JP5397218B2 - CMP slurry for silicon film - Google Patents

Description

  The present invention relates to a CMP slurry for a silicon film that can provide excellent flatness and wafer in-plane uniformity with a small number of steps in CMP (Chemical Mechanical Polishing) of a silicon film used for forming a contact plug.

  In order to increase the integration density of semiconductor elements, in particular in memory elements such as DRAMs and SRAMs, it is essential to form contact plugs by a self-alignment method in order to connect the source and drain of MOS transistors to the upper layer wiring. FIG. 1 shows a schematic diagram of a cross section of a semiconductor element when a contact hole is formed by a self-alignment method and then a polysilicon film as a conductive material is formed on the entire surface of the wafer. In FIG. 1, 1 is a silicon substrate, 2 is a gate insulating film, and 3 is a gate structure. The gate structure 3 has a structure having a gate cap layer 4 of an insulating film on a conductive layer. A two-layer structure made of metal silicide 9 and polysilicon 10 is used for the gate conductive layer, and a silicon nitride film is used for the gate cap layer 4. 5 denotes a gate spacer, 6 denotes an etch stopper, and a silicon nitride film is used for the gate spacer 5 and the etch stopper 6. Reference numeral 7 denotes an insulating film, and a silicon oxide film or a BPSG film is used for the insulating film 7.

  The contact hole is formed by removing the insulating film 7 by dry etching using a photoresist. Reference numeral 8 denotes a polysilicon film serving as a conductive material for the contact plug.

  In order to form a contact plug, it is necessary to remove an unnecessary portion of the polysilicon film 8 by CMP and to remove a part of the gate cap layer 4 in order to prevent a short circuit between contact holes. However, since it is necessary to leave the gate cap layer 4 after CMP, the polishing rate of the silicon nitride film constituting the gate cap layer 4 should not be too high. Accordingly, the polishing rate ratio between the polysilicon film and the silicon nitride film, that is, the polishing rate of the polysilicon film: the polishing rate of the silicon nitride film is appropriately 5 to 50: 1.

  Over-polishing for removing a part of the gate cap layer 4 and completely removing an unnecessary part of the polysilicon film 8 is performed with the insulating film 7 exposed. At this time, if the polishing rate of the insulating film 7 is high, the gate cap layer 4 disappears and the polishing progresses to the gate conductive layer, leading to a decrease in device yield and reliability. Therefore, the polishing rate of the silicon oxide film that forms the insulating film 7 is sufficiently lower than that of the silicon nitride film that forms the gate cap layer 4, and it is necessary for CMP to substantially stop. However, if the silicon oxide film is not polished at all, the flatness is adversely affected. Therefore, 1/3 to 1/20 of the silicon nitride film is appropriate for the polishing rate of the silicon oxide film. A cross-sectional view of the semiconductor element after CMP is shown in FIG.

  In the semiconductor element as shown in FIG. 1, the polysilicon film 8 has a thickness of 100 to 400 nm, and the gate cap layer 4 has a thickness of about 10 to 100 nm. In such a case, in order to perform CMP with one kind of slurry, the polishing rate of the polysilicon film is 100 to 300 nm / min, the polishing rate of the silicon nitride film is 5.0 to 30 nm / min, and the silicon oxide film A polishing rate of 0.3 to 3 nm / min is appropriate, and a polishing rate ratio between the polysilicon film and the silicon nitride film, that is, a polishing rate of the polysilicon film: a polishing rate of the silicon nitride film is 5 to 50: 1, The polishing rate ratio between the silicon nitride film and the silicon oxide film, that is, the polishing rate of the silicon nitride film: the polishing rate of the silicon oxide film is suitably 3 to 20: 1.

  However, in the prior art, there is no slurry that can obtain the above polishing rate and polishing rate ratio with one type of slurry with respect to the polysilicon film, silicon nitride film, and silicon oxide film. Therefore, a method such as performing two-stage CMP using two types of slurry is required, and an increase in process cost has been a big problem.

  US Patent Application Publication No. 2006/0105569 describes a CMP in which the polishing rate of a polysilicon film: the polishing rate of a silicon nitride film: the polishing rate of a silicon oxide film is 1: 1: 1 to 4: 1: 1. A method of performing CMP with one kind of slurry under conditions is shown. However, in this method, since the polishing rate ratio between the silicon nitride film and the silicon oxide film, that is, the polishing rate of the silicon nitride film: the polishing rate of the silicon oxide film is as small as 1: 1, the silicon oxide film becomes the CMP stop layer. Therefore, it is considered difficult to control the polishing amount.

  Japanese Patent Laid-Open No. 2002-305167 proposes a method using a polishing liquid containing polyethyleneimine and a choline derivative. With this polishing liquid, it is said that a polysilicon film polishing rate of 600 nm / min, a silicon oxide film polishing rate of 15.2 nm / min, and a silicon nitride film polishing rate of 33.4 nm / min can be obtained. However, even in this method, since the polishing rate ratio between the silicon nitride film and the silicon oxide film, that is, the polishing rate of the silicon nitride film: the polishing rate of the silicon oxide film is as small as 2.2: 1, the silicon oxide film stops the CMP. It is considered that it is difficult to control the polishing amount without forming a layer.

  Japanese Patent No. 3457144 discloses a method using a polysilicon polishing composition containing a basic organic compound. In this method, the polishing rate ratio between the polysilicon film and the silicon oxide film is large, but because the polishing rate of the silicon nitride film is low, the CMP for forming the contact plug cannot be performed with one type of slurry.

  Japanese Patent No. 3190742 discloses a method of polishing a silicon nitride film using an abrasive containing phosphoric acid. In this method, the polishing rate of the silicon nitride film is 120 nm / min, the polishing rate of the silicon oxide film is 15 nm / min, and the polishing rate ratio of the silicon oxide film to the silicon nitride film is sufficiently small. Is slow at 70 nm / min. Therefore, also in this case, the CMP for forming the contact plug cannot be performed with one type of slurry.

  As described above, no CMP slurry capable of performing contact plug formation CMP with one type of slurry has been obtained in the prior art.

  SUMMARY OF THE INVENTION An object of the present invention is to provide a CMP slurry for silicon film that can perform CMP for forming a contact plug by a self-alignment method with one kind of slurry. It is to provide a CMP slurry for a silicon film.

  The present invention relates to a CMP slurry for silicon film that solves the above problems by using a cationic surfactant. Another aspect of the present invention relates to a CMP slurry for a silicon film containing abrasive grains, a cationic surfactant and water and adjusting the pH to an optimum range.

  According to the CMP slurry for silicon film of the present invention, a silicon film, a silicon nitride film, and a silicon oxide film can be CMPed at an appropriate polishing rate and polishing rate ratio. CMP can be performed with one kind of slurry. Thereby, the manufacturing cost of the semiconductor element can be reduced.

FIG. 1 is a cross-sectional view showing a semiconductor element before CMP. FIG. 2 is a cross-sectional view showing the semiconductor element after CMP.

  The best mode for carrying out the invention will be described in detail below.

  The CMP slurry for silicon film of the present invention contains abrasive grains, a cationic surfactant and water as one embodiment, and is useful for CMP of a silicon film such as a polysilicon film or an amorphous silicon film. It is.

  Examples of the abrasive grains used in the present invention include silica, alumina, ceria, zirconia, titania, germania and the like. Among these abrasive grains, silica is preferable, and colloidal silica is particularly preferable in that abrasive grains having a small particle diameter can be obtained at low cost and polishing scratches can be reduced.

  Since the generation of polishing flaws reduces the yield of LSIs, the demand for reduction of polishing flaws becomes more severe as LSIs become finer. Therefore, the average particle diameter of the secondary particles of the abrasive grains before preparation of the CMP slurry is preferably 5 to 150 nm, more preferably 10 to 100 nm as the average grain diameter of the abrasive grains. Moreover, the average particle diameter of the secondary particles of the abrasive grains after the CMP slurry preparation is preferably 5 to 200 nm, more preferably 10 to 150 nm. When the average particle size of the secondary particles of the abrasive grains before and after the CMP slurry preparation is out of the above range, there is a possibility that polishing scratches are likely to occur. Here, “after CMP slurry preparation” refers to after about 24 hours have elapsed since the CMP slurry preparation. Moreover, the average particle diameter of the secondary particles of the abrasive grains can be measured by a dynamic light scattering method. Specifically, it can be measured by a submicron particle analyzer N5 manufactured by Beckman Coulter.

  The concentration of abrasive grains in the CMP slurry for silicon film is preferably 0.1 to 10% by weight, more preferably 0.5 to 5% by weight. When the concentration of the abrasive grains is less than 0.1% by weight, the polishing rate of the silicon film tends to be slow, and when it exceeds 10% by weight, polishing flaws tend to occur.

  In the present invention, by using a cationic surfactant, a high polishing rate of the silicon film, a sufficient polishing rate ratio of the silicon nitride film to the silicon oxide film, and a sufficient polishing rate ratio of the silicon film to the silicon nitride film are obtained. Can do. Further, the optimum pH for obtaining such an effect is in a neutral region of 6.0 to 8.0, and the polishing rate of the silicon nitride film is reduced by the polishing rate of the silicon oxide film because the pH is in the above range. It becomes faster, the ratio of the polishing rate of the silicon nitride film to the polishing rate of the silicon oxide film becomes larger, and it becomes easy to improve the polishing selectivity of the silicon nitride film. When the pH is higher than 8.0, the polishing rate of the silicon film is increased, but the polishing rate of the silicon nitride film is slower than the polishing rate of the silicon oxide film, and as a result, an appropriate polishing rate ratio cannot be obtained. When the pH is less than 6.0, the polishing rate of the silicon film becomes slow, and the ratio of the polishing rate of the silicon film to the polishing rate of the silicon nitride film becomes small. A preferable polishing rate and a preferable polishing rate ratio of each film will be described later.

  The cationic surfactant used in the present invention is not particularly limited as long as it has a chemical structure having a hydrophilic portion and a hydrophobic portion in the molecule and the hydrophilic portion becomes a positive ion in the CMP slurry. Examples thereof include aliphatic amines or salts thereof, and aliphatic ammonium salts.

  As the aliphatic ammonium salt, a compound represented by the following general formula (1) is preferably used.

[R ¹ N (R ² ) ₃ ] ⁺ X ⁻ (1)
(In the formula, R ¹ is a monovalent alkyl group having 8 to 18 carbon atoms in the main chain, and R ² independently represents a monovalent substituent.)
Aliphatic ammonium salt represented by the general formula (1) has a monovalent alkyl group of the long chain as R ^1, from the viewpoint of storage stability of the polishing rate and the slurry of the silicon film, R ¹ is primary A monovalent alkyl group having 8 to 18 carbon atoms in the chain is preferable, and a monovalent alkyl group having 10 to 16 carbon atoms is more preferable. If the carbon number is too small, the polishing rate of the silicon film tends to be slow, so 8 or more is preferable and 10 or more is more preferable. If the carbon number is too large, the stability of the CMP slurry tends to deteriorate, so 18 or less is preferable, and 16 or less is more preferable. In the general formula (1), X is not particularly limited as long as it becomes a negative ion for the cation moiety, and examples thereof include Cl, Br, NO ₃ , CH ₃ COO, and OH. Moreover, the aliphatic ammonium salt represented by the general formula (1) may be a compound represented by the general formula (1) in the CMP slurry, and [R ¹ N (R ² ) ₃ ] A substance that becomes ⁺ and a substance that becomes X ⁻ may be mixed in water. When a quaternary ammonium salt such as tetraethylammonium hydroxide that does not have a long-chain alkyl group is used, the polishing rate of the silicon film becomes slow, particularly in the neutral region of pH 6.0 to 8.0. The polishing rate of the film is increased.

The aliphatic ammonium salt represented by the general formula (1) is R ^{2 in} terms of the polishing rate of the silicon film, the polishing rate ratio of the silicon film to the silicon nitride film, and the polishing rate ratio of the silicon nitride film to the silicon oxide film. Is more preferably alkyltrimethylammonium represented by the following general formula (2).

[C _n H _{2n + 1} N (CH ₃ ) ₃ ] ⁺ X ⁻ (2)
(In the formula, n is an integer of 8 to 18.)
Further, as the aliphatic ammonium salt represented by the general formula (1), a monovalent alkyl radical R ¹ is the number of carbon atoms in the main chain having 8 to 18, one of R ² is the same as R ¹ It is also preferred to use a dialkyldimethylammonium whose other is a methyl group, an alkyldimethylbenzylammonium whose one of R ² is a benzyl group and the other is a methyl group.

  As said fatty amine or its salt, a monoamine, diamine, or those salts are preferable. As the aliphatic diamine, a compound represented by the following general formula (3) is preferably used.

H ₂ N—R ³ —NH ₂ (3)
(In the formula, R ³ represents a divalent alkyl group having 8 to 18 carbon atoms in the main chain.)
Moreover, it is preferable to use the methonium compound represented by following General formula (4) as a salt of aliphatic ammonium.

((CH ₃ ) ₃ N—R ³ —N (CH ₃ ) ₃ ) ²⁺ 2X ⁻ (4)
(In the formula, R ³ represents a divalent alkyl group having 8 to 18 carbon atoms in the main chain.)
The compound represented by the general formula (3) or (4) has the same characteristics as the compound represented by the general formula (1), but is excellent in that the foaming of the CMP slurry can be reduced. In the general formula (3) or (4), R ³ is preferably 8 or more, more preferably 10 or more, because the polishing rate of the silicon film tends to be slow when the number of carbon atoms in the main chain is too small. If the carbon number is too large, the stability of the CMP slurry tends to deteriorate, so 18 or less is preferable, and 16 or less is more preferable. In the general formula (4), X is not particularly limited as long as it becomes a negative ion with respect to the cation moiety, and examples thereof include Cl, Br, NO ₃ , CH ₃ COO, and OH.

  Specific examples of the cationic surfactant used in the present invention include octyltrimethylammonium bromide, decyltrimethylammonium bromide, lauryltrimethylammonium chloride, myristyltrimethylammonium chloride, cetyltrimethylammonium chloride, and stearyltrimethylammonium bromide. Aliphatic ammonium salts; fats such as octylamine, decylamine, dodecylamine, 1,8-diaminooctane, 1,10-diaminodecane, 1,12-diaminododecane, 1,14-diaminotetradecane, 1,16-diaminohexadecane Group amines; methenium compounds such as octamethonium chloride, decamethonium bromide, dodecamethonium bromide, tetradecamethonium chloride, hexadecamethonium chloride;

  The concentration of the cationic surfactant in the CMP slurry for silicon film is preferably 1 to 1000 ppm, more preferably 5 to 500 ppm (ppm is all in terms of weight). When the concentration of the cationic surfactant is less than 1 ppm, the polishing rate of the silicon film is slow, and the polishing rate ratio of the silicon film to the polishing rate of the silicon nitride film tends to decrease. Aggregation of abrasive grains occurs, and the storage stability of the CMP slurry tends to deteriorate.

  In the present invention, by adding a cationic surfactant, a high polishing rate of the silicon film and a low polishing rate of the silicon oxide film can be achieved in a neutral region of pH 6.0 to 8.0. The ratio of the polishing rate of the silicon film to the polishing rate of the silicon nitride film and the ratio of the polishing rate of the silicon oxide film to the polishing rate of the silicon nitride film can be made appropriate.

  The CMP slurry for silicon film of the present invention is a slurry in which abrasive grains are dispersed in water. The amount of water added is the remainder relative to the total amount of the various components described above.

  The pH of the CMP slurry for silicon film is 6.0 to 8.0, preferably 6.2 to 7.8. In the CMP slurry for silicon film of the present invention, in the region where the pH is 6.0 to 8.0, the lower the pH, the higher the polishing rate of the silicon nitride film, whereas the polishing rate of the silicon film and the silicon oxide film The change in polishing rate is small. Therefore, it is possible to easily adjust the polishing rate ratio of each polishing film by adjusting the pH. When the pH of the CMP slurry for silicon film is less than 6.0, the polishing rate of the silicon film becomes slow and the polishing rate of the silicon nitride film becomes fast, so that an appropriate polishing rate ratio cannot be obtained. When the pH exceeds 8.0, the polishing rate of the silicon nitride film is slower than the polishing rate of the silicon oxide film, and an appropriate polishing rate ratio cannot be obtained. The pH of the CMP slurry can be measured by using a pH meter.

  For adjusting the pH of the CMP slurry for silicon film, an appropriate acid or alkali can be used as necessary. The acid is not particularly limited, and inorganic acids such as hydrochloric acid, nitric acid and sulfuric acid, and organic acids such as oxalic acid, acetic acid and malic acid can be used. There is no restriction | limiting in particular as an alkali, Ammonia, an amine, quaternary ammonium hydroxide, potassium hydroxide etc. can be used. Although the compounding quantity of the said acid or alkali is selected suitably, it is 1-1000 ppm with respect to the CMP slurry for silicon films normally.

  In the slurry containing the basic organic compound disclosed in the above-mentioned Japanese Patent No. 3457144, it is possible to obtain a high polishing rate of the silicon film and a low polishing rate of the silicon oxide film, but the pH is less than 6.0. If it exists, the polishing rate of the silicon film becomes slow. If the pH exceeds 8, the polishing rate of the silicon nitride film becomes slow, and an appropriate polishing rate ratio cannot be obtained.

  The CMP slurry for silicon film of the present invention has a small amount of addition of the cationic surfactant and the acid or alkali used for pH adjustment, so that the aggregation of abrasive grains hardly occurs and the storage stability is excellent.

  Further, since the CMP slurry for silicon film of the present invention is stable even when the components of the CMP slurry are concentrated, a method of diluting and using it at the time of use is also possible. Thereby, it is possible to further reduce the cost of the CMP slurry.

  In the CMP process of the silicon film during contact plug formation by the self-alignment method, an appropriate polishing rate and polishing rate ratio of each film can be obtained according to the thickness of each of the silicon film, silicon nitride film, and silicon oxide film. Thus, it is necessary to adjust the polishing conditions. However, it is considered that the polishing rate of each film varies depending on various factors such as the film quality, the type of polishing pad, and the type of polishing apparatus. For these factors, the range that can be adjusted by the polishing conditions such as the polishing pressure and the number of rotations of the polishing platen is limited. It is difficult to get. Therefore, it is essential to adjust the polishing rate and the polishing rate ratio with the CMP slurry.

  In the CMP slurry for silicon film of the present invention, by adjusting the pH, it is possible to adjust only the polishing speed of the silicon nitride film while keeping the polishing speed of the silicon film and the polishing speed of the silicon oxide film substantially constant. Adjustment of the speed ratio is facilitated, and an appropriate polishing speed and polishing speed ratio can be easily achieved.

Next, when the CMP slurry for silicon film of the present invention is used, an appropriate polishing rate for each film will be described. The polishing rate R (pSi) of the silicon film is preferably 100 nm / min or more, more preferably 100 to 300 nm / min, and even more preferably 110 to 250 nm / min. When the polishing rate R (pSi) of the silicon film is less than 100 nm / min, the polishing time becomes long, so the productivity is lowered, and when it exceeds 300 nm / min, the flatness tends to deteriorate due to excessive polishing. It is in. The polishing rate R (SiN) of the silicon nitride film is preferably 5.0 to 30 nm / min, and more preferably 5.0 to 20 nm / min. When the polishing rate R (SiN) of the silicon nitride film is less than 5.0 nm / min, it is necessary to increase the polishing time of the silicon nitride film, so that the productivity tends to decrease, and 30 nm / min. When exceeding, flatness tends to deteriorate due to excessive polishing. The polishing rate R (SiO ₂ ) of the silicon oxide film is preferably 0.3 to 3 nm / min, and more preferably 0.3 to 2.5 nm / min. When the polishing rate R (SiO ₂ ) of the silicon oxide film is less than 0.3 nm / min, the natural oxide film on the surface of the silicon film becomes difficult to be polished. When it exceeds 3 nm / min, flatness tends to deteriorate due to excessive polishing.

  Moreover, when using the CMP slurry for silicon film of the present invention, it is preferable that an appropriate polishing rate ratio of each film satisfies both the following formulas (5) and (6) simultaneously.

R (pSi) / R (SiN)> 5 (5)
R (SiN) / R (SiO ₂ )> 2 (6)
The formula (5) represents the ratio of the polishing rate of the silicon film to the polishing rate of the silicon nitride film, and the value of R (pSi) / R (SiN) is preferably greater than 5 and greater than 5 and 50 or less. More preferably, it is 9 or more and 50 or less. When the value of R (pSi) / R (SiN) is 5 or less, the silicon nitride film is excessively polished and flatness tends to decrease when overpolishing is performed to remove unnecessary polysilicon film. It is in. The above formula (6) shows the polishing rate ratio of the silicon nitride film to the polishing rate of the silicon oxide film, and the value of R (SiN) / R (SiO ₂ ) is preferably larger than 2, and larger than 2. It is more preferably 20 or less, and particularly preferably 2.5 or more and 20 or less. When the value of R (SiN) / R (SiO ₂ ) is 2 or less, flatness tends to deteriorate.

  The CMP polishing method using the CMP slurry for silicon film of the present invention polishes a substrate on which a polishing film including a silicon film, a silicon nitride film and a silicon oxide film is formed using the CMP slurry for silicon film of the present invention. To do. The target films to be polished are a silicon film, a silicon nitride film, and a silicon oxide film, and each of these films may be a single layer or a stacked layer. In the present invention, the silicon film is a polysilicon film or an amorphous silicon film.

  As the substrate, an insulating layer is formed on a semiconductor substrate such as a substrate related to the manufacture of a semiconductor device, for example, a semiconductor substrate at a stage where a circuit element and a wiring pattern are formed, or a semiconductor substrate at a stage where a circuit element is formed. Examples include substrates.

  The polishing of the film to be polished is performed by chemical mechanical polishing. Specifically, the CMP for silicon film of the present invention is performed in a state where the substrate on which the surface to be polished is pressed against the polishing cloth (pad) of the polishing surface plate. The surface to be polished is polished by relatively moving the polishing platen and the substrate while supplying the slurry.

  As an apparatus for polishing, for example, when polishing with a polishing cloth, a general apparatus having a holder that can hold a substrate to be polished and a surface plate that is connected to a motor that can change the number of rotations and to which the polishing cloth is attached. A polishing apparatus can be used. For example, Mirra manufactured by Applied Materials can be used.

  As an abrasive cloth, a general nonwoven fabric, a polyurethane foam, a porous fluororesin, etc. can be used, and there is no restriction | limiting in particular. The polishing conditions are not limited, but the rotation speed of the surface plate is preferably 130 rpm or less so that the substrate does not jump out. The pressing pressure (polishing pressure) of the substrate having the surface to be polished to the polishing cloth is preferably 3 to 60 kPa. More preferably, it is 40 kPa.

  During polishing, the CMP slurry for silicon film is continuously supplied to the polishing cloth with a pump or the like. The supply amount of the CMP slurry for silicon film is not limited, but it is preferable that the surface of the polishing cloth is always covered with the CMP slurry for silicon film.

  The substrate after polishing is preferably washed in running water and then dried after removing water droplets adhering to the substrate using spin drying or the like. In order to perform CMP with the surface state of the polishing cloth always the same, it is preferable to perform a conditioning process of the polishing cloth before polishing. For example, the polishing cloth is conditioned with a liquid containing at least water using a dresser with diamond particles. Subsequently, it is preferable to perform a CMP polishing step according to the present invention and further add a substrate cleaning step.

  When CMP of a semiconductor device having a cross section as shown in FIG. 1 is performed using the CMP slurry for silicon film of the present invention, the gate cap layer 4 and the insulating film 7 are exposed after the polysilicon film 8 is polished. . Thereafter, appropriate overpolishing is performed. In the CMP using the CMP slurry for silicon film of the present invention, the polishing speed of the polysilicon film 8, the polishing speed of the gate cap layer 4, the polishing speed of the insulating film 7, and the polishing of the polysilicon film 8 with respect to the polishing speed of the gate cap layer 4. Since the speed ratio and the polishing rate ratio of the gate cap layer 4 to the polishing rate of the insulating film 7 are appropriate, a part of the gate cap layer 4 is removed without exposing the gate conductive layer as shown in FIG. Then, the unnecessary polysilicon film 8 can be completely removed. Therefore, good flatness and in-plane uniformity can be obtained by CMP using one kind of slurry, and the manufacturing cost of the semiconductor element can be reduced, the yield can be improved, and the reliability can be improved.

  Examples of the present invention will be described below. The present invention is not limited by these examples.

Examples 1-15
In Examples 1 to 15, water, colloidal silica, and a cationic surfactant shown in Table 1 or 2 were mixed, and then malic acid was added to adjust the pH to Table 1 or 2 to prepare a CMP slurry. . The pH was measured with a pH meter (model number HM-21P manufactured by Toa DKK Corporation). Specifically, standard buffer solution (phthalate pH buffer solution pH: 4.01 (25 ° C.), neutral phosphate pH buffer solution pH 6.86 (25 ° C.), borate standard solution pH: 9. 18 (25 ° C.) was used, and after calibrating three points, the electrode was put in a CMP slurry, and the value after 10 minutes or more had elapsed and stabilized was measured.

  The concentration of colloidal silica in the CMP slurry was 3% by weight. The average particle size of the secondary particles of colloidal silica was about 10 nm before the CMP slurry preparation and about 20 nm after the slurry preparation, and this average particle diameter hardly changed even after being left at room temperature for one month after the slurry preparation. The average particle size was measured using a submicron particle analyzer N5 (manufactured by Beckman Coulter).

  The concentration of the cationic surfactant in the CMP slurry is 100 ppm in Examples 1 to 13 and 40 ppm in Examples 14 and 15 (ppm is all in terms of weight). Moreover, the compounding quantity of malic acid used so that the pH of the CMP slurry became the value of Table 1 or 2 was between 5 and 100 ppm in the CMP slurry.

  Using each wafer shown below in which a polysilicon film, a silicon nitride film, and a silicon oxide film are formed, each CMP slurry of Examples 1 to 15 is dropped on a pad attached to a surface plate, and the following is shown. CMP treatment was performed under polishing conditions. Each film thickness before and after the CMP treatment was measured with a light interference film thickness meter, and the polishing rate was calculated from the film thickness difference and the polishing time. The results are shown in Table 1 or 2.

(Wafer)
For CMP of the polysilicon film, a wafer in which a silicon oxide film of 100 nm was formed on a silicon wafer having a diameter (φ) of 8 inches and then a polysilicon film of 500 nm was formed by CVD (Chemical Vapor Deposition) was used.

  For CMP of a silicon nitride film, a wafer having a silicon nitride film of 200 nm formed by CVD on a silicon wafer having a diameter (φ) of 8 inches was used.

  For CMP of a silicon oxide film, a wafer in which a silicon oxide film of 500 nm was formed by plasma CVD on a silicon wafer having a diameter (φ) of 8 inches was used.

(Polishing conditions)
Polishing device: Surface plate size 600 mmφ, rotary type Polishing pad: Polyurethane foam resin Pad groove: Concentric circular polishing pressure: 210 hPa
Number of rotations of wafer substrate: 80 min ⁻¹
Number of rotations of polishing platen: 80 min ⁻¹
Slurry flow rate: 200 ml / min
Polishing time: 1 minute for each film

  As shown in Table 1 or 2, in any of Examples 1 to 15, the polysilicon film polishing rate, the silicon nitride film polishing rate, the silicon oxide film polishing rate, and the silicon nitride film polishing rate Good values were obtained for both the polishing rate ratio of the silicon film and the polishing rate ratio of the silicon nitride film to the polishing rate of the silicon oxide film. Further, if the pH is reduced, the polishing rate of the silicon nitride film becomes slower. Therefore, it is apparent that the polishing rate of the silicon nitride film can be adjusted by adjusting the pH. When a BPSG film is used instead of a silicon oxide film, the polishing rate is expected to increase up to about twice, but from the results of this example, the CMP slurry of the present invention is applicable even when BPSG is used. Is possible.

Comparative Example 1
Use tetramethylammonium hydroxide in place of the cationic surfactant, add tetramethylammonium hydroxide in the CMP slurry to a concentration of 100 ppm, and add malic acid to a pH of 7.2. Except for this, a CMP slurry was prepared in the same manner as in the Example, and the polishing rate of each film was measured. The results are shown in Table 3.

Comparative Example 2
Use tetramethylammonium hydroxide in place of the cationic surfactant, add tetramethylammonium hydroxide in the CMP slurry to a concentration of 100 ppm, and add malic acid to a pH of 6.9. Except for this, a CMP slurry was prepared in the same manner as in the Example, and the polishing rate of each film was measured. The results are shown in Table 3.

Comparative Example 3
Implemented except that lauryltrimethylammonium chloride is used as a cationic surfactant, and the concentration of lauryltrimethylammonium chloride in the CMP slurry is 100 ppm, and malic acid is added so that the pH is 5.7. A CMP slurry was prepared in the same manner as in the example, and the polishing rate of each film was measured. The results are shown in Table 3.

Comparative Example 4
Use lauryltrimethylammonium chloride as the cationic surfactant, add lauryltrimethylammonium chloride in the CMP slurry to a concentration of 100 ppm, and add tetramethylammonium hydroxide to a pH of 8.3. Except for the above, a CMP slurry was prepared in the same manner as in the example, and the polishing rate of each film was measured. The results are shown in Table 3.

  As shown in Table 3, Comparative Examples 1 and 2, which do not use a cationic surfactant, have a lower polishing rate for the polysilicon film and a higher polishing rate for the silicon oxide film than Examples 1-15. Yes. From these results, it is clear that a CMP slurry not using a cationic surfactant cannot obtain an appropriate polishing rate and polishing rate ratio for each film. In Comparative Example 3 where the pH of the CMP slurry is low, the polishing rate of the polysilicon film is slow, and the polishing rate ratio of the polysilicon film to the polishing rate of the silicon nitride film is insufficient. In Comparative Example 4 where the pH of the CMP slurry is high, the polishing rate of the silicon nitride film is slower than the polishing rate of the silicon oxide film. From these results, it can be seen that when the pH of the CMP slurry is less than 6.0 or greater than 8.0, appropriate polishing rates and polishing rate ratios of the three types of films cannot be obtained.

Claims (11)

A CMP slurry for polishing a substrate having a silicon film selected from the group consisting of polysilicon and amorphous silicon , a silicon nitride film, and a silicon oxide film ,
The CMP slurry contains abrasive grains, a cationic surfactant and water,
pH is 6.0-8.0,
A CMP slurry in which the cationic surfactant contains an aliphatic ammonium salt represented by the following general formula (1).
[R ¹ N (R ² ) ₃ ] ⁺ X ⁻ (1)
(In the formula, R ¹ is a monovalent alkyl group having 8 to 18 carbon atoms in the main chain, and R ² independently represents a monovalent substituent.) A CMP slurry for polishing a substrate having a silicon film selected from the group consisting of polysilicon and amorphous silicon , a silicon nitride film, and a silicon oxide film ,
The CMP slurry contains abrasive grains, a cationic surfactant and water,
pH is 6.0-8.0,
CMP slurry in which the cationic surfactant contains an aliphatic ammonium salt represented by the following general formula (2).
_{[C n H 2n + 1 N} (CH 3) 3] + X - ···· (2)
(In the formula, n is an integer of 8 to 18.) The CMP slurry according to claim 1 or 2, wherein the cationic surfactant contains one or more aliphatic ammonium salts selected from alkyltrimethylammonium, dialkyldimethylammonium, and alkyldimethylbenzylammonium. A CMP slurry for polishing a substrate having a silicon film selected from the group consisting of polysilicon and amorphous silicon , a silicon nitride film, and a silicon oxide film ,
The CMP slurry contains abrasive grains, a cationic surfactant and water,
pH is 6.0-8.0,
A CMP slurry in which the cationic surfactant contains an aliphatic amine represented by the following general formula (3).
H ₂ N—R ³ —NH ₂ (3)
(In the formula, R ³ represents a divalent alkyl group having 8 to 18 carbon atoms in the main chain.) A CMP slurry for polishing a substrate having a silicon film selected from the group consisting of polysilicon and amorphous silicon , a silicon nitride film, and a silicon oxide film ,
The CMP slurry contains abrasive grains, a cationic surfactant and water,
pH is 6.0-8.0,
CMP slurry in which the cationic surfactant contains an aliphatic ammonium salt represented by the following general formula (4).
((CH ₃ ) ₃ N—R ³ —N (CH ₃ ) ₃ ) ²⁺ 2X ⁻ (4)
(In the formula, R ³ represents a divalent alkyl group having 8 to 18 carbon atoms in the main chain.) The polishing rate R (pSi) of the silicon film is 100 nm / min or more, the polishing rate R (SiN) of the silicon nitride film is 5.0 to 30 nm / min, and the polishing rate R (SiO ₂ ) of the silicon oxide film is 0.3 to The CMP slurry according to any one of claims 1 to 5, which is 3 nm / min. The polishing rate ratio of the silicon film to the polishing rate of the silicon nitride film: R (pSi) / R (SiN) is greater than 5, and the polishing rate ratio of the silicon nitride film to the polishing rate of the silicon oxide film: R (SiN) / R (SiO ₂₎ is greater than 2, CMP slurry according to any one of claims 1 to 6.   The CMP slurry according to any one of claims 1 to 7, wherein the abrasive grains are silica.   A substrate having a silicon nitride film and at least a silicon film on the silicon nitride film is polished using the CMP slurry according to claim 1, and unnecessary portions of the silicon film are polished. A method for polishing a substrate, wherein the polishing is stopped after the silicon nitride film is removed and a part of the silicon nitride film is removed.   A substrate having a silicon nitride film, a silicon oxide film, and at least the silicon nitride film and a silicon film on the silicon oxide film is polished using the CMP slurry according to claim 1. Then, after unnecessary portions of the silicon film are removed and the silicon nitride film and the silicon oxide film are exposed, polishing is stopped when the silicon nitride film and a part of the silicon oxide film are removed. Polishing method.   The method for polishing a substrate according to claim 9 or 10, wherein a contact plug is formed.

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