina, silica or cerium oxide particles contained in the slurry, metal impurities derived from chemicals constituting the surface to be polished and the slurry. These contaminants cause pattern defects, adhesion defects, electrical characteristics defects and the like, so they need to be completely removed before the next step.
- brush cleaning which combines the chemical action of the cleaning liquid and the physical action of a polyvinyl alcohol sponge brush or the like is performed.
- Patent Document 1 proposes a hydrofluoric acid-ammonium salt-based cleaning solution as an acidic cleaning solution to be used for a substrate having cerium oxide attached to the surface.
- a hydrofluoric acid-ammonium salt-based cleaning solution as an acidic cleaning solution to be used for a substrate having cerium oxide attached to the surface.
- SiO 2 in order to obtain sufficient detergency, it is necessary to increase the high density or processing time of hydrofluoric acid, not only to remove contaminants, SiO 2 to form a layer on the substrate surface Etching of Si 3 N 4 and Si may also occur, which may cause damage to the substrate.
- hydrofluoric acid since hydrofluoric acid has high toxicity, there are also safety issues such as the need for careful attention when working.
- Patent Document 2 proposes a strong acid-water-based cleaning solution such as sulfuric acid as an acidic cleaning solution for cleaning a supply device of a slurry containing cerium oxide.
- a cleaning solution containing sulfuric acid is used, cleaning is generally performed under high temperature conditions (120 to 150 ° C.), and the cleaning device members are corroded, so brush scrub cleaning attached to a CMP apparatus can not be applied.
- Patent Document 3 proposes an ammonia-hydrogen peroxide water-water-based cleaning solution as an alkaline cleaning solution.
- the treatment time needs to be extended, but also the problem of working environment may occur because the generation of ammonia gas is accompanied by a strong odor.
- Patent Document 4 proposes a cleaning solution including three components of an acid, a reducing agent and a fluorine ion for cleaning the surface of a glass material after polishing using an abrasive containing cerium oxide.
- concentration of fluoride ion in the chemical solution is substantially limited to a very low range as there is a risk of latent damage to the glass material, and further, there is no disclosure or suggestion of an embodiment including the use of a surfactant. For this reason, it is expected that the effect of cleaning with the chemical solution is limited.
- SiO 2 silicon oxide
- Si 3 N 4 silicon nitride
- the present inventors are cleaning solution compositions for cleaning the surface of a semiconductor substrate or a glass substrate, which are inorganic acids or salts thereof containing fluorine atoms in the structure.
- the cleaning liquid composition can be used under processing conditions applicable to the brush scrub cleaning chamber of the CMP apparatus without damage to the substrate, and compounds derived from abrasive grains in the slurry, particularly cerium oxide, cerium hydroxide And the like, and as a result of further researches, the present invention has been accomplished.
- a cleaning solution composition for cleaning the surface of a semiconductor substrate or a glass substrate comprising one or more inorganic acids containing a fluorine atom in the structure thereof or one or more salts thereof, water, one or more reducing agents
- the cleaning solution composition containing two or more species and one or more species of anionic surfactant, and having a hydrogen ion concentration (pH) of less than 7.
- the cleaning solution composition according to ⁇ 1>, wherein the inorganic acid containing a fluorine atom in the structure is hydrofluoric acid, hexafluorosilicic acid, tetrafluoroboric acid or a combination thereof.
- cleaning-liquid composition as described in ⁇ 1> whose salt of the mineral acid containing ⁇ 3> fluorine atom is ammonium salt, an amine salt, quaternary ammonium salt, or these combination.
- ⁇ 4> The cleaning solution composition according to any one of ⁇ 1> to ⁇ 3>, wherein the reducing agent is selected from the group consisting of a five-membered ring or a six-membered ring compound having two or more hydroxyl groups.
- ⁇ 5> The cleaning solution composition according to ⁇ 4>, wherein the five-membered ring or the six-membered ring compound having two or more hydroxyl groups is ascorbic acid, catechol, resorcinol, hydroquinone, pyrogallol or methyl catechol.
- ⁇ 6> The cleaning solution composition according to any one of ⁇ 1> to ⁇ 5>, wherein the anionic surfactant is a condensate of naphthalene sulfonic acid and formaldehyde or a salt thereof.
- ⁇ 7> The cerium compound remaining on the surface of the semiconductor substrate or the glass substrate is cleaned when chemical mechanical polishing (CMP) of the surface of the semiconductor substrate or the glass substrate is performed using a slurry containing a cerium compound as abrasive grains.
- CMP chemical mechanical polishing
- ⁇ 8> The stock solution composition for a cleaning solution composition according to any one of ⁇ 1> to ⁇ 7>, which is used to obtain the cleaning solution composition by diluting 10 times to 1000 times. The said stock solution composition.
- CMP Chemical mechanical polishing
- a cleaning liquid composition for cleaning the surface of a semiconductor substrate or glass substrate which is an inorganic acid containing a fluorine atom in the structure (excluding hydrofluoric acid) or a salt thereof, or one or two kinds thereof.
- the cleaning solution composition containing the above and water, and having a hydrogen ion concentration (pH) of less than 7.
- the cleaning solution composition according to [1] wherein the inorganic acid containing a fluorine atom in the structure is hexafluorosilicic acid or tetrafluoroboric acid or a combination thereof.
- a method of cleaning a cerium compound remaining on the surface of a semiconductor substrate or a glass substrate when chemical mechanical polishing (CMP) of the surface of the semiconductor substrate or the glass substrate is performed using a slurry containing a cerium compound as abrasive grains.
- the cleaning liquid composition according to any one of [1] to [7].
- CMP Chemical mechanical polishing
- Cleaning liquid composition of the present invention in the manufacturing process of electronic devices such as semiconductor devices, during washing of a semiconductor substrate or a glass substrate surface, to SiO 2, Si 3 N 4 and Si or the like to form a layer on the substrate surface No damage, can be used under the processing conditions applicable to the brush scrub cleaning chamber with CMP equipment (processing temperature: near room temperature, processing time: within a few minutes, no corrosion of equipment members), It is possible to enhance the removability of the particle-derived compound.
- CMP equipment processing temperature: near room temperature
- processing time within a few minutes, no corrosion of equipment members
- FIG. 1 is a pH-electrogram of a cerium (Ce) -water system.
- FIG. 2 is a graph showing the pH dependency of the zeta potential of each of cerium oxide (CeO 2 ) and silicon oxide (SiO 2 ).
- FIG. 3 is a view showing the relationship between the type of reducing agent contained in the solution for measurement of reduction potential and the reduction potential.
- FIG. 4 is a view showing the type of acid contained in the cleaning solution composition, the type of the reducing agent or the relationship between the presence or absence thereof and the cleaning property.
- FIG. 1 is a pH-electrogram of a cerium (Ce) -water system.
- FIG. 2 is a graph showing the pH dependency of the zeta potential of each of cerium oxide (CeO 2 ) and silicon oxide (SiO 2 ).
- FIG. 3 is a view showing the relationship between the type of reducing agent contained in the solution for measurement of reduction potential and the reduction potential.
- FIG. 4 is
- FIG. 5 is a view showing the relationship between the type of acid contained in the cleaning solution composition, the type or presence or absence of a reducing agent, and the presence or absence of an anionic surfactant and the etching rate for a TEOS wafer.
- FIG. 6 is a view showing the relationship between the type of acid contained in the cleaning solution composition, the type or presence of a reducing agent, and the presence or absence of an anionic surfactant and the solubility of abrasive grains.
- FIG. 7 shows the type of acid contained in the cleaning liquid composition, the type of the reducing agent, the presence or absence of the reducing agent, the presence or absence of the anionic surfactant, and the zeta potential for each particle of CeO 2 , SiO 2 and Si 3 N 4 FIG.
- FIG. 8 is a diagram showing the relationship between the type of acid contained in the cleaning solution composition, the type or absence of reducing agent, and the presence or absence of an anionic surfactant, and the cleaning property of each of TEOS and Si 3 N 4 wafers. It is.
- FIG. 9 is a view showing the relationship between the type of acid contained in the cleaning solution composition, the type of reducing agent, and the presence or absence of an anionic surfactant and the cleaning property to a TEOS wafer.
- FIG. 10 is a view showing the relationship between the type of acid contained in the cleaning solution composition, the presence or absence of hydrogen peroxide (H 2 O 2 ), and the amount of cerium oxide dissolved.
- H 2 O 2 hydrogen peroxide
- FIG. 11 is a view showing the relationship between the pH of the cleaning solution composition and the presence or absence of hydrogen peroxide (H 2 O 2 ) and the amount of cerium oxide dissolved.
- FIG. 12 is a view showing the relationship between the type of acid contained in the cleaning solution composition, the presence or absence of a surfactant, and the zeta potential of cerium oxide.
- FIG. 13 is a view showing the relationship between the type of acid contained in the cleaning solution composition, the presence or absence of a surfactant, and the zeta potential of silicon oxide.
- FIG. 14 is a view showing the relationship between the type of acid contained in the cleaning liquid composition, the presence or absence of a surfactant, and the zeta potential of silicon nitride.
- FIG. 12 is a view showing the relationship between the type of acid contained in the cleaning solution composition, the presence or absence of a surfactant, and the zeta potential of cerium oxide.
- FIG. 13 is a view showing the relationship between the type of acid contained in
- FIG. 15 is a view showing the relationship between the type of acid contained in the cleaning liquid composition, the presence or absence of a surfactant, and the zeta potential of silicon.
- FIG. 16 is a graph showing the relationship between the pH of the cleaning liquid composition and the presence or absence of a surfactant and the zeta potential of cerium oxide.
- FIG. 17 shows that (a) before immersion in the cleaning liquid composition, (b) after immersion in the cleaning liquid composition containing a surfactant, and (c) both the surfactant and hydrogen peroxide (H 2 O 2 )
- FIG. 6 is a view showing an AFM three-dimensional image of the surface of a silicon oxide wafer after immersion in a cleaning liquid composition containing FIG.
- FIG. 6 is a view showing an AFM three-dimensional image of the surface of a silicon nitride wafer after immersion in a cleaning liquid composition containing
- the cleaning solution composition of the present invention is a cleaning solution composition for cleaning the surface of a semiconductor substrate or a glass substrate, comprising one or more inorganic acids or salts thereof containing fluorine atoms in their structures, water, reduction It is the said washing
- cleaning-liquid composition which contains 1 or 2 types of agents, 1 type or 2 types or more of anionic surfactant, and whose hydrogen ion concentration (pH) is less than 7.
- the inorganic acid or a salt thereof containing a fluorine atom in the structure which is used in the cleaning solution composition of the present invention, causes the compound derived from the abrasive grains in the slurry remaining on the substrate surface to be detached from the substrate surface to make the cleaning solution composition. It mainly has an action to dissolve.
- a cleaning solution composition that does not contain a fluorine atom-containing inorganic acid or a salt thereof in the above-mentioned structure has a poor ability to dissolve the compound derived from the abrasive grains in the slurry, and thus the cleaning ability of the substrate surface may not be sufficient.
- the cleaning liquid composition containing hydrofluoric acid not only has insufficient cleaning ability on the substrate surface, but also may cause safety problems due to high toxicity of hydrofluoric acid.
- the inorganic acid or a salt thereof containing a fluorine atom in the structure that can be used in the cleaning solution composition of the present invention, but hydrofluoric acid, hexafluorosilicic acid or tetrafluoroboric acid or a salt thereof Is preferably used.
- the salt ammonium salt, amine salt or quaternary ammonium salt is preferably used. These acids or salts may be used alone or in combination.
- the content of the inorganic acid or a salt thereof containing a fluorine atom in the structure in the cleaning liquid composition of the present invention is not particularly limited, but is preferably 5 to 100 mM, more preferably 20 to 50 mM. preferable.
- the reducing agent that can be used in the cleaning liquid composition of the present invention is not particularly limited, and examples thereof include 5- or 6-membered cyclic compounds having two or more hydroxyl groups, and reducing sugars such as glucose and fructose. Among these, five-membered ring or six-membered ring compounds having two or more hydroxyl groups are preferably used. These reducing agents may be used alone or in combination.
- the five- or six-membered ring constituting a compound having two or more hydroxyl groups may be a saturated or unsaturated five- or six-membered ring, and may be an aromatic five- or six-membered ring. It can also be.
- the five-membered ring or six-membered ring may be composed of only carbon atoms, or may be composed of carbon atoms and hetero atoms (nitrogen atom, oxygen atom, sulfur atom, etc.).
- a reducing agent that is a six-membered ring compound having two or more hydroxyl groups, particularly an aromatic six-membered ring compound having two or more hydroxyl groups, is preferably used in the present invention.
- the reducing agent that can be used in the cleaning solution composition of the present invention is more preferably a five-membered ring or a six-membered ring compound having two or more hydroxyl groups, and ascorbic acid, gallic acid, catechol, resorcinol, hydroquinone, pyrogallol. Or methyl catechol is particularly preferred, with catechol, resorcinol, hydroquinone, pyrogallol or 4-methyl catechol being very particularly preferred.
- the reducing agent that can be used for the cleaning liquid composition of the present invention can be appropriately selected depending on the state of the surface of the semiconductor substrate or the glass substrate to be cleaned, the mode of cleaning, and the like. For example, it is possible to grasp the strength of the reducing power by measuring the reduction potential of the reducing agent, and to appropriately select the reducing agent depending on the desired washing mode.
- the content of the reducing agent is not particularly limited, but is preferably 0.01 to 500 mM, more preferably 0.1 to 50 mM.
- anionic surfactant that can be used in the cleaning solution composition of the present invention, but a condensate of naphthalenesulfonic acid and formaldehyde or a salt thereof is preferably used.
- the content of the anionic surfactant in the cleaning liquid composition of the present invention is not particularly limited, but it is preferably 5 to 1000 ppm, and more preferably 50 to 100 ppm.
- the pH of the cleaning composition of the present invention is less than 7, preferably less than 3.
- the compound derived from abrasive grains in the slurry tends to exhibit high solubility in the cleaning solution composition of the present invention, which is convenient for dissolving and removing the compound in the cleaning solution composition.
- a cerium (Ce) compound such as cerium oxide or cerium hydroxide
- the cerium compound tends to be solid in a high pH range (alkali range), and easily ionizes in a low pH range (acid range). For this reason, it can be understood that in order to dissolve and remove the cerium compound, the solution is preferably in a low pH range.
- the pH of the cleaning liquid composition of the present invention There is no lower limit to the pH of the cleaning liquid composition of the present invention, but 1.0 or more is preferable, and 1.5 or more is more preferable.
- An acid or an alkali other than the inorganic acid containing a fluorine atom in the above structure may be used to adjust the pH of the cleaning liquid composition of the present invention.
- the cleaning liquid composition of the present invention an embodiment containing hydrofluoric acid as an inorganic acid containing a fluorine atom in the structure is exemplified. Another embodiment is an embodiment in which hydrofluoric acid is not contained as an inorganic acid containing a fluorine atom in the structure.
- the cleaning solution composition of the present invention preferably does not contain hydrogen peroxide, particularly hydrogen peroxide water.
- the cleaning liquid composition of the present invention exhibits excellent removability with respect to the compound derived from abrasive grains in the slurry is not clear, the following reason is considered.
- CMP chemical mechanical polishing
- the substrate surface surface of a semiconductor substrate, glass substrate, etc.
- a slurry containing cerium compound as abrasive grains not only the cerium compound but also the cerium compound and the substrate on the substrate surface
- a reactant having a Ce—O—Si bond hereinafter also referred to as “cerium-substrate reactant”
- the cerium-substrate reactant forms a chemical bond with the substrate, which makes removal very difficult.
- the reducing agent contained in the cleaning liquid composition changes the valence of cerium present on the surface of the cerium-substrate reactant from Ce 4+ to Ce 3+ Let This cleaves or weakens the Ce-O-Si bond formed by the cerium-substrate reactant.
- the Ce—O—Si bond formed by the cerium-substrate reactant is completely cut.
- the inorganic acid functions as a complexing agent, it forms a complex with the cerium-substrate reactant whose Ce-O-Si bond is broken to promote dissolution in the cleaning liquid composition and detachment from the substrate surface. Conceivable.
- the cerium compound used as the abrasive it is considered that the cerium in the cerium compound is reduced to Ce 3+ by the reducing agent to improve the solubility in the cleaning liquid composition, and as a result, the cleaning property is improved.
- the surfactant contained in the cleaning solution composition of the present invention covers the surface of the abrasive-derived compound in the slurry to form particles surrounded by the surfactant.
- the zeta potentials of the particles and the substrate surface are in the same sign relation with each other to generate a repulsive force between the particles and the substrate surface, the particles are easily separated from the substrate surface, and the cleaning property of the cleaning liquid composition Is considered to improve.
- zeta of cerium oxide (CeO 2 ) and silicon oxide (SiO 2 ) can be used to remove abrasive grains when a substrate whose surface layer is silicon oxide is polished using a slurry containing cerium oxide as abrasive grains. It is necessary to consider the potential (Fig. 2).
- the zeta potential of the cerium oxide compound forming the abrasive grains is + (plus) in the pH range of about 1.5 to less than about 6, and the zeta potential of the substrate surface formed of silicon oxide is- Because the zeta potentials are negative (minus), the zeta potentials of the two have a different sign, and an attractive force is generated between the cerium oxide compound forming the abrasive grains and the substrate surface.
- the use of a surfactant which is considered to reverse the sign of the zeta potential of the cerium oxide compound is considered to be effective for removing the cerium oxide compound from the substrate surface.
- the surfactant Since both of the cerium oxide compounds are considered to have the effect of increasing the absolute value of the zeta potential, they are considered effective for removing the cerium oxide compounds from the substrate surface.
- Abrasive particles to be removed by the cleaning liquid composition of the present invention that is, abrasive particles used to polish a semiconductor substrate or a glass substrate
- silicon such as silicon oxide (SiO 2 ; also called silica)
- cerium compounds such as cerium oxide (CeO 2 ; also called ceria) and cerium hydroxide (Ce (OH) 4 ) are preferred.
- Cerium compounds such as cerium hydroxide and cerium oxide, and more preferable is cerium oxide.
- the layer forming the surface of the semiconductor substrate to be cleaned by the cleaning liquid composition of the present invention includes silicon oxide, silicon nitride and silicon, and combinations thereof.
- the glass substrate to be cleaned by the cleaning liquid composition of the present invention is also not particularly limited.
- One of the preferable embodiments of the present invention is to clean a cerium compound remaining on the surface of a semiconductor substrate or a glass substrate by chemical mechanical polishing (CMP) using a slurry containing a cerium compound as abrasive grains. And a cleaning solution composition.
- the semiconductor substrate is, for example, a semiconductor substrate for manufacturing a semiconductor device
- the glass substrate is, for example, a glass substrate for manufacturing a hard disk or a flat panel display.
- the components contained in the cleaning solution composition in the present embodiment and the preferred embodiments thereof are the same as the components contained in the cleaning solution composition of the present invention and the preferred embodiments thereof.
- the present invention also relates to the stock solution composition for the washing solution composition of the present invention, which is used to obtain the washing solution composition by diluting 10 times to 1000 times.
- the stock solution composition of the present invention can be obtained by diluting to obtain the cleaning solution composition of the present invention, and the stock solution composition is, for example, 10 times or more, preferably 10 to 1000 times, more preferably 50 to 200.
- the cleaning liquid composition of the present invention can be obtained by diluting twice, the degree of dilution can be appropriately determined by the composition to be formed, and is not limited thereto.
- CMP chemical mechanical polishing
- the retention of the compound derived from the abrasive grains in the slurry used in chemical mechanical polishing can be suppressed to a very low level, so that a high performance device can be manufactured with a high yield. It becomes possible.
- the present invention will be described in more detail by way of Examples and Comparative Examples and Reference Examples and Reference Comparative Examples described below for the cleaning liquid composition of the present invention, but the present invention is not limited thereto.
- the content (mM) is the content in the cleaning composition in each example and comparative example and reference examples and reference comparative examples. (Concentration) is shown.
- the cleaning solution composition can be obtained by dissolving the components shown in the table in water (ultrapure water (DIW)) and then adding methanesulfonic acid (Kanto Chemical) to adjust the pH. .
- DIW ultrapure water
- Kanto Chemical methanesulfonic acid
- anionic surfactant and “surfactant” described in each table are condensates of naphthalene sulfonic acid and formaldehyde (San-yo Kasei).
- ⁇ Evaluation B Detergency of Cleaning Composition (Ce Surface Concentration)> (Preparation of CMP polishing liquid) A cerium oxide slurry (slurry P, manufactured by Hitachi Chemical Co., Ltd.) having an average particle diameter of 0.1 ⁇ m was diluted 10 times to obtain a CMP polishing liquid. (Creating a wafer to be polished) A 1000 nm thick TEOS (Si (OC 2 H 5 ) 4 ) wafer was obtained on a 200 mm diameter silicon substrate by plasma CVD.
- TEOS Si (OC 2 H 5 ) 4
- the wafer to be polished was polished for 30 seconds by using a polishing apparatus (CMP polishing apparatus manufactured by Matt Co., model number: ARW-681 MSII) using the above CMP polishing liquid. After polishing, the wafer was rinsed for 10 seconds using 100 mL of ultrapure water (DIW) while rotating the wafer. Using the cleaning liquid composition having the composition of Table 2, the wafer was cleaned for a predetermined time by rolling a polyvinyl alcohol brush (manufactured by Sof Engineering Co., Ltd.) while rotating the rinsed wafer. A wafer for measurement was obtained by rinsing the cleaned wafer with 300 mL of ultrapure water (DIW) for 30 seconds while rotating, and further drying for 30 seconds at 25 ° C. while rotating.
- DIW ultrapure water
- the Ce concentration on the surface of the wafer for measurement was measured by TXRF (total reflection fluorescent X-ray analyzer) (manufactured by RIGAKU Co., Ltd., model number: 3800 e) to evaluate the cleaning property of the cleaning solution composition.
- the Ce concentration was evaluated by the number of Ce atoms per 1 cm 2 of the wafer surface.
- the results corresponding to each cleaning solution composition and cleaning time are shown in Table 2 and FIG. The obtained results suggest that the lower the reduction potential of the reducing agent, that is, the higher the reducing power of the reducing agent, the higher the detergency.
- ⁇ Evaluation C Damage to Cleaning Composition (Etching Rate)> (Wafer (before immersion) creation)
- a silicon oxide film having a thickness of 1000 nm was formed on a silicon substrate having a diameter of 200 mm by plasma CVD to obtain a TEOS (Si (OC 2 H 5 ) 4 ) wafer (before immersion).
- TEOS Si (OC 2 H 5 ) 4
- the above TEOS wafer (before immersion) was immersed in 100 mL of the cleaning liquid composition having the composition of Table 3 and allowed to stand at room temperature for 5 minutes. Thereafter, the wafer was taken out and rinsed for 1 minute with 5000 mL of ultrapure water (DIW) to obtain a TEOS wafer (after immersion).
- DIW ultrapure water
- the film thickness of the above TEOS wafer (before immersion) is measured by a reflection spectroscopy film thickness meter (manufactured by Otsuka Electronics, model number: FE-3000), and the film thickness of the above TEOS wafer (after immersion) is a reflection spectroscopy film thickness meter (Otsuka Electronics
- the etching rate (E.R.) of the cleaning solution composition with respect to TEOS was calculated from the difference in film thickness before and after immersion, by measurement according to Model No .: FE-3000). The results are shown in Table 4 and FIG.
- ⁇ Evaluation E Measurement of Zeta Potential of CeO 2 , SiO 2 and Si 3 N 4 Particles in Cleaning Composition> 0.05 g of cerium oxide spherical powder having an average particle diameter of 0.6 ⁇ m is mixed with 20 mL of ultrapure water, and stirred for 10 minutes using an ultrasonic device for uniform dispersion, and then 0.05 mL of this solution is collected. The solution was added to 20 mL of the washing solution composition having the composition of These solutions were further stirred and homogenized, and the zeta potential of cerium oxide was measured using a zeta potential measurement device (manufactured by Otsuka Electronics Co., Ltd., model number: ELS-Z2). The zeta potential (mV) of each particle of silicon oxide and silicon nitride was also measured in the same manner as for cerium oxide. The results are shown in Table 4 and FIG.
- ⁇ Evaluation F Detergency of Cleaning Composition (Ce Surface Concentration)> (Creating a wafer to be polished)
- a TEOS film with a thickness of 1000 nm or a Si 3 N 4 film with a thickness of 100 nm was formed by plasma CVD on a silicon substrate with a diameter of 200 mm to obtain a wafer to be polished.
- Wafer polishing and measurement of Ce concentration on wafer surface For Examples 6 and 7 and Comparative Examples 2 and 3, using the cleaning liquid composition having the composition of Table 3, the polishing of the wafer and the measurement of the Ce concentration on the wafer surface described in the above evaluation B were performed.
- the washing time in the washing step was 40 seconds.
- the cleaning solution compositions of Examples 6 and 7 have the solubility of abrasive grains (CeO 2 particles) and the etching on the TEOS wafer as compared with the cleaning solution compositions of Comparative Examples 3 and 4. Despite the low rate, the washability was good. This is because, in the cleaning liquid composition of the present invention, the solubility of the abrasive grains and only the slight etching effect of the substrate do not contribute to the cleaning property, but the Ce- formed between the wafer and the abrasive grains.
- the cleaning liquid composition of the present invention is characterized by the combination of a fluorine atom-containing inorganic acid or salt thereof and a combination of an anionic surfactant and a reducing agent, between the wafer and the abrasive grains. This leads to a further improvement of the washability based on the new washing procedure which weakens the Ce-O-Si bond formed between them.
- ⁇ Evaluation 3 Measurement of zeta potential of each particle of CeO 2 , SiO 2 , Si 3 N 4 and Si in the cleaning liquid composition (acid dependency)> 0.05 g of cerium oxide spherical powder having an average particle diameter of 0.6 ⁇ m is mixed with 20 mL of ultrapure water, and stirred for 10 minutes using an ultrasonic device for uniform dispersion, and then 0.05 mL of this solution is collected.
- the solution was added to 20 mL of the washing solution composition having the composition of These solutions were further stirred and homogenized, and the zeta potential of cerium oxide was measured using a zeta potential measurement device (manufactured by Otsuka Electronics Co., Ltd., model number: ELS-Z2).
- the zeta potential (mV) of each of the particles of silicon oxide, silicon nitride and silicon was also measured in the same manner as for cerium oxide. The results are shown in Table 8 and Figures 12-15.
- ⁇ Evaluation 4 Measurement of zeta potential of CeO 2 particles in the cleaning liquid composition (pH dependency)> 0.05 g of cerium oxide spherical powder having an average particle diameter of 0.6 ⁇ m is mixed with 20 mL of ultrapure water, and stirred for 10 minutes using an ultrasonic device for uniform dispersion, and then 0.05 mL of this solution is collected. The solution was added to 20 mL of the washing solution composition having the composition of These solutions were further stirred and homogenized, and the zeta potential of cerium oxide was measured using a zeta potential measurement device (manufactured by Otsuka Electronics Co., Ltd., model number: ELS-Z2). The results are shown in Table 9 and FIG.
- ⁇ Evaluation 5 Detergency of Cleaning Composition (Ce Surface Concentration, Number of Defects)> (Preparation of CMP polishing liquid)
- a cerium oxide slurry (slurry P, manufactured by Hitachi Chemical Co., Ltd.) having an average particle diameter of 0.1 ⁇ m was diluted 10 times to obtain a CMP polishing liquid.
- a silicon oxide film having a thickness of 1000 nm was formed on a silicon substrate having a diameter of 200 mm by plasma CVD to obtain a wafer to be polished.
- the wafer to be polished was polished for 30 seconds by using a polishing apparatus (CMP polishing apparatus manufactured by Matt Co., model number: ARW-681 MSII) using the above CMP polishing liquid. After polishing, the wafer was rinsed for 10 seconds using 100 mL of ultrapure water (DIW) while rotating the wafer. Using the cleaning liquid composition having the composition of Table 10, while rotating the rinsed wafer, the wafer was cleaned for a predetermined time by rolling a polyvinyl alcohol brush (manufactured by Sof Engineering Co., Ltd.). A wafer for measurement was obtained by rinsing the cleaned wafer with 300 mL of ultrapure water (DIW) for 30 seconds while rotating, and further drying for 30 seconds at 25 ° C. while rotating.
- DIW ultrapure water
- the Ce concentration and the number of defects on the surface of the wafer for the above measurement are TXRF (total reflection X-ray fluorescence analyzer) (manufactured by Rigaku, model number: 3800e) and surface inspection unit (manufactured by Topcon Corporation, model number: WM-10)
- TXRF total reflection X-ray fluorescence analyzer
- surface inspection unit manufactured by Topcon Corporation, model number: WM-10
- the washability of the washing composition was evaluated.
- the Ce concentration was evaluated by the number of Ce atoms per 1 cm 2 of the wafer surface, and the number of defects was obtained by measuring the number of defects of more than 80 nm present on the wafer surface by scattered light.
- the results corresponding to each wash composition and wash time are shown in Table 11.
- ⁇ Evaluation 6 Damage property of cleaning solution composition (etching rate, surface roughness)> (Wafer (before immersion) creation)
- a silicon oxide film having a thickness of 1000 nm was formed on a silicon substrate having a diameter of 200 mm by plasma CVD to obtain a SiO 2 wafer (before immersion).
- a Si 3 N 4 wafer (before immersion) was obtained by the LP-CVD method.
- the above SiO 2 wafer (before immersion) was immersed in 100 mL of the cleaning liquid composition having the composition of Table 12, and left at room temperature for 60 minutes.
- the wafer was taken out and rinsed for 1 minute with 5000 mL of ultrapure water (DIW) to obtain a SiO 2 wafer (after immersion).
- DIW ultrapure water
- the Si 3 N 4 wafer (before immersion) was also immersed in the cleaning liquid composition and rinsed in the same manner as described above to obtain a Si 3 N 4 wafer (after immersion).
- the cleaning liquid composition of the present example is superior to the conventional cleaning liquid composition in terms of the solubility of abrasive grains and the pH stability thereof, and a repulsive force is generated between the substrate and the abrasive grains. It is excellent in zeta potential expression and its pH stability, and there are few residues of abrasive grains on the semiconductor substrate (wafer) after cleaning, and there is also little damage to the wafer.
- the cleaning liquid composition of the present embodiment is a method of forming a layer on the surface of a semiconductor substrate or a glass substrate in the process of manufacturing an electronic device such as a semiconductor device, SiO 2 , Si 3 N 4 and There is no damage to Si etc., and it can be used under processing conditions (processing temperature: near room temperature, processing time: within a few minutes, no corrosion of equipment members) applicable to a brush scrub cleaning chamber with a CMP device.
- processing temperature near room temperature
- processing time within a few minutes, no corrosion of equipment members
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Abstract
Description
近年は、層数の増加に伴い高速研磨が求められる。特に、微細化による記憶容量の向上が困難となってきていることから開発が進められているメモリーセルを立体的に積層した三次元NANDフラッシュメモリーでは、さらに多くの層の絶縁膜を研磨するため、スループット向上やコスト低減には高速研磨が必須である。
さらに、基板上に素子分離領域を形成する工程においては、予め基板表面に溝を設け、この溝を埋めるように絶縁膜がCVDなどによって形成される。その後、絶縁膜表面をCMPによって平坦化することによって、素子分離領域が形成される。素子分離領域の狭幅化に対応するため、シャロー・トレンチ分離(STI)を採用した場合、基板上に形成した絶縁膜の不要な部分を高速研磨で除去することが要求される。
これらのプロセスでは、酸化セリウム、水酸化セリウムなどのセリウム化合物を砥粒としたスラリーの導入が進んでいる。このスラリーは、絶縁膜を高速研磨できることに加えて、研磨時に表面に生じるスクラッチと呼ばれる疵が従来のシリカ系スラリーと比較して低減でき、ストップ膜として使用される窒化シリコン膜との研磨選択性が高いことも利点である。
特許文献1には、酸化セリウムが表面に付着した基板に使用する酸性洗浄液としてフッ化水素酸-アンモニウム塩系洗浄液が提案されている。しかしながら、十分な洗浄性を得るためには、フッ化水素酸の濃度を高くしたり処理時間を長くする必要があるため、汚染物を除去するのみでなく、基板表面の層を形成するSiO2、Si3N4およびSi等のエッチングも生じ、基板へのダメージが加わる恐れがある。また、フッ化水素酸は高い毒性を有するため、作業の際に十分な注意が必要となるなどの安全上の問題もある。
したがって、本発明の目的は、半導体基板またはガラス基板表面を洗浄する際に、基板表面の層を形成する酸化ケイ素(SiO2)(例えば、TEOSなど)、窒化ケイ素(Si3N4)およびケイ素(Si)等へのダメージがなく、CMP装置付帯のブラシスクラブ洗浄チャンバーに適用可能な処理条件(処理温度:室温付近、処理時間:数分以内、装置部材の腐食なし)下で使用することができ、スラリー中の砥粒由来の化合物、特に酸化セリウムや水酸化セリウムなどのセリウム化合物に対して除去性の高い洗浄液組成物を提供することにある。
<1> 半導体基板またはガラス基板表面を洗浄するための洗浄液組成物であって、構造内にフッ素原子を含んだ無機酸またはその塩を1種または2種以上、水、還元剤を1種または2種以上、およびアニオン性界面活性剤を1種または2種以上含有し、かつ、水素イオン濃度(pH)が7未満である、前記洗浄液組成物。
<2> 構造内にフッ素原子を含んだ無機酸が、フッ化水素酸、ヘキサフルオロケイ酸もしくはテトラフルオロホウ酸またはこれらの組み合わせである、<1>に記載の洗浄液組成物。
<3> フッ素原子を含んだ無機酸の塩が、アンモニウム塩、アミン塩もしくは第四級アンモニウム塩またはこれらの組み合わせである、<1>に記載の洗浄液組成物。
<4> 還元剤が、2以上のヒドロキシル基を有する五員環または六員環化合物からなる群から選択される、<1>~<3>のいずれか一項に記載の洗浄液組成物。
<5> 2以上のヒドロキシル基を有する五員環または六員環化合物が、アスコルビン酸、カテコール、レゾルシノール、ヒドロキノン、ピロガロールまたはメチルカテコールである、<4>に記載の洗浄液組成物。
<6> アニオン性界面活性剤が、ナフタレンスルホン酸とホルムアルデヒドとの縮合物またはその塩である、<1>~<5>のいずれか一項に記載の洗浄液組成物。
<7> セリウム化合物を砥粒としたスラリーを用いて、半導体基板またはガラス基板表面の化学的機械研磨(CMP)を行った際に、前記半導体基板またはガラス基板表面に残留したセリウム化合物を洗浄するための、<1>~<6>のいずれか一項に記載の洗浄液組成物。
<8> <1>~<7>のいずれか一項に記載の洗浄液組成物用の原液組成物であって、10倍~1000倍に希釈することにより前記洗浄液組成物を得るために用いられる、前記原液組成物。
<9> セリウム化合物を砥粒としたスラリーを用いて半導体基板またはガラス基板表面の化学的機械研磨(CMP)を行い、次いで<1>~<7>のいずれか一項に記載の洗浄液組成物を用いて前記半導体基板またはガラス基板表面に残留したセリウム化合物を洗浄する工程を含む、電子デバイスの製造方法。
[1] 半導体基板またはガラス基板表面を洗浄するための洗浄液組成物であって、構造内にフッ素原子を含んだ無機酸(ただし、フッ化水素酸を除く)またはその塩を1種または2種以上と水とを含有し、水素イオン濃度(pH)が7未満である、前記洗浄液組成物。
[2] 構造内にフッ素原子を含んだ無機酸がヘキサフルオロケイ酸もしくはテトラフルオロホウ酸またはこれらの組み合わせである、[1]に記載の洗浄液組成物。
[3] 界面活性剤を1種または2種以上含有する、[1]または[2]に記載の洗浄液組成物。
[4] 界面活性剤がナフタレンスルホン酸とホルムアルデヒドとの縮合物またはその塩である、[3]に記載の洗浄液組成物。
[5] 水素イオン濃度(pH)が3未満である、[1]~[4]のいずれか一つに記載の洗浄液組成物。
[6] 過酸化物を1種または2種以上含有する、[1]~[5]のいずれか一つに記載の洗浄液組成物。
[7] 過酸化物が過酸化水素である、[6]に記載の洗浄液組成物。
[9] [1]~[8]のいずれか一つに記載の洗浄液組成物用の原液組成物であって、10倍~1000倍に希釈することにより前記洗浄液組成物を得るために用いられる、前記原液組成物。
[10] セリウム化合物を砥粒としたスラリーを用いて半導体基板またはガラス基板表面の化学的機械研磨(CMP)を行い、次いで[1]~[8]のいずれか一つに記載の洗浄液組成物を用いて前記半導体基板またはガラス基板表面に残留したセリウム化合物を洗浄する工程を含む、電子デバイスの製造方法。
本発明の洗浄液組成物は、半導体素子などの電子デバイスの製造工程における、半導体基板またはガラス基板表面の洗浄の際に、基板表面の層を形成するSiO2、Si3N4およびSi等へのダメージがなく、CMP装置付帯のブラシスクラブ洗浄チャンバーに適用可能な処理条件(処理温度:室温付近、処理時間:数分以内、装置部材の腐食なし)下で使用することができ、スラリー中の砥粒由来の化合物に対して除去性を高めることができる。
まず、本発明の洗浄液組成物について説明する。
本発明の洗浄液組成物は、半導体基板またはガラス基板表面を洗浄するための洗浄液組成物であって、構造内にフッ素原子を含んだ無機酸またはその塩を1種または2種以上、水、還元剤を1種または2種以上、およびアニオン性界面活性剤を1種または2種以上含有し、かつ、水素イオン濃度(pH)が7未満である、前記洗浄液組成物である。
前記構造内にフッ素原子を含んだ無機酸またはその塩を含有しない洗浄液組成物は、スラリー中の砥粒由来の化合物を溶解させる能力に乏しいため、基板表面の洗浄能力が十分でない恐れがある。また、フッ化水素酸を含有する洗浄液組成物は、基板表面の洗浄能力が十分でないのみでなく、フッ化水素酸の高い毒性による安全上の問題が生じる恐れがある。
本発明の洗浄液組成物における、前記構造内にフッ素原子を含んだ無機酸またはその塩の含有量には特に制限がないが、5~100mMであることが好ましく、20~50mMであることがより好ましい。
2以上のヒドロキシル基を有する化合物を構成する五員環または六員環は、飽和または不飽和の五員環または六員環であることができ、また、芳香族五員環または六員環であることもできる。さらに、前記五員環または六員環は炭素原子のみにより構成されていてもよく、あるいは、炭素原子とヘテロ原子(窒素原子、酸素原子、硫黄原子等)とにより構成されていてもよい。例えば、2以上のヒドロキシル基を有する六員環化合物、特に、2以上のヒドロキシル基を有する芳香族六員環化合物、である還元剤は、本発明において好ましく用いられる。
還元剤の含有量には特に制限がないが、0.01~500mMであることが好ましく、0.1~50mMであることがより好ましい。
本発明の洗浄液組成物における、アニオン性界面活性剤の含有量には特に制限がないが、5~1000ppmであることが好ましく、50~100ppmであることがより好ましい。
例えば、酸化セリウム、水酸化セリウム等のセリウム(Ce)化合物を砥粒としたスラリーを用いた場合における該化合物の除去には、セリウム-水系のpH-電位図を考慮する必要がある(図1)。セリウム-水系においては、高いpH領域(アルカリ領域)でセリウム化合物は固体となりやすく、低いpH領域(酸性領域)ではイオン化しやすい。このため、セリウム化合物を溶解させて除去するためには、溶液は低いpH領域にあることが好ましいと理解することができる。
本発明の洗浄液組成物のpHに特に下限はないが、1.0以上が好ましく、1.5以上がより好ましい。
また、本発明の洗浄液組成物は、過酸化水素、特に過酸化水素水、を含有しないことが好ましい。
セリウム化合物を砥粒としたスラリーを用いて基板表面(半導体基板、ガラス基板等の表面)の化学的機械研磨(CMP)を行うと、基板表面にはセリウム化合物のみでなく、セリウム化合物と基板とがCe-O-Si結合を形成した反応物(以下、「セリウム-基板反応物」ともいう)が残留すると考えられている。特に、セリウム-基板反応物は基板との間に化学結合を形成するため、除去がきわめて困難である。
砥粒として用いられたセリウム化合物についても同様に、セリウム化合物中のセリウムが還元剤によってCe3+に還元されて洗浄液組成物への溶解性が向上し、その結果、洗浄性が向上すると考えられる。
本態様における洗浄液組成物が含有する成分およびその好ましい態様は、本発明の洗浄液組成物が含有する成分およびその好ましい態様と同様である。
本発明の原液組成物は、希釈することにより本発明の洗浄液組成物を得られるものであり、該原液組成物を、例えば、10倍以上、好ましくは10~1000倍、より好ましくは50~200倍に希釈することにより本発明の洗浄液組成物を得ることができるが、希釈の度合は構成される組成により適宜決められるものであって、これに限定されない。
各表に示した洗浄液組成物の実施例および比較例ならびに参考例および参考比較例において、含量(mM)は、各実施例および比較例ならびに参考例および参考比較例における洗浄液組成物中での含量(濃度)を示す。別途記載がない限り、洗浄液組成物は、表に示した成分を水(超純水(DIW))に溶解した後、pHの調整のためメタンスルホン酸(関東化学)を添加することにより得られる。また、別途記載がない限り、各表に記載される「アニオン性界面活性剤」および「界面活性剤」は、ナフタレンスルホン酸とホルムアルデヒドとの縮合物(三洋化成)である。
<評価A:還元剤の還元力(還元電位の測定)>
(セリア基板の作成)
直径200mmのシリコン基板上に、蒸着法により厚さ50nmのセリア(CeO2)膜を成膜し、セリア基板を得た。
(還元電位測定用溶液の作成)
塩化水素水溶液(10mM;pH=2)に対して還元剤を添加し、還元電位測定用溶液をそれぞれ調製した。なお、還元剤を添加しなかった塩化水素水溶液を、参照の還元電位測定用溶液とした。
(還元電位の測定)
上記セリア基板を還元電位測定用溶液に浸漬し、それぞれの溶液についてポテンショガルバノスタット(Solartron Analytical社製、型番:SI1287)を用いて還元電位を測定した。測定される還元電位が低いほど、還元剤の還元力が強いと評価される。
表1および図3に還元電位測定用溶液の組成および結果を示す。
(CMP研磨液の調製)
平均粒径が0.1μmの酸化セリウムスラリー(スラリーP、日立化成製)を10倍希釈して、CMP研磨液を得た。
(研磨対象ウエハの作成)
直径200mmのシリコン基板上に、プラズマCVD法により厚さ1000nmのTEOS(Si(OC2H5)4)ウエハを得た。
(ウエハの研磨)
上記CMP研磨液を用いて、研磨装置(マット社製のCMP研磨装置、型番:ARW-681MSII)により30秒間、上記研磨対象ウエハを研磨した。研磨終了後、ウエハを回転させながら超純水(DIW)100mLを用いて10秒間リンスした。表2の組成を有する洗浄液組成物を用いて、リンスしたウエハを回転させながらポリビニルアルコール製のブラシ(ソフエンジニアリング社製)を転がすことにより、ウエハの洗浄を所定時間行った。洗浄されたウエハを回転させながら超純水(DIW)300mLを用いて30秒間リンスし、さらに回転させながら25℃で30秒乾燥することによって、測定用のウエハを得た。
上記測定用のウエハ表面のCe濃度を、TXRF(全反射蛍光X線分析装置)(リガク社製、型番:3800e)により測定し、洗浄液組成物の洗浄性を評価した。Ce濃度はウエハ表面1cm2当たりのCe原子数で評価した。各洗浄液組成物および洗浄時間に対応する結果を、表2および図4に示す。
得られた結果は、還元剤の還元電位が低いほど、すなわち、還元剤の還元力が強いほど洗浄性が高いことを示唆している。
(ウエハ(浸漬前)の作成)
直径200mmのシリコン基板上に、プラズマCVD法により厚さ1000nmの酸化ケイ素膜を成膜し、TEOS(Si(OC2H5)4)ウエハ(浸漬前)を得た。
(洗浄液組成物へのウエハの浸漬)
上記TEOSウエハ(浸漬前)を、表3の組成を有する洗浄液組成物100mL中に浸漬し、5分間室温にて静置した。その後ウエハを取り出し、超純水(DIW)5000mLを用いて1分間リンスすることにより、TEOSウエハ(浸漬後)を得た。
上記TEOSウエハ(浸漬前)の膜厚を反射分光膜厚計(大塚電子製、型番:FE-3000)で測定し、上記TEOSウエハ(浸漬後)の膜厚を反射分光膜厚計(大塚電子製、型番:FE-3000)で測定することで、浸漬前後の膜厚差より、洗浄液組組成物のTEOSに対するエッチングレート(E.R.)を算出した。
表4および図5に結果を示す。
<評価D:洗浄液組成物への砥粒(CeO2粒子)の溶解性>
表3の組成を有する洗浄液組成物50gに酸化セリウム(平均粒径10μm 関東化学製)0.1gを浸漬し、30分間室温にて静置した。固体をろ過後、ろ液中のセリウム濃度をICP-AES(誘導結合プラズマ発光分析装置)(アジレントテクノロジー社製、型番:Agilent720)により分析した。
表4および図6に結果を示す。
平均粒径0.6μmの酸化セリウム球状粉末0.05gを超純水20mLと混合し、超音波装置を用いて10分間撹拌させ均一に分散させた後、この溶液0.05mLを採取し表3の組成を有する洗浄液組成物20mLに加えた。これらの溶液をさらに撹拌、均一にし、ゼータ電位測定装置(大塚電子社製、型番:ELS-Z2)を用いて酸化セリウムのゼータ電位を測定した。
酸化ケイ素および窒化ケイ素の各粒子についても、酸化セリウムと同様の方法でゼータ電位(mV)を測定した。
表4および図7に結果を示す。
(研磨対象ウエハの作成)
直径200mmのシリコン基板上に、プラズマCVD法により厚さ1000nmのTEOS膜または厚さ100nmのSi3N4膜を成膜し、研磨対象ウエハを得た。
(ウエハの研磨およびウエハ表面のCe濃度の測定)
実施例6および7ならびに比較例2および3については、表3の組成を有する洗浄液組成物を用いて、上記評価Bで述べたウエハの研磨およびウエハ表面のCe濃度の測定を行った。なお、洗浄工程における洗浄時間は40秒であった。
比較例4については、ウエハの洗浄工程として、表3の組成を有する洗浄液組成物を用いて洗浄時間10秒の洗浄の後、0.3MのNH4OHおよび1.4MのH2O2を含有する水溶液(SC-1)を用いて30秒の洗浄を行ったほかは、実施例6および7ならびに比較例2および3と同様に、ウエハの研磨およびウエハ表面のCe濃度の測定を行った。
表4および図8に結果を示す。
また、比較例2の洗浄液組成物は、砥粒の溶解性およびTEOSウエハに対するエッチングレートが低く、かつ、洗浄性も劣っていた。
洗浄液組成物の組成と結果を表5および図9に示す。
[参考例1~6、参考比較例1~5]
<評価1:洗浄液組成物への砥粒(CeO2粒子)の溶解性(酸依存性)>
洗浄液組成物50gに酸化セリウム(平均粒径10μm 関東化学製)0.5gを浸漬し、30分間室温にて静置した。固体をろ過後、ろ液中のセリウム濃度をICP-MS(誘導結合プラズマ質量分析装置)(アジレントテクノロジー社製、型番:7500cs)により分析した。表6および図10に洗浄液組成物の組成および結果を示す。
<評価2:洗浄液組成物への砥粒(CeO2粒子)の溶解性(pH依存性)>
表6、7の組成を有する洗浄液組成物を使用した以外は、評価1と同様の方法を用いて酸化セリウムの溶解量を算出した。表7および図11に結果を示す。
平均粒径0.6μmの酸化セリウム球状粉末0.05gを超純水20mLと混合し、超音波装置を用いて10分間撹拌させ均一に分散させた後、この溶液0.05mLを採取し表8の組成を有する洗浄液組成物20mLに加えた。これらの溶液をさらに撹拌、均一にし、ゼータ電位測定装置(大塚電子社製、型番:ELS-Z2)を用いて酸化セリウムのゼータ電位を測定した。
酸化ケイ素、窒化ケイ素およびケイ素の各粒子についても、酸化セリウムと同様の方法でゼータ電位(mV)を測定した。
表8および図12~15に結果を示す。
平均粒径0.6μmの酸化セリウム球状粉末0.05gを超純水20mLと混合し、超音波装置を用いて10分間撹拌させ均一に分散させた後、この溶液0.05mLを採取し表9の組成を有する洗浄液組成物20mLに加えた。これらの溶液をさらに撹拌、均一にし、ゼータ電位測定装置(大塚電子社製、型番:ELS-Z2)を用いて酸化セリウムのゼータ電位を測定した。
表9および図16に結果を示す。
(CMP研磨液の調製)
平均粒径が0.1μmの酸化セリウムスラリー(スラリーP、日立化成製)を10倍希釈して、CMP研磨液を得た。
(研磨対象ウエハの作成)
直径200mmのシリコン基板上に、プラズマCVD法により厚さ1000nmの酸化ケイ素膜を成膜し、研磨対象ウエハを得た。
(ウエハの研磨)
上記CMP研磨液を用いて、研磨装置(マット社製のCMP研磨装置、型番:ARW-681MSII)により30秒間、上記研磨対象ウエハを研磨した。研磨終了後、ウエハを回転させながら超純水(DIW)100mLを用いて10秒間リンスした。表10の組成を有する洗浄液組成物を用いて、リンスしたウエハを回転させながらポリビニルアルコール製のブラシ(ソフエンジニアリング社製)を転がすことにより、ウエハの洗浄を所定時間行った。洗浄されたウエハを回転させながら超純水(DIW)300mLを用いて30秒間リンスし、さらに回転させながら25℃で30秒乾燥することによって、測定用のウエハを得た。
上記測定用のウエハ表面のCe濃度および欠陥数を、それぞれ、TXRF(全反射蛍光X線分析装置)(リガク社製、型番:3800e)および表面検査装置(トプコン社製、型番:WM-10)により測定し、洗浄液組成物の洗浄性を評価した。Ce濃度はウエハ表面1cm2当たりのCe原子数で評価し、欠陥数はウエハ表面に存在する80nm超の欠陥の数を散乱光により測定して求めた。各洗浄液組成物および洗浄時間に対応する結果を、表11に示す。
(ウエハ(浸漬前)の作成)
直径200mmのシリコン基板上に、プラズマCVD法により厚さ1000nmの酸化ケイ素膜を成膜し、SiO2ウエハ(浸漬前)を得た。
また、LP-CVD法により、Si3N4ウエハ(浸漬前)を得た。
(洗浄液組成物へのウエハの浸漬)
上記SiO2ウエハ(浸漬前)を、表12の組成を有する洗浄液組成物100mL中に浸漬し、60分間室温にて静置した。その後ウエハを取り出し、超純水(DIW)5000mLを用いて1分間リンスすることにより、SiO2ウエハ(浸漬後)を得た。
Si3N4ウエハ(浸漬前)に対しても、上記と同様の方法で、洗浄液組成物への浸漬およびリンスを行うことにより、Si3N4ウエハ(浸漬後)を得た。
上記SiO2またはSi3N4ウエハ(浸漬前)の膜厚を反射分光膜厚計(大塚電子製、型番:FE-3000)で測定し、上記SiO2またはSi3N4ウエハ(浸漬後)の膜厚を反射分光膜厚計(大塚電子製、型番:FE-3000)で測定することで、浸漬前後の膜厚差より、洗浄液組組成物のSiO2またはSi3N4に対するエッチングレート(E.R.)を算出した。結果を表12および13に示す。
(ウエハ(浸漬後)の表面ラフネスの測定)
上記SiO2またはSi3N4ウエハ(浸漬後)それぞれについて、走査型プローブ顕微鏡(SIIナノテクノロジー、型番:SPA400)を用いてウエハ表面の三次元像を得た。さらに、走査型プローブ顕微鏡による測定データをもとにウエハ表面のRa(平均面粗さ)を求め、表面ラフネスの評価を行った。結果を表12および13ならびに図17および18に示す。
以上の結果から明らかなように、本参考例の洗浄液組成物は、従来の洗浄液組成物に比して、砥粒の溶解性およびそのpH安定性に優れ、基板-砥粒間に斥力が生じるゼータ電位発現性およびそのpH安定性に優れ、洗浄後の半導体基板(ウエハ)に砥粒の残留が少なく、ウエハへのダメージも少ない。このため、本参考例の洗浄液組成物は、半導体素子などの電子デバイスの製造工程における、半導体基板またはガラス基板表面の洗浄の際に、基板表面の層を形成するSiO2、Si3N4およびSi等へのダメージがなく、CMP装置付帯のブラシスクラブ洗浄チャンバーに適用可能な処理条件(処理温度:室温付近、処理時間:数分以内、装置部材の腐食なし)下で使用することができ、スラリー中の砥粒由来の化合物に対して除去性を高めることができる。
Claims (9)
- 半導体基板またはガラス基板表面を洗浄するための洗浄液組成物であって、構造内にフッ素原子を含んだ無機酸またはその塩を1種または2種以上、水、還元剤を1種または2種以上、およびアニオン性界面活性剤を1種または2種以上含有し、かつ、水素イオン濃度(pH)が7未満である、前記洗浄液組成物。
- 構造内にフッ素原子を含んだ無機酸が、フッ化水素酸、ヘキサフルオロケイ酸もしくはテトラフルオロホウ酸またはこれらの組み合わせである、請求項1に記載の洗浄液組成物。
- フッ素原子を含んだ無機酸の塩が、アンモニウム塩、アミン塩もしくは第四級アンモニウム塩またはこれらの組み合わせである、請求項1に記載の洗浄液組成物。
- 還元剤が、2以上のヒドロキシル基を有する五員環または六員環化合物からなる群から選択される、請求項1~3のいずれか一項に記載の洗浄液組成物。
- 2以上のヒドロキシル基を有する五員環または六員環化合物が、アスコルビン酸、カテコール、レゾルシノール、ヒドロキノン、ピロガロールまたはメチルカテコールである、請求項4に記載の洗浄液組成物。
- アニオン性界面活性剤が、ナフタレンスルホン酸とホルムアルデヒドとの縮合物またはその塩である、請求項1~5のいずれか一項に記載の洗浄液組成物。
- セリウム化合物を砥粒としたスラリーを用いて、半導体基板またはガラス基板表面の化学的機械研磨(CMP)を行った際に、前記半導体基板またはガラス基板表面に残留したセリウム化合物を洗浄するための、請求項1~6のいずれか一項に記載の洗浄液組成物。
- 請求項1~7のいずれか一項に記載の洗浄液組成物用の原液組成物であって、10倍~1000倍に希釈することにより前記洗浄液組成物を得るために用いられる、前記原液組成物。
- セリウム化合物を砥粒としたスラリーを用いて半導体基板またはガラス基板表面の化学的機械研磨(CMP)を行い、次いで請求項1~7のいずれか一項に記載の洗浄液組成物を用いて前記半導体基板またはガラス基板表面に残留したセリウム化合物を洗浄する工程を含む、電子デバイスの製造方法。
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JP7316112B2 (ja) * | 2019-06-25 | 2023-07-27 | 花王株式会社 | 基板の洗浄方法 |
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Family Cites Families (37)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR0183826B1 (ko) * | 1996-03-04 | 1999-05-01 | 김광호 | 연마공정 후처리용 세정 용액 및 그를 이용하는 세정 방법 |
KR100190102B1 (ko) * | 1996-10-19 | 1999-06-01 | 윤종용 | 세정 용액 및 이를 이용한 세정방법 |
JP2007053388A (ja) * | 2000-01-24 | 2007-03-01 | Mitsubishi Chemicals Corp | 表面に遷移金属又は遷移金属化合物を有する半導体デバイス用基板の洗浄液及び洗浄方法 |
US7468105B2 (en) * | 2001-10-16 | 2008-12-23 | Micron Technology, Inc. | CMP cleaning composition with microbial inhibitor |
US7543592B2 (en) * | 2001-12-04 | 2009-06-09 | Ekc Technology, Inc. | Compositions and processes for photoresist stripping and residue removal in wafer level packaging |
TWI302950B (en) * | 2002-01-28 | 2008-11-11 | Mitsubishi Chem Corp | Cleaning solution and method of cleanimg board of semiconductor device |
US20030171239A1 (en) * | 2002-01-28 | 2003-09-11 | Patel Bakul P. | Methods and compositions for chemically treating a substrate using foam technology |
JP4252758B2 (ja) * | 2002-03-22 | 2009-04-08 | 関東化学株式会社 | フォトレジスト残渣除去液組成物 |
JP4336524B2 (ja) | 2002-05-31 | 2009-09-30 | Hoya株式会社 | 情報記録媒体用ガラス基材の製造方法 |
US7384870B2 (en) | 2002-05-31 | 2008-06-10 | Hoya Corporation | Method for manufacturing glass substrate |
JP4419528B2 (ja) | 2003-01-07 | 2010-02-24 | 東ソー株式会社 | 洗浄液及びそれを用いた洗浄方法 |
JP4270544B2 (ja) * | 2003-03-06 | 2009-06-03 | 花王株式会社 | 剥離剤組成物 |
WO2005076332A1 (ja) * | 2004-02-09 | 2005-08-18 | Mitsubishi Chemical Corporation | 半導体デバイス用基板洗浄液及び洗浄方法 |
JP4744228B2 (ja) * | 2004-08-10 | 2011-08-10 | 株式会社東芝 | 半導体基板洗浄液及び半導体基板洗浄方法 |
JP2006310603A (ja) * | 2005-04-28 | 2006-11-09 | Nissan Chem Ind Ltd | ホウ素化合物を含む半導体用洗浄液組成物及び洗浄方法 |
US9058975B2 (en) * | 2006-06-09 | 2015-06-16 | Lam Research Corporation | Cleaning solution formulations for substrates |
US7947637B2 (en) * | 2006-06-30 | 2011-05-24 | Fujifilm Electronic Materials, U.S.A., Inc. | Cleaning formulation for removing residues on surfaces |
JP4642001B2 (ja) * | 2006-10-24 | 2011-03-02 | 関東化学株式会社 | フォトレジスト残渣及びポリマー残渣除去液組成物 |
SG10201610631UA (en) * | 2006-12-21 | 2017-02-27 | Entegris Inc | Liquid cleaner for the removal of post-etch residues |
JP2009099945A (ja) * | 2007-09-28 | 2009-05-07 | Fujifilm Corp | 半導体デバイス用洗浄剤及びそれを用いた洗浄方法 |
CN101959977B (zh) * | 2008-02-29 | 2013-12-04 | 安万托特性材料股份有限公司 | 微电子基底清洁组合物 |
TWI460557B (zh) * | 2008-03-07 | 2014-11-11 | Wako Pure Chem Ind Ltd | 半導體表面用處理劑組成物及使用半導體表面用處理劑組成物之半導體表面處理方法 |
US9048088B2 (en) * | 2008-03-28 | 2015-06-02 | Lam Research Corporation | Processes and solutions for substrate cleaning and electroless deposition |
JP5561914B2 (ja) * | 2008-05-16 | 2014-07-30 | 関東化学株式会社 | 半導体基板洗浄液組成物 |
US8324143B2 (en) | 2008-12-19 | 2012-12-04 | Sanyo Chemical Industries, Ltd. | Cleaning agent for electronic materials |
TWI488960B (zh) * | 2008-12-22 | 2015-06-21 | Fujifilm Corp | 半導體裝置用洗淨液及洗淨方法 |
SG176188A1 (en) | 2009-05-21 | 2011-12-29 | Stella Chemifa Corp | Cleaning liquid and cleaning method |
JP2012079365A (ja) * | 2010-09-30 | 2012-04-19 | Konica Minolta Opto Inc | 情報記録媒体用ガラス基板の製造方法 |
KR101846597B1 (ko) * | 2010-10-01 | 2018-04-06 | 미쯔비시 케미컬 주식회사 | 반도체 디바이스용 기판의 세정액 및 세정 방법 |
JP2012134357A (ja) | 2010-12-22 | 2012-07-12 | Hitachi Chem Co Ltd | Cmp研磨液用洗浄液、これを用いた洗浄方法、並びにこれを用いた半導体基板の製造方法 |
JP5894369B2 (ja) | 2011-02-03 | 2016-03-30 | ステラケミファ株式会社 | 洗浄液及び洗浄方法 |
WO2013122172A1 (ja) * | 2012-02-17 | 2013-08-22 | 三菱化学株式会社 | 半導体デバイス用洗浄液及び半導体デバイス用基板の洗浄方法 |
US9058976B2 (en) * | 2012-11-06 | 2015-06-16 | International Business Machines Corporation | Cleaning composition and process for cleaning semiconductor devices and/or tooling during manufacturing thereof |
US9771550B2 (en) * | 2013-12-11 | 2017-09-26 | Fujifilm Electronic Materials U.S.A., Inc. | Cleaning formulation for removing residues on surfaces |
JP2016037569A (ja) * | 2014-08-08 | 2016-03-22 | 日立化成株式会社 | Cmp用研磨液及びこれを用いた研磨方法 |
JP6713044B2 (ja) * | 2016-06-02 | 2020-06-24 | 富士フイルム株式会社 | 処理液、基板の洗浄方法及びレジストの除去方法 |
JP6663498B2 (ja) * | 2016-07-29 | 2020-03-11 | 富士フイルム株式会社 | 処理液及び基板洗浄方法 |
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