JP2015205348A - Abrasive, abrasive set and substrate abrasion method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an abrasive which can improve the abrasion selectivity of an insulating film for a stopper film.SOLUTION: An abrasive comprises an abrasive grain comprising a hydroxide particle of a tetravalent metal element, a compound in which at least one of oxyethylene and oxypropylene is added to ethylenediamine, and liquid medium.

Description

  The present invention relates to an abrasive, an abrasive set, and a method for polishing a substrate.

  In recent semiconductor device manufacturing processes, the importance of processing technology for higher density and miniaturization is increasing. One of the processing technologies, CMP (Chemical Mechanical Polishing), is the formation of shallow trench isolation (STI, Shallow Trench Isolation), pre-metal insulating film or interlayer in the manufacturing process of semiconductor devices. This technique is indispensable for planarizing an insulating film, forming a plug or a buried metal wiring, and the like.

  The most frequently used abrasives are silica-based abrasives containing silica (silicon oxide) particles such as fumed silica and colloidal silica as abrasive grains. Silica-based abrasives are characterized by high versatility, and by appropriately selecting the abrasive content, pH, additives, etc., a wide variety of films can be polished regardless of insulating films and conductive films. it can.

  On the other hand, there is an increasing demand for abrasives containing cerium compound particles as abrasive grains mainly for insulating films such as silicon oxide films. For example, a cerium oxide-based abrasive containing cerium oxide (ceria) particles as abrasive grains can polish a silicon oxide film at high speed even with a lower abrasive grain content than a silica-based abrasive (see, for example, Patent Documents 1 and 2 below) ).

  By the way, in recent years, in the manufacturing process of a semiconductor element, it has been required to achieve further miniaturization of wiring, and polishing scratches generated during polishing have become a problem. That is, even if a fine polishing flaw occurs when polishing using a conventional cerium oxide-based abrasive, there is no problem if the size of the polishing flaw is smaller than the conventional wiring width. However, when trying to achieve further miniaturization of the wiring, there is a problem even if the polishing scratches are minute.

  In order to solve this problem, an abrasive using a hydroxide particle of a tetravalent metal element has been studied (for example, see Patent Documents 3 to 5 below). Further, a method for producing hydroxide particles of a tetravalent metal element has been studied (for example, see Patent Documents 6 and 7 below). These techniques try to reduce polishing scratches caused by particles by making the mechanical action as small as possible while taking advantage of the chemical action of the hydroxide particles of the tetravalent metal element.

  In addition, in the CMP process for forming the STI, a stopper film (polishing stop layer) disposed on the convex portion of the substrate having the concavo-convex pattern, and the substrate and the stopper film so as to fill the concave portion of the concavo-convex pattern. In polishing a laminated body having an insulating film (for example, a silicon oxide film) disposed, the insulating film is polished using a stopper film. This is because it is difficult to control the polishing amount of the insulating film (film thickness removed in the insulating film), and the degree of polishing is controlled by polishing the insulating film until the stopper film is exposed. In this case, in the polishing, it is necessary that the stopper film is hardly removed while the insulating film is sufficiently removed. That is, in the polishing characteristics of the abrasive, it is necessary to increase the polishing selectivity of the insulating film with respect to the stopper film (polishing speed ratio: polishing speed of the insulating film / polishing speed of the stopper film).

  In response to such a demand, an abrasive containing an additive is known (for example, see Patent Document 8 below). According to this technique, the abrasive contains the hydroxide particles of the tetravalent metal element and at least one of the cationic polymer and the polysaccharide, whereby the silicon oxide film is polished at high speed, and silicon nitride is obtained. An excellent polishing selectivity with respect to the film can be obtained.

Japanese Patent Laid-Open No. 10-106994 Japanese Patent Application Laid-Open No. 08-022970 International Publication No. 2002/067309 International Publication No. 2012/070541 International Publication No. 2012/070542 JP 2006-249129 A International Publication No. 2009/131133 International Publication No. 2012/070544

  Conventionally, a silicon nitride film is used as the stopper film, but in recent years, the use of a polysilicon film as the stopper film is increasing. In this case, it is necessary to further improve the polishing selectivity of the insulating film with respect to the polysilicon film. However, there are few known abrasives that have excellent polishing selectivity of the insulating film with respect to the polysilicon film.

  Moreover, the stopper film used may differ with the structure of a semiconductor element. However, even if the polishing agent has high polishing selectivity for a certain type of stopper film, high polishing selectivity is often not obtained for another type of stopper film. In this way, many abrasives are inferior in versatility, and the present situation is that the abrasives are selectively used depending on the type of the stopper film.

  An object of the present invention is to provide an abrasive, an abrasive set, and a substrate polishing method capable of improving the polishing selectivity of an insulating film with respect to a stopper film. And

  More specifically, an object of the present invention is to provide a polishing agent, a polishing agent set, and a substrate polishing method capable of improving the polishing selectivity of an insulating film with respect to a polysilicon film. Another object of the present invention is to provide a polishing agent, a polishing agent set, and a substrate polishing method that are capable of improving the polishing selectivity of an insulating film with respect to a silicon nitride film and that are excellent in versatility. .

  A first aspect of the abrasive according to the present invention is an abrasive comprising a hydroxide particle of a tetravalent metal element and a compound in which at least one of oxyethylene and oxypropylene is added to ethylenediamine (hereinafter referred to as “EOPO addition” in some cases). And a liquid medium.

  According to the abrasive | polishing agent which concerns on a 1st aspect, the grinding | polishing selectivity of the insulating film with respect to a stopper film can be improved. Thereby, the insulating film can be satisfactorily polished using the stopper film.

  For example, according to the abrasive | polishing agent which concerns on a 1st aspect, the grinding | polishing selectivity of the insulating film with respect to a polysilicon film can be improved. Thereby, even if a polysilicon film is used as the stopper film, the insulating film can be satisfactorily polished using the polysilicon film. Moreover, according to the abrasive | polishing agent which concerns on a 1st aspect, the grinding | polishing selectivity of the insulating film with respect to a silicon nitride film can be improved. As a result, even when a silicon nitride film is used as the stopper film, the insulating film can be satisfactorily polished using the silicon nitride film. Since the abrasive | polishing agent which concerns on such a 1st aspect can acquire high grinding | polishing selectivity irrespective of the kind of stopper film | membrane, versatility is high.

  Further, according to the polishing agent according to the first aspect, in the CMP technique for flattening the shallow trench isolation insulating film, the premetal insulating film, the interlayer insulating film, etc., the insulating film is polished at a high speed and an advanced flat surface is obtained. You can also. Furthermore, according to the abrasive | polishing agent which concerns on a 1st aspect, while being able to grind | polish an insulating film at high speed, an insulating film can also be grind | polished with a low grinding | polishing scratch.

  A second aspect of the abrasive according to the present invention is an aspect in which the abrasive according to the first aspect further contains polyvinylpyrrolidone. By using polyvinylpyrrolidone in combination with the EOPO adduct, the polishing rate of the insulating film can be further improved and the polishing selectivity of the insulating film with respect to the stopper film can be further improved as compared with the first embodiment.

  A third aspect of the abrasive according to the present invention is an aspect in which the abrasive according to the first aspect further contains a glycerin compound. By using a glycerin compound in combination with the EOPO adduct, the polishing rate of the insulating film is further improved and the polishing rate of the stopper film is further suppressed as compared with the first embodiment. Polishing selectivity can be further improved.

  The 4th aspect of the abrasive | polishing agent which concerns on this invention is an aspect in which the abrasive | polishing agent which concerns on the said 1st aspect further contains polyvinylpyrrolidone and a glycerol compound. In this case, by using both the polyvinylpyrrolidone and the glycerin compound together with the EOPO adduct, the polishing rate of the insulating film can be further improved as compared with the first aspect. Polishing selectivity can be further improved.

  The glycerol compound is preferably at least one selected from the group consisting of polyglycerol, diglycerol derivatives and polyglycerol derivatives. By using these compounds together with the EOPO adduct, the polishing selectivity of the insulating film with respect to the stopper film can be further improved.

  In the present specification, “polyglycerin” is polyglycerin (polyglycerin of trimer or higher) having an average degree of polymerization of glycerin of 3 or more. In the present specification, “diglycerin derivative” is a compound in which a functional group is introduced into diglycerin, and “polyglycerin derivative” introduces a functional group into polyglycerol having an average degree of polymerization of glycerin of 3 or more. It is a compound. Details will be described later.

  The glycerol compound is more preferably at least one selected from the group consisting of polyglycerol and diglycerol derivatives. Thereby, compared with the case where another glycerol compound is used, the polishing rate of an insulating film can further be improved.

  More preferably, the glycerin compound is polyglycerin. Thereby, compared with the case where other glycerol compounds are used, the polishing rate of the stopper film can be further suppressed. In particular, when the stopper film is a polysilicon film, the polishing rate of the stopper film can be further suppressed.

  In addition, this effect is more remarkable in the abrasive of the fourth aspect (abrasive that uses both polyvinylpyrrolidone and a glycerin compound in combination with the EOPO adduct). That is, when polyglycerin is used as the glycerin compound, the polishing rate of the insulating film is further improved and the polishing rate of the stopper film is further suppressed. As a result, the polishing selectivity of the insulating film with respect to the stopper film is increased. Further improvement can be achieved.

  The tetravalent metal element hydroxide particles are preferably at least one selected from the group consisting of rare earth metal hydroxide particles and zirconium hydroxide particles. Thereby, the polishing rate of the insulating film can be further improved.

  The content of the EOPO adduct is preferably 0.01% by mass or more and 10% by mass or less based on the total mass of the abrasive. Thereby, the polishing rate of the stopper film can be further suppressed.

  Further, one embodiment of the present invention relates to the use of the above polishing agent for polishing a surface to be polished containing silicon oxide. For example, the surface to be polished containing silicon oxide is polished to remove excess silicon oxide. It relates to the use of said abrasive for polishing. That is, one embodiment of the abrasive according to the present invention is preferably used for polishing a surface to be polished containing silicon oxide. For example, the surface to be polished containing silicon oxide is polished to remove excess silicon oxide. It is preferably used for removing.

  In the abrasive set according to the present invention, the constituents of the abrasive are stored separately in a first liquid and a second liquid, the first liquid includes abrasive grains and a liquid medium, and the second liquid is Including the EOPO adduct and a liquid medium. According to the abrasive | polishing agent set which concerns on this invention, the said effect similar to the abrasive | polishing agent which concerns on this invention can be acquired.

  In the abrasive set according to the present invention, the second liquid may further include polyvinyl pyrrolidone, or the second liquid may further include a glycerin compound.

  The substrate polishing method according to the present invention includes a step of polishing a surface to be polished of the substrate using the abrasive. According to the substrate polishing method of the present invention, the same effect as that of the abrasive according to the present invention can be obtained by using the abrasive.

  According to the present invention, the polishing selectivity of the insulating film with respect to the stopper film can be improved. Thereby, the insulating film can be satisfactorily polished using the stopper film.

  For example, according to the present invention, the polishing selectivity of the insulating film with respect to the polysilicon film can be improved and the polishing selectivity of the insulating film with respect to the silicon nitride film can be improved. Thereby, even when a polysilicon film or a silicon nitride film is used as the stopper film, the insulating film can be polished satisfactorily using the stopper film.

  In addition, according to the present invention, as a technique for planarizing a substrate surface in the manufacture of a semiconductor device, for example, in a CMP technique for planarizing a shallow trench isolation insulating film, a premetal insulating film, an interlayer insulating film, etc., the insulating film can be formed at high speed. It is possible to obtain a highly flat surface while polishing. Furthermore, according to the present invention, the insulating film can be polished at high speed, and the insulating film can be polished with low polishing scratches.

  Hereinafter, the abrasive | polishing agent which concerns on embodiment of this invention, an abrasive | polishing agent set, and the grinding | polishing method of the base | substrate using these are demonstrated in detail.

<Definition>
As used herein, “abrasive” is defined as a composition that touches the surface to be polished during polishing. The phrase “abrasive” itself does not limit the components contained in the abrasive. As will be described later, the abrasive according to the present embodiment contains abrasive grains. Abrasive grains are also referred to as “abrasive particles”, but are referred to herein as “abrasive grains”. Abrasive grains are generally solid particles, and the object to be removed is removed during polishing by the mechanical action of the abrasive grains and the chemical action of the abrasive grains (mainly the surface of the abrasive grains). However, it is not limited to this.

<Abrasive>
The abrasive according to this embodiment can be used as, for example, an abrasive for CMP (hereinafter referred to as “CMP abrasive”). Specifically, the first aspect of the abrasive according to the present embodiment is (A) abrasive grains containing hydroxide particles of a tetravalent metal element, and (B) at least one of oxyethylene and oxypropylene in ethylenediamine. Containing a compound (EOPO adduct) and a liquid medium. The second aspect of the abrasive according to the present embodiment includes (A) abrasive grains containing hydroxide particles of a tetravalent metal element, (B) the EOPO adduct, (C) polyvinylpyrrolidone, and a liquid medium. And containing. A third aspect of the abrasive according to the present embodiment includes (A) abrasive grains containing hydroxide particles of a tetravalent metal element, (B) the EOPO adduct, (D) a glycerin compound, and a liquid medium. And containing. A fourth aspect of the abrasive according to the present embodiment includes (A) abrasive grains containing hydroxide particles of a tetravalent metal element, (B) the EOPO adduct, (C) polyvinyl pyrrolidone, and (D ) A glycerin compound and a liquid medium are contained. Hereinafter, essential components and components that can be optionally added will be described.

[Abrasive grain]
The abrasive | polishing agent which concerns on this embodiment contains the particle | grains of the hydroxide of a tetravalent metal element as an abrasive grain. The hydroxide particles of the tetravalent metal element are more reactive with the constituent material of the insulating film (for example, silicon oxide) than the conventional abrasive grains made of silica or ceria, and the insulating film is polished at a high polishing rate. Can be polished. Moreover, it can grind | polish with a low grinding | polishing damage | wound compared with the conventional abrasive grain which consists of silica or ceria.

  Other abrasive grains that can be used in combination with the hydroxide particles of the tetravalent metal element in the abrasive according to the present embodiment include particles of silica, alumina, ceria, and the like. In addition, as abrasive grains containing tetravalent metal element hydroxide particles, composite particles containing tetravalent metal element hydroxide and silica can also be used.

  In the abrasive grains, the content of the tetravalent metal element hydroxide particles is preferably 80% by mass or more, more preferably 90% by mass or more, still more preferably 95% by mass or more, based on the whole abrasive grains. Mass% or more is particularly preferable, and 99 mass% or more is extremely preferable. From the viewpoint of easy preparation of an abrasive and further excellent polishing characteristics, the abrasive grains are composed of hydroxide particles of the tetravalent metal element (100% by mass of the abrasive grains is water of the tetravalent metal element). Most preferred are oxide particles).

  The tetravalent metal element hydroxide particles are preferably at least one selected from the group consisting of rare earth metal hydroxide particles and zirconium hydroxide particles. The tetravalent metal element hydroxide particles are preferably rare earth metal hydroxide particles from the viewpoint of further improving the polishing rate of the insulating film. Examples of the rare earth metal element capable of taking tetravalence include lanthanoids such as cerium, praseodymium, and terbium. Among these, cerium is preferable from the viewpoint of further improving the polishing rate of the insulating film. Rare earth metal hydroxide particles and zirconium hydroxide particles may be used in combination, or two or more rare earth metal hydroxide particles may be selected and used.

  As a method for producing hydroxide particles of a tetravalent metal element, a technique of mixing a salt of a tetravalent metal element and an alkali solution can be used. This method is described in, for example, “Science of rare earths” (edited by Adiya Ginya, Kagaku Dojin, 1999), pages 304-305.

As a salt of a tetravalent metal element, a conventionally known salt can be used without particular limitation, and M (SO ₄ ) ₂ , M (NH ₄ ) ₂ (NO ₃ ) ₆ , M (NH ₄ ) ₄ (SO ₄ ) ₄ (M represents a rare earth metal element), Zr (SO ₄ ) ₂ .4H ₂ O, and the like. M is preferably chemically active cerium (Ce).

  A conventionally well-known thing can be especially used as an alkaline liquid without a restriction | limiting. Basic compounds in the alkaline solution include organic bases such as imidazole, tetramethylammonium hydroxide (TMAH), guanidine, triethylamine, pyridine, piperidine, pyrrolidine, chitosan; ammonia, potassium hydroxide, sodium hydroxide, calcium hydroxide. Inorganic bases such as Among these, from the viewpoint of further improving the polishing rate of the insulating film, ammonia and imidazole are preferable, and imidazole is more preferable. The hydroxide particles of the tetravalent metal element synthesized by the above method can be washed to remove metal impurities. For washing the hydroxide particles of the tetravalent metal element, a method of repeating solid-liquid separation several times by centrifugation or the like can be used. Moreover, it can also wash | clean in processes, such as centrifugation, dialysis, ultrafiltration, and the removal of ion by an ion exchange resin.

  When the hydroxide particles of the tetravalent metal element obtained above are aggregated, it is preferably dispersed in a liquid medium (for example, water) by an appropriate method. As a method of dispersing tetravalent metal element hydroxide particles in a liquid medium, a dispersion process using an ordinary stirrer; mechanical dispersion using a homogenizer, an ultrasonic disperser, a wet ball mill, etc .; centrifugation, dialysis, limiting Examples thereof include external filtration and removal of contaminating ions by an ion exchange resin. For the dispersion method and the particle size control method, for example, the method described in “Dispersion Technology Complete Collection” [Information Organization Co., Ltd., July 2005] Chapter 3, “Latest Development Trends and Selection Criteria of Various Dispersers” Can be used. Further, by reducing the electrical conductivity of the dispersion containing the hydroxide particles of the tetravalent metal element (for example, 500 mS / m or less) by performing the above-described washing treatment, the hydroxide of the tetravalent metal element is also reduced. Since the dispersibility of the particles can be improved, the washing treatment may be applied or used in combination as a dispersion treatment.

  In addition, about the manufacturing method of an abrasive grain demonstrated above, it describes in detail in the said patent document 8, The description is referred to this invention.

From the viewpoint of further improving the polishing rate of the insulating film, the abrasive grains containing the tetravalent metal element hydroxide particles have a wavelength of 400 nm in an aqueous dispersion in which the content of the abrasive grains is adjusted to 1.0 mass%. It is preferable to give an absorbance of 1.00 or more to the light. The “aqueous dispersion” in which the content of abrasive grains is adjusted to a predetermined amount means a liquid containing a predetermined amount of abrasive grains and water. The reason why the polishing rate can be improved is not necessarily clear, but the present inventor thinks as follows. That is, it consists of a tetravalent metal (M ⁴⁺ ), 1 to 3 hydroxyl groups (OH ⁻ ), and 1 to 3 anions (X ^c− ), depending on the production conditions of the tetravalent metal element hydroxide. It is considered that particles containing M (OH) _a X _b (where a + b × c = 4) are generated as part of the abrasive grains (note that such particles are also a hydroxylated tetravalent metal element). Particles of things). In M (OH) _{a Xb} , the electron-withdrawing anion (X ^c− ) acts to improve the reactivity of the hydroxyl group, and polishing increases as the amount of M (OH) _{a Xb} increases. It is thought that speed will improve. And since the particle | grains containing M (OH) _{a Xb} absorb the light of wavelength 400nm, since the abundance of M (OH) _{a Xb} increases and the light absorbency with respect to the light of wavelength 400nm becomes high, polishing rate Is thought to improve.

Note that the abrasive grains containing tetravalent metal element hydroxide particles contain M (OH) _a X _b after the abrasive grains are thoroughly washed with pure water and then subjected to FT-IR ATR (Fourier transform Infra Red Spectrometer). This can be confirmed by a method of detecting a peak corresponding to an anion (X ^c− ) by an Attenuated Total Reflection method or a Fourier transform infrared spectrophotometer total reflection measurement method). The presence of an anion (X ^c− ) can also be confirmed by XPS (X-ray Photoelectron Spectroscopy, X-ray photoelectron spectroscopy).

In addition, from the viewpoint of further improving the polishing rate of the insulating film, the abrasive has an absorbance of 1.000 with respect to light having a wavelength of 290 nm in an aqueous dispersion in which the content of the abrasive is adjusted to 0.0065% by mass. It is preferable to provide the above. The reason why the polishing rate can be improved is not necessarily clear, but the present inventor thinks as follows. That is, a particle containing M (OH) _a X _b produced according to the production conditions of a tetravalent metal element hydroxide has an absorption peak near a wavelength of 290 nm, for example, Ce ⁴⁺ ( Particles composed of OH ⁻ ) ₃ NO ₃ ^— have an absorption peak at a wavelength of 290 nm. Therefore, it is considered that the polishing rate is improved as the abundance of M (OH) _{a Xb} increases and the absorbance to light having a wavelength of 290 nm increases.

Further, the hydroxide (M (OH) _a X _b ) of the tetravalent metal element tends not to absorb light with a wavelength of 450 nm or more, particularly 450 to 600 nm. Therefore, from the viewpoint of suppressing an adverse effect on polishing due to the inclusion of impurities and polishing the insulating film at a further excellent polishing rate, the abrasive grains have a content of the abrasive grains of 0.0065 mass. In the aqueous dispersion adjusted to%, it is preferable to give an absorbance of 0.010 or less to light having a wavelength of 450 to 600 nm.

  From the viewpoint of further improving the polishing rate of the insulating film, the abrasive grains have a light transmittance of 50% / light with respect to light having a wavelength of 500 nm in an aqueous dispersion in which the content of the abrasive grains is adjusted to 1.0 mass%. It is preferable that it gives cm or more. The reason why the polishing rate can be improved is not necessarily clear, but the present inventor thinks as follows. That is, it is considered that the chemical action is more dominant than the mechanical action of the action of the tetravalent metal element hydroxide particles as the abrasive grains. Therefore, it is considered that the number of abrasive grains contributes more to the polishing rate than the size of the abrasive grains.

  When the light transmittance is low in an aqueous dispersion in which the content of abrasive grains is 1.0% by mass, the abrasive grains present in the aqueous dispersion are particles having a large particle diameter (hereinafter referred to as “coarse particles”). It is considered that there are relatively many. When an additive is added to an abrasive containing such abrasive grains, other particles aggregate with coarse particles as nuclei. As a result, the number of abrasive grains acting on the surface to be polished per unit area (the number of effective abrasive grains) is reduced, and the specific surface area of the abrasive grains in contact with the surface to be polished is reduced, which may reduce the polishing rate. it is conceivable that.

  On the other hand, when the light transmittance is high in an aqueous dispersion having an abrasive content of 1.0% by mass, it is considered that the abrasive grains present in the aqueous dispersion are in a state where there are few “coarse particles”. In this way, when the amount of coarse particles is small, even if an additive is added to the abrasive, there are few coarse particles that become the core of agglomeration. Particle size is reduced. As a result, the number of abrasive grains (number of effective abrasive grains) acting on the surface to be polished per unit area is maintained, and the specific surface area of the abrasive grains in contact with the surface to be polished is maintained. Thus, it is considered that the polishing rate of the insulating film is easily improved.

  The absorbance and light transmittance in the aqueous dispersion can be measured using, for example, a spectrophotometer (device name: U3310) manufactured by Hitachi, Ltd. Specifically, for example, an aqueous dispersion in which the content of abrasive grains is adjusted to 1.0 mass% or 0.0065 mass% is prepared as a measurement sample. About 4 mL of this measurement sample is put into a 1 cm square cell, and the cell is set in the apparatus. Next, the absorbance is measured in the wavelength range of 200 to 600 nm, and the absorbance and light transmittance are determined from the obtained chart.

  The absorbance and light transmittance that the abrasive grains contained in the abrasive give in the aqueous dispersion are obtained by removing the solid components other than abrasive grains and the liquid components other than water, and then removing the aqueous dispersion having a predetermined abrasive grain content. It can be prepared and measured using the aqueous dispersion. Although it depends on the components contained in the abrasive, the solid component or liquid component can be removed by centrifugation using a centrifugal machine that can apply gravitational acceleration of several thousand G or less, Centrifugal methods such as ultracentrifugation using a centrifuge; chromatography methods such as distribution chromatography, adsorption chromatography, gel permeation chromatography, ion exchange chromatography; natural filtration, vacuum filtration, pressure filtration, ultrafiltration Filtration methods such as distillation; distillation methods such as vacuum distillation and atmospheric distillation can be used, and these may be combined as appropriate.

  For example, when a compound having a weight average molecular weight of tens of thousands or more (for example, 50,000 or more) is included, a chromatography method, a filtration method and the like can be mentioned, and gel permeation chromatography and ultrafiltration are preferable. When the filtration method is used, the abrasive grains contained in the abrasive can be passed through the filter by setting appropriate conditions. When a compound having a weight average molecular weight of tens of thousands or less (for example, less than 50,000) is used, examples thereof include a chromatography method, a filtration method, and a distillation method, and gel permeation chromatography, ultrafiltration, and vacuum distillation are preferable. When multiple kinds of abrasive grains are included, filtration methods, centrifugation methods, and the like can be mentioned. In the case of filtration methods, particles of tetravalent metal element hydroxide particles are in the filtrate, in the case of centrifugation methods, in the liquid phase. More included.

  As a method for separating the abrasive grains by the chromatography method, for example, the abrasive grain components and / or other components can be separated under the following conditions.

Sample solution: 100 μL of abrasive
Detector: UV-VIS detector manufactured by Hitachi, Ltd., trade name “L-4200”, wavelength: 400 nm
Integrator: GPC integrator manufactured by Hitachi, Ltd., trade name “D-2500”
Pump: manufactured by Hitachi, Ltd., trade name “L-7100”
Column: Hitachi Chemical Co., Ltd. water-based HPLC packed column, trade name “GL-W550S”
Eluent: Deionized water Measurement temperature: 23 ° C
Flow rate: 1 mL / min (pressure: about 40-50 kg / cm ² )
Measurement time: 60 minutes

  In addition, it is preferable to perform a deaeration process of the eluent using a deaerator before performing the chromatography. However, if the eluent cannot be used, it is preferable to deaerate the eluent in advance with ultrasonic waves or the like.

  Depending on the components contained in the abrasive, the abrasive components may not be separated under the above conditions.In that case, by optimizing the sample solution amount, column type, eluent type, measurement temperature, flow rate, etc. Can be separated. In addition, by adjusting the pH of the abrasive, the distillation time of the components contained in the abrasive may be adjusted and separated from the abrasive grains. When there are insoluble components in the abrasive, it is preferable to remove the insoluble components by filtration, centrifugation or the like, if necessary.

  From the viewpoint of further improving the polishing rate of the insulating film, the lower limit of the average grain size of the abrasive grains in the abrasive is preferably 1 nm or more, more preferably 2 nm or more, and further preferably 3 nm or more. The upper limit of the average grain size of the abrasive grains is preferably 300 nm or less, more preferably 250 nm or less, and still more preferably 200 nm or less, from the viewpoint of further suppressing the surface to be polished from being scratched. From the above viewpoint, the average grain size of the abrasive grains is more preferably 1 nm or more and 300 nm or less.

  The “average particle diameter” of the abrasive grains means the average secondary particle diameter of the abrasive grains in the abrasive. When measuring the average particle size of the abrasive grains, a light diffraction scattering type particle size distribution meter (for example, COULTER Electronics, trade name: COULTER N4SD, or Malvern Instruments, trade name: Zeta Sizer 3000HSA) can be used. .

  From the viewpoint of further improving the polishing rate of the insulating film, the lower limit of the abrasive content is preferably 0.005% by mass or more, more preferably 0.01% by mass or more, based on the total mass of the abrasive. 02 mass% or more is still more preferable, and 0.04 mass% or more is especially preferable. The upper limit of the abrasive content is preferably 20% by mass or less, more preferably 15% by mass or less, and even more preferably 10% by mass or less, based on the total mass of the abrasive, from the viewpoint of increasing the storage stability of the abrasive. preferable. From the above viewpoint, the content of the abrasive grains is more preferably 0.005% by mass or more and 20% by mass or less based on the total mass of the abrasive.

  Further, it is preferable in that the cost and polishing scratches can be further reduced by further reducing the content of abrasive grains. When the content of abrasive grains decreases, the polishing rate for an insulating film or the like also tends to decrease. On the other hand, abrasive grains containing a hydroxide of a tetravalent metal element can obtain a predetermined polishing rate even with a small amount, so that the balance between the polishing rate and the advantage of reducing the content of abrasive grains is balanced. Further, the content of abrasive grains can be further reduced. From such a viewpoint, the content of the abrasive grains is preferably 5% by mass or less, more preferably 3% by mass or less, still more preferably 1% by mass or less, particularly preferably 0.5% by mass or less, and 0.3% by mass. % Or less is very preferable.

[Additive]
The abrasive | polishing agent which concerns on this embodiment contains an additive. Here, the “additive” means a polishing agent other than the liquid medium and the abrasive grains in order to adjust polishing characteristics such as polishing rate and polishing selectivity; and abrasive characteristics such as abrasive dispersibility and storage stability. Refers to the substance contained.

{First additive}
The abrasive | polishing agent which concerns on this embodiment contains the compound (EOPO adduct) which at least one of oxyethylene and oxypropylene added to ethylenediamine as a 1st additive. The first additive has an effect of improving the polishing selectivity of the insulating film with respect to the stopper film. It is considered that the interaction between the abrasive grains and the stopper film can be reduced by the interaction of the first additive with the stopper film.

  “At least one of oxyethylene and oxypropylene is added to ethylenediamine” means that a hydrogen atom bonded to a nitrogen atom of ethylenediamine is substituted by at least one of oxyethylene and oxypropylene. Since ethylenediamine has four hydrogen atoms bonded to a nitrogen atom, four substituents can be added to ethylenediamine, but any structure having at least one substituent added thereto may be used. Examples of the substituent include oxyethylene-oxypropylene copolymer, oxyethylene homopolymer, oxypropylene homopolymer, oxyethylene (single), and oxypropylene (single). The first additive preferably contains a compound having a structure in which an oxyethylene-oxypropylene copolymer is added to ethylenediamine.

［式（Ｉ）中、ａ１１、ａ１２、ａ１３及びａ１４は、それぞれ独立に０〜１０００の整数を示し、ｂ１１、ｂ１２、ｂ１３及びｂ１４は、それぞれ独立に０〜５００の整数を示す。但し、ａ１１、ａ１２、ａ１３、ａ１４、ｂ１１、ｂ１２、ｂ１３及びｂ１４の少なくとも一つは１以上である。］ Examples of the first additive include a compound represented by the following general formula (I) (Sequential poloxamine), a compound represented by the following general formula (II) (Reversepoloxamine), and the like.

[In Formula (I), a11, a12, a13 and a14 each independently represent an integer of 0 to 1000, and b11, b12, b13 and b14 each independently represent an integer of 0 to 500. However, at least one of a11, a12, a13, a14, b11, b12, b13, and b14 is 1 or more. ]

［式（ＩＩ）中、ａ２１、ａ２２、ａ２３及びａ２４は、それぞれ独立に０〜１０００の整数を示し、ｂ２１、ｂ２２、ｂ２３及びｂ２４は、それぞれ独立に０〜５００の整数を示す。但し、ａ２１、ａ２２、ａ２３、ａ２４、ｂ２１、ｂ２２、ｂ２３及びｂ２４の少なくとも一つは１以上である。］

[In Formula (II), a21, a22, a23 and a24 each independently represents an integer of 0 to 1000, and b21, b22, b23 and b24 each independently represents an integer of 0 to 500. However, at least one of a21, a22, a23, a24, b21, b22, b23 and b24 is 1 or more. ]

  In the compound represented by the general formula (I), a11, a12, a13 and a14 may be the same numerical values or may be different numerical values. In the compound represented by the general formula (I), b11, b12, b13 and b14 may be the same numerical values or different numerical values. In the compound represented by the general formula (II), a21, a22, a23 and a24 may be the same numerical values or different numerical values. In the compound represented by the general formula (II), b21, b22, b23 and b24 may be the same numerical values or different numerical values.

  The compound represented by the general formula (I) includes a compound in which at least one of a11, a12, a13 and a14 is 1 or more and at least one of b11, b12, b13 and b14 is 1 or more. preferable. The compound represented by the general formula (II) includes a compound in which at least one of a21, a22, a23 and a24 is 1 or more and at least one of b21, b22, b23 and b24 is 1 or more. preferable. The compound represented by the general formula (I) preferably contains at least one oxyethylene-oxypropylene copolymer bonded to a nitrogen atom derived from ethylenediamine. The compound represented by the general formula (II) preferably contains at least one oxyethylene-oxypropylene copolymer bonded to a nitrogen atom derived from ethylenediamine.

  Examples of the oxyethylene-oxypropylene copolymer include a random copolymer of oxyethylene and oxypropylene, an alternating copolymer, a block copolymer, etc. Among them, from the viewpoint of ease of production and availability. A block copolymer is preferred.

  The first additive preferably contains poloxamines. Here, poloxamines refer to poloxamine and reverse poloxamine. Poloxamine is a compound in which an oxypropylene moiety in an oxyethylene-oxypropylene copolymer (ethylene glycol-propylene glycol copolymer) is bonded to a nitrogen atom of ethylenediamine (in the above formula (I), a11, a12, a13, a14, b11). , B12, b13 and b14 are 1 or more). As the poloxamine, Tetronic series (manufactured by BASF), Adekapluronic TR series (manufactured by ADEKA) or the like can be used.

  Reverse poloxamine is a compound in which an oxyethylene moiety in an oxyethylene-oxypropylene copolymer is bonded to a nitrogen atom of ethylenediamine (in formula (II), a21, a22, a23, a24, b21, b22, b23 and b24 are One or more compounds). As such a compound, Adeka Pluronic TR series reverse type (manufactured by ADEKA) or the like can be used.

  The upper limit of the total molecular weight of the oxypropylene part (propylene glycol part) in the first additive is preferably 20,000 or less, and preferably 15,000, from the viewpoint of further improving the polishing selectivity of the insulating film with respect to the stopper film. The following is more preferable, and 10,000 or less is more preferable. The lower limit of the total molecular weight of the oxypropylene moiety in the first additive is preferably 300 or more, more preferably 500 or more, still more preferably 700 or more, from the viewpoint of further improving the polishing selectivity of the insulating film with respect to the stopper film. 1200 or more is particularly preferable. From the above viewpoint, the total molecular weight of the oxypropylene moiety in the first additive is more preferably 300 or more and 20,000 or less.

  The upper limit of the mass ratio of the entire oxyethylene moiety (ethylene glycol moiety) in the first additive (the mass ratio of the entire oxyethylene moiety in the total molecule) is a viewpoint of further improving the polishing selectivity of the insulating film with respect to the stopper film. Therefore, 80% or less is preferable, 70% or less is more preferable, and 60% or less is still more preferable. The lower limit of the mass ratio of the entire oxyethylene portion in the first additive is preferably 3% or more, more preferably 5% or more, and more preferably 10% or more from the viewpoint of further improving the polishing selectivity of the insulating film with respect to the stopper film. Further preferred. From the above viewpoint, the mass ratio of the entire oxyethylene portion in the first additive is more preferably 3% or more and 80% or less.

The molecular weight of the oxypropylene moiety in the first additive and the mass ratio of the entire oxyethylene moiety can be measured by the following method.
Equipment used: FT-NMR (for example, 500 MHz manufactured by JEOL)
Solvent: deuterated chloroform, deuterated DMSO (dimethyl sulfoxide) or deuterated water Measuring method: 1H-NMR spectrum is measured for the first additive, and the signals are integrated to obtain an oxyethylene part, an oxypropylene part, and an ethylenediamine part. The molar ratio of is calculated.

［式（Ｉａ）中、ａ１１、ａ１２、ａ１３及びａ１４は、それぞれ独立に０〜１０００の整数を示し、ｂ１１、ｂ１２、ｂ１３及びｂ１４は、それぞれ独立に０〜５００の整数を示す。但し、ａ１１、ａ１２、ａ１３、ａ１４、ｂ１１、ｂ１２、ｂ１３及びｂ１４の少なくとも一つは１以上である。］

［式（ＩＩａ）中、ａ２１、ａ２２、ａ２３及びａ２４は、それぞれ独立に０〜１０００の整数を示し、ｂ２１、ｂ２２、ｂ２３及びｂ２４は、それぞれ独立に０〜５００の整数を示す。但し、ａ２１、ａ２２、ａ２３、ａ２４、ｂ２１、ｂ２２、ｂ２３及びｂ２４の少なくとも一つは１以上である。］ Examples of the compound represented by the general formula (I) include compounds represented by the following general formula (Ia). Examples of the compound represented by the general formula (II) include compounds represented by the following (IIa).

[In formula (Ia), a11, a12, a13 and a14 each independently represent an integer of 0 to 1000, and b11, b12, b13 and b14 each independently represent an integer of 0 to 500. However, at least one of a11, a12, a13, a14, b11, b12, b13, and b14 is 1 or more. ]

[In Formula (IIa), a21, a22, a23 and a24 each independently represents an integer of 0 to 1000, and b21, b22, b23 and b24 each independently represents an integer of 0 to 500. However, at least one of a21, a22, a23, a24, b21, b22, b23 and b24 is 1 or more. ]

  Each of a11, a12, a13 and a14 in the formula (I) and a21, a22, a23 and a24 in the formula (II) is one or more from the viewpoint of further improving the polishing selectivity of the insulating film with respect to the stopper film. Preferably, 2 or more is more preferable. Each of a11, a12, a13, a14, a21, a22, a23 and a24 is preferably 910 or less, more preferably 680 or less, and even more preferably 400 or less, from the viewpoint of further improving the polishing selectivity of the insulating film with respect to the stopper film. preferable.

  Each of b11, b12, b13 and b14 in the formula (I) and b21, b22, b23 and b24 in the formula (II) is at least one from the viewpoint of further improving the polishing selectivity of the insulating film with respect to the stopper film. Preferably, 2 or more is more preferable. Each of b11, b12, b13, b14, b21, b22, b23, and b24 is preferably 350 or less, more preferably 320 or less, and even more preferably 300 or less, from the viewpoint of further improving the polishing selectivity of the insulating film with respect to the stopper film. preferable.

  The first additive can be used alone or in combination of two or more for the purpose of adjusting the polishing selectivity of the insulating film with respect to the stopper film. In addition, a plurality of compounds having different degrees of polymerization can be used in combination.

  From the viewpoint of further improving the polishing rate of the insulating film, the lower limit of the content of the first additive is preferably 0.01% by mass or more, more preferably 0.03% by mass or more based on the total mass of the abrasive. 0.05 mass% or more is more preferable, and 0.10 mass% or more is particularly preferable. The upper limit of the content of the first additive is preferably 10% by mass or less, more preferably 5% by mass or less, based on the total mass of the abrasive, from the viewpoint of suppressing the viscosity of the abrasive from becoming excessively high. . In view of the above, the content of the first additive is more preferably 0.01% by mass or more and 10% by mass or less based on the total mass of the abrasive. In addition, when using a some compound as a 1st additive, it is preferable that the sum total of content of each compound satisfy | fills the said range.

{Second additive}
The abrasive according to this embodiment preferably contains at least one selected from the group consisting of (C) polyvinylpyrrolidone and (D) glycerin compound as the second additive.

  Each of the second additives has an effect of further improving the polishing rate of the insulating film. For polyvinylpyrrolidone, the interaction between the abrasive grains and the insulating film is increased, and it is considered that the polishing rate of the insulating film is further improved. As for the glycerin compound, since the hydroxyl group of the glycerin compound interacts with the abrasive grains and the insulating film, and the abrasive grains and the insulating film are bridged by hydrogen bonds, the interaction between the abrasive grains and the insulating film increases. It is considered that the polishing rate of the insulating film is further improved.

  The second additive can be used alone or in combination of two or more for the purpose of adjusting the polishing selectivity of the insulating film with respect to the stopper film, the flatness and the polishing rate of the insulating film. In addition, a plurality of compounds having different degrees of polymerization can be used in combination.

(Polyvinylpyrrolidone)
From the viewpoint of further improving the polishing rate of the insulating film, the upper limit of the polymerization average molecular weight of the polyvinylpyrrolidone is preferably 2 million or less, more preferably 1.5 million or less, still more preferably 1 million or less, and particularly preferably 750,000 or less, 500,000 or less is very preferable. From the viewpoint of further improving the polishing rate of the insulating film, the lower limit of the polymerization average molecular weight of polyvinylpyrrolidone is preferably 1000 or more, more preferably 2000 or more, still more preferably 5000 or more, and particularly preferably 10,000 or more. From the above viewpoint, the weight average molecular weight of polyvinylpyrrolidone is more preferably 1000 or more and 2 million or less.

  In addition, the weight average molecular weight of polyvinylpyrrolidone can be measured on condition of the following by the gel permeation chromatography method (GPC) using the calibration curve of a standard polystyrene, for example.

Equipment used: Hitachi L-6000 (manufactured by Hitachi, Ltd.)
Column: Gel Pack GL-R420 + Gel Pack GL-R430 + Gel Pack GL-R440 [trade name, manufactured by Hitachi Chemical Co., Ltd., 3 in total]
Eluent: Tetrahydrofuran Measurement temperature: 40 ° C
Flow rate: 1.75 mL / min Detector: L-3300RI [manufactured by Hitachi, Ltd.]

  The lower limit of the content of polyvinylpyrrolidone is preferably 0.001% by mass or more, more preferably 0.002% by mass or more, based on the total mass of the abrasive, from the viewpoint of further improving the polishing rate of the insulating film. 005% by mass or more is more preferable, and 0.008% by mass or more is particularly preferable. The upper limit of the content of polyvinylpyrrolidone is preferably 10% by mass or less, more preferably 5% by mass or less, based on the total mass of the abrasive, from the viewpoint of suppressing the viscosity of the abrasive from becoming excessively high. In view of the above, the content of polyvinyl pyrrolidone is more preferably 0.001% by mass or more and 10% by mass or less based on the total mass of the abrasive. In addition, when using a some compound as polyvinylpyrrolidone, it is preferable that the sum total of content of each compound satisfy | fills the said range.

(Glycerin compound)
A glycerin compound is a compound having a glycerin skeleton. The glycerol compound is preferably at least one selected from the group consisting of polyglycerol, diglycerol derivatives and polyglycerol derivatives, more preferably at least one selected from the group consisting of polyglycerol and diglycerol derivatives. More preferred is polyglycerin.

  Polyglycerol is defined as polyglycerol having an average degree of polymerization of glycerol of 3 or more (polyglycerol having an average trimer or more). The average degree of polymerization of polyglycerol is preferably 4 or more from the viewpoint of further improving the polishing rate of the insulating film. The upper limit of the average degree of polymerization of polyglycerol is not particularly limited, but is preferably 100 or less, more preferably 50 or less, and still more preferably 30 or less, from the viewpoint of availability.

  Examples of the polyglycerin include polyglycerin # 310, polyglycerin # 500, and polyglycerin # 750 (trade names: all manufactured by Sakamoto Pharmaceutical Co., Ltd.).

  A diglycerin derivative is a compound in which a functional group is introduced into diglycerin. Examples of the functional group include a polyoxyalkylene group, a fatty acid ester group, and an ether group. Examples of the diglycerin derivative having a polyoxyalkylene group introduced include polyoxyalkylene diglyceryl ether. Diglycerin fatty acid ester etc. are mentioned as a diglycerol derivative which introduce | transduced the fatty acid ester group. Examples of the diglycerin derivative introduced with an ether group include diglycerin alkyl ether and diglycerin polyalkyl ether.

  The diglycerin derivative is preferably at least one selected from the group consisting of polyoxyalkylene diglyceryl ether, diglycerin fatty acid ester, diglycerin alkyl ether and diglycerin polyalkyl ether. Thereby, the polishing rate of the insulating film can be further improved, and the polishing selectivity of the insulating film with respect to the stopper film can be further improved.

  Examples of the polyoxyalkylene diglyceryl ether include polyoxyethylene diglyceryl ether (Sakamoto Pharmaceutical Co., Ltd., SC-E series, SC-P series, etc.), polyoxypropylene diglyceryl ether (Sakamoto Pharmaceutical Co., Ltd., SY-DP series, etc.). Examples of the diglycerin fatty acid ester include MCA-150 manufactured by Sakamoto Pharmaceutical Co., Ltd. Examples of the diglycerin alkyl ether include 3- [2-alkoxy-1- (methoxymethyl) ethoxy] -1,2-propanediol.

  A polyglycerin derivative is a compound in which a functional group is introduced into polyglycerin having an average degree of polymerization of glycerin of 3 or more. Examples of the functional group include a polyoxyalkylene group, a fatty acid ester group, and an ether group. The average degree of polymerization of the polyglycerol skeleton in the polyglycerol derivative is 3 or more and preferably 4 or more from the viewpoint of further improving the polishing rate of the insulating film. From the viewpoint of production, the upper limit of the average degree of polymerization of the polyglycerol skeleton in the polyglycerol derivative is preferably 100 or less, more preferably 50 or less, and even more preferably 30 or less.

  Examples of the polyglycerin derivative include polyoxyalkylene polyglyceryl ether, polyglycerin fatty acid ester, polyglycerin alkyl ether, and the like. Examples of the polyoxyalkylene polyglyceryl ether include polyoxyethylene polyglyceryl ether (Sakamoto Pharmaceutical Co., Ltd., # 310-EO60, etc.), polyoxypropylene polyglyceryl ether, and the like. Examples of the polyglycerin fatty acid ester include glycerin fatty acid ester (Sakamoto Pharmaceutical Co., Ltd., SY glycerase series, etc.). Examples of the polyglycerin alkyl ether include pentaglycerin dodecyl ether.

  The upper limit of the polymerization average molecular weight of the glycerin compound is not particularly limited, but is preferably 5000 or less, more preferably 3000 or less, and still more preferably 2000 or less from the viewpoint of workability and foamability. From the viewpoint of further improving the polishing rate of the insulating film, the lower limit of the polymerization average molecular weight of the glycerin compound is preferably 250 or more, more preferably 400 or more, and still more preferably 500 or more. From the above viewpoint, the weight average molecular weight of the glycerin compound is more preferably 250 or more and 5000 or less.

  The weight average molecular weight of the glycerin compound can be measured, for example, by gel permeation chromatography (GPC) using a standard polystyrene calibration curve under the same conditions as the weight average molecular weight of polyvinylpyrrolidone.

  The lower limit of the content of the glycerin compound is preferably 0.001% by mass or more, more preferably 0.002% by mass or more, based on the total mass of the abrasive, from the viewpoint of further improving the polishing rate of the insulating film. 005% by mass or more is more preferable, and 0.008% by mass or more is particularly preferable. The upper limit of the content of the glycerin compound is preferably 10% by mass or less, and more preferably 5% by mass or less, based on the total mass of the abrasive, from the viewpoint of suppressing the viscosity of the abrasive from becoming excessively high. In view of the above, the content of the glycerin compound is more preferably 0.001% by mass or more and 10% by mass or less based on the total mass of the abrasive. In addition, when using a some compound as a glycerol compound, it is preferable that the sum total of content of each compound satisfy | fills the said range.

  When the polyvinyl pyrrolidone and the glycerin compound are used in combination as the second additive, the lower limit of the content of the second additive (the total of the content of the polyvinyl pyrrolidone and the content of the glycerin compound) is an insulating film. From the viewpoint of further improving the polishing rate, the amount is preferably 0.001% by mass or more, more preferably 0.002% by mass or more, still more preferably 0.005% by mass or more, based on the total mass of the abrasive. A mass% or more is particularly preferred. The upper limit of the content of the second additive is preferably 10% by mass or less, more preferably 5% by mass or less, based on the total mass of the abrasive, from the viewpoint of suppressing the viscosity of the abrasive from becoming excessively high. . In view of the above, the content of the second additive is more preferably 0.001% by mass or more and 10% by mass or less based on the total mass of the abrasive.

{Other additives}
The abrasive according to the present embodiment includes the first additive and the second additive for the purpose of adjusting polishing characteristics such as polishing rate; abrasive characteristics such as abrasive dispersibility and storage stability. May further contain other different additives.

  Examples of other additives include carboxylic acid, amino acid, water-soluble polymer, oxidizing agent (for example, hydrogen peroxide) and the like, and these can be used alone or in combination of two or more.

  When other additives are used, the content is 0.0001% by mass or more and 10% by mass based on the total mass of the abrasive from the viewpoint of obtaining the additive effect while suppressing sedimentation of the abrasive grains. The following is preferred. In addition, when using a some compound as another additive, it is preferable that the sum total of content of each compound satisfy | fills the said range.

  Carboxylic acid has the effect of stabilizing the pH and further improving the polishing rate of the insulating film. Examples of the carboxylic acid include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, and lactic acid.

  The amino acid has an effect of improving dispersibility of the abrasive grains (particularly, hydroxide particles of the tetravalent metal element) and further improving the polishing rate of the insulating film. Amino acids include arginine, lysine, aspartic acid, glutamic acid, asparagine, glutamine, histidine, proline, tyrosine, tryptophan, serine, threonine, glycine, alanine, β-alanine, methionine, cysteine, phenylalanine, leucine, valine, isoleucine, etc. Can be mentioned.

  Water-soluble polymers are flatness, in-plane uniformity, polishing selectivity of silicon oxide film to silicon nitride film (silicon oxide film polishing rate / silicon nitride film polishing rate), silicon oxide film polishing to polysilicon film There is an effect of adjusting polishing characteristics such as selectivity. Here, the “water-soluble polymer” is defined as a polymer that dissolves 0.1 g or more in 100 g of water. The polymer corresponding to the first additive and the second additive is not included in the “water-soluble polymer”.

The water-soluble polymer is not particularly limited, and is a polysaccharide such as alginic acid, pectic acid, carboxymethylcellulose, agar, curdlan, dextrin, cyclodextrin, chitosan, chitosan derivative, pullulan;
Vinyl polymers such as polyvinyl alcohol and polyacrolein;
Acrylic polymers such as polyacrylamide and polydimethylacrylamide;
Amine polymers such as polyallylamine, polyethyleneimine, polydiallylamines;
Examples include polyethylene glycol, polyoxypropylene, and polyoxyethylene-polyoxypropylene condensate. Among the water-soluble polymers, polyallylamine is preferable from the viewpoint of further improving the polishing selectivity of the insulating film with respect to the stopper film. A water-soluble polymer can be used individually or in combination of 2 or more types.

  The polymerization average molecular weight of the water-soluble polymer is preferably 100 or more, more preferably 300 or more, still more preferably 500 or more, and particularly preferably 1000 or more from the viewpoint of further improving the polishing selectivity of the insulating film with respect to the stopper film. The polymerization average molecular weight of the water-soluble polymer is preferably 1,000,000 or less, more preferably 700,000 or less, further preferably 500,000 or less, and more preferably 300,000 or less, from the viewpoint of further improving the polishing selectivity of the insulating film with respect to the stopper film. Is particularly preferred. The weight average molecular weight of the water-soluble polymer can be measured by the same method as the weight average molecular weight of the second additive.

  When the water-soluble polymer is used, the content of the water-soluble polymer is 0 based on the total mass of the abrasive from the viewpoint of obtaining the effect of adding the water-soluble polymer while suppressing sedimentation of abrasive grains. 0.0001 mass% or more is preferable, 0.00015 mass% or more is more preferable, and 0.0002 mass% or more is still more preferable. The content of the water-soluble polymer is preferably 10% by mass or less, preferably 5% by mass or less based on the total mass of the abrasive from the viewpoint of obtaining the effect of adding the water-soluble polymer while suppressing sedimentation of abrasive grains. Is more preferable, 3% by mass or less is further preferable, and 1% by mass or less is particularly preferable. When using a some compound as said water-soluble polymer, it is preferable that the sum total of content of each compound satisfy | fills the said range.

[Liquid medium]
The liquid medium in the abrasive according to this embodiment is not particularly limited, but water such as deionized water or ultrapure water is preferable. The content of the liquid medium may be the remainder of the abrasive excluding the content of other components, and is not particularly limited.

[Abrasive properties]
The pH (25 ° C.) of the abrasive according to this embodiment is preferably 3.0 or more and 12.0 or less from the viewpoint of excellent storage stability of the abrasive and further improving the polishing rate of the insulating film. The pH of the abrasive mainly affects the polishing rate. The lower limit of pH is more preferably 4.0 or more, further preferably 4.5 or more, and particularly preferably 5.0 or more, from the viewpoint of further improving the polishing rate of the insulating film. Further, the upper limit of the pH is more preferably 11.0 or less, and even more preferably 10.0 or less, from the viewpoint of further improving the polishing rate of the insulating film.

  The pH of the polishing agent can be adjusted by adding an acid component such as an inorganic acid or an organic acid; an alkali component such as ammonia, sodium hydroxide, tetramethylammonium hydroxide (TMAH), or imidazole. A buffer may be added to stabilize the pH. Examples of such a buffer include acetate buffer and phthalate buffer.

  The pH of the abrasive according to this embodiment can be measured with a pH meter (for example, model number PHL-40 manufactured by Electrochemical Instrument Co., Ltd.). Specifically, for example, after calibrating two pH meters using a phthalate pH buffer solution (pH 4.01) and a neutral phosphate pH buffer solution (pH 6.86) as standard buffers, The value is measured after the electrode is placed in an abrasive and stabilized after 2 minutes or more. At this time, the liquid temperature of the standard buffer and the abrasive is both 25 ° C.

  The abrasive according to this embodiment may be stored as a one-part abrasive containing at least abrasive grains, a first additive, and a liquid medium. A slurry (first liquid) and an additive liquid (first liquid) 2 components) may be mixed and stored as a two-component abrasive set in which the constituents of the abrasive are divided into a slurry and an additive solution. The slurry includes at least abrasive grains and a liquid medium, for example. The additive liquid includes, for example, at least a first additive and a liquid medium. The additive (first additive, second additive, and other additives) is preferably included in the additive solution. In particular, when the second additive is contained in the additive liquid, it becomes easy to suppress the aggregation of abrasive grains. The constituents of the abrasive may be stored as an abrasive set divided into three or more liquids.

  In the abrasive set, slurry and additive liquid are mixed immediately before or during polishing to produce an abrasive. In addition, the one-component abrasive may be stored as an abrasive stock solution in which the content of the liquid medium is reduced, and may be diluted with the liquid medium during polishing. The two-component abrasive set may be stored as a slurry storage solution and an additive storage solution with a reduced content of the liquid medium, and may be diluted with the liquid medium during polishing.

  In the case of a one-component abrasive, the method for supplying the abrasive onto the polishing surface plate is, for example, a method in which the abrasive is directly fed and supplied; a storage solution for abrasive and a liquid medium are sent through separate pipes. And a method of supplying them by mixing them, mixing them, and a method of supplying a stock solution for abrasives and a liquid medium after mixing them in advance.

  When storing as a two-component type abrasive set divided into slurry and additive solution, the polishing rate can be adjusted by arbitrarily changing the mixing ratio of these two components. In the case of polishing using an abrasive set, methods for supplying the abrasive onto the polishing surface plate include the following methods. For example, a method in which slurry and additive liquid are fed through separate pipes, and these pipes are combined, mixed and supplied; a slurry storage liquid, an additive liquid storage liquid, and a liquid medium are fed through separate pipes. , A method of supplying these by mixing and mixing them; a method of supplying the slurry and the additive solution by mixing them in advance; a method of supplying the slurry storage solution, the additive solution storage solution and the liquid medium by mixing them in advance, etc. Can be used. Moreover, the method of supplying the slurry and additive liquid in the said abrasive | polishing agent set on a polishing surface plate, respectively can also be used. In this case, the surface to be polished is polished using an abrasive obtained by mixing the slurry and the additive liquid on the polishing platen.

  The abrasive set according to the present embodiment may be divided into an abrasive containing at least the essential components and an additive liquid containing at least an optional component such as an oxidizing agent (for example, hydrogen peroxide). . In this case, polishing is performed using a mixed liquid obtained by mixing the abrasive and the additive liquid (the mixed liquid also corresponds to “abrasive”). Further, the abrasive set according to the present embodiment is an abrasive set divided into three or more liquids, a liquid containing at least a part of the essential components, a liquid containing at least the remainder of the essential components, and an optional component. The mode may be divided into the additive solution containing at least. Each liquid constituting the abrasive set may be stored as a storage liquid in which the content of the liquid medium is reduced.

<Polishing method of substrate>
The substrate polishing method according to the present embodiment includes a polishing step of polishing the surface to be polished of the substrate using the abrasive. In the polishing step, for example, the abrasive is supplied between the film to be polished and the polishing pad in a state where the film to be polished of the substrate having the film to be polished is pressed against the polishing pad (polishing cloth) of the polishing surface plate. However, the film to be polished is polished by relatively moving the substrate and the polishing surface plate. In the polishing step, for example, at least a part of the film to be polished is removed by polishing.

  Examples of the substrate to be polished include a substrate. For example, a film to be polished is formed on a substrate for manufacturing a semiconductor element (for example, a semiconductor substrate on which an STI pattern, a gate pattern, a wiring pattern, etc. are formed). A substrate is mentioned. Examples of the film to be polished include an insulating film such as a silicon oxide film; a polysilicon film; a silicon nitride film. The film to be polished may be a single film or a plurality of films. When a plurality of films are exposed on the surface to be polished, they can be regarded as a film to be polished.

  Polishing a film to be polished (such as an insulating film such as a silicon oxide film) formed on such a substrate with the above-mentioned polishing agent, and removing the excess portion, eliminates the unevenness of the surface of the film to be polished, A smooth surface can be obtained over the entire surface of the film to be polished. The abrasive according to this embodiment is preferably used for polishing a surface to be polished containing silicon oxide.

  In the present embodiment, insulation in a base body having an insulating film (for example, a silicon oxide film) containing at least silicon oxide on the surface, a stopper film disposed under the insulating film, and a semiconductor substrate disposed under the stopper film. The film can be polished. The stopper film has a lower polishing rate than the film to be polished, and is preferably a polysilicon film, a silicon nitride film, or the like. In such a substrate, by stopping polishing when the stopper film is exposed, it is possible to prevent the insulating film from being excessively polished, so that the flatness of the insulating film after polishing can be improved.

  As a method for producing a film to be polished by the abrasive according to this embodiment, a CVD method represented by a low pressure CVD method, a quasi-atmospheric pressure CVD method, a plasma CVD method, etc .; a liquid material is applied to a rotating substrate Examples include a spin coating method.

The silicon oxide film can be obtained, for example, by thermally reacting monosilane (SiH ₄ ) and oxygen (O ₂ ) using a low pressure CVD method. The silicon oxide film can be obtained by, for example, thermally reacting tetraethoxysilane (Si (OC ₂ H ₅ ) ₄ ) and ozone (O ₃ ) using a quasi-atmospheric pressure CVD method. As another example, a silicon oxide film can be similarly obtained by causing plasma reaction between tetraethoxysilane and oxygen.

  The silicon oxide film is obtained by applying a liquid raw material containing, for example, inorganic polysilazane, inorganic siloxane or the like on a substrate using a spin coating method and performing a thermosetting reaction in a furnace body or the like.

  Examples of the method for forming a polysilicon film include a low pressure CVD method in which monosilane is thermally reacted, a plasma CVD method in which monosilane is subjected to plasma reaction, and the like.

  In order to stabilize film quality such as a silicon oxide film and a polysilicon film obtained by the above method, heat treatment may be performed at a temperature of 200 to 1000 ° C. as necessary. In addition, the silicon oxide film obtained by the above method may contain a small amount of boron (B), phosphorus (P), carbon (C), or the like in order to improve the embedding property.

  Hereinafter, the polishing method according to this embodiment will be further described by taking as an example a polishing method for a semiconductor substrate on which an insulating film is formed. In the polishing method according to the present embodiment, as a polishing apparatus, a general polishing apparatus having a holder capable of holding a substrate such as a semiconductor substrate having a surface to be polished and a polishing surface plate to which a polishing pad can be attached. Can be used. Each of the holder and the polishing surface plate is provided with a motor capable of changing the number of rotations. As a polishing apparatus, a polishing apparatus manufactured by Applied Materials, such as Reflexion, can be used.

  As the polishing pad, a general nonwoven fabric, foam, non-foam, or the like can be used. As the material of the polishing pad, polyurethane, acrylic, polyester, acrylic-ester copolymer, polytetrafluoroethylene, polypropylene, polyethylene, poly-4-methylpentene, cellulose, cellulose ester, polyamide (for example, nylon (trade name), Aramid), polyimide, polyimide amide, polysiloxane copolymer, oxirane compound, phenol resin, polystyrene, polycarbonate, epoxy resin and the like can be used. As the material of the polishing pad, foamed polyurethane and non-foamed polyurethane are particularly preferable from the viewpoint of polishing speed and flatness. It is preferable that the polishing pad is grooved so as to collect the abrasive.

Although there is no limitation on polishing conditions, the rotation speed of the surface plate is preferably 200 min ⁻¹ or less so that the semiconductor substrate does not pop out, and the polishing pressure (working load) applied to the semiconductor substrate is sufficient to cause polishing flaws. 100 kPa or less is preferable from the viewpoint of suppressing the above. During polishing, it is preferable to continuously supply the polishing agent to the polishing pad with a pump or the like. Although there is no restriction | limiting in this supply amount, it is preferable that the surface of a polishing pad is always covered with the abrasive | polishing agent.

  The semiconductor substrate after the polishing is preferably washed well under running water to remove particles adhering to the substrate. For cleaning, dilute hydrofluoric acid or ammonia water may be used in addition to pure water, and a brush may be used in combination to increase cleaning efficiency. Further, after cleaning, it is preferable to dry the semiconductor substrate after water droplets adhering to the semiconductor substrate are removed using a spin dryer or the like.

  The abrasive | polishing agent, abrasive | polishing agent set, and grinding | polishing method which concern on this embodiment can be used conveniently for formation of STI. In order to form STI, it is preferable that the polishing rate ratio of the insulating film (for example, silicon oxide film) to the stopper film (for example, polysilicon film) is 30 or more. When the polishing rate ratio is less than 30, the polishing rate of the insulating film relative to the polishing rate of the stopper film is small, and it is difficult to stop polishing at a predetermined position when forming the STI. On the other hand, if the polishing rate ratio is 30 or more, it is easy to stop polishing, which is more suitable for formation of STI.

  The abrasive | polishing agent, abrasive | polishing agent set, and grinding | polishing method which concern on this embodiment can be used also for grinding | polishing of a premetal insulating film. As a constituent material of the premetal insulating film, for example, phosphorus-silicate glass or boron-phosphorus-silicate glass is used in addition to silicon oxide, and silicon oxyfluoride, fluorinated amorphous carbon, or the like can also be used.

  The abrasive, the abrasive set, and the polishing method according to the present embodiment can be applied to a film other than an insulating film such as a silicon oxide film. Examples of such films include high dielectric constant films such as Hf-based, Ti-based, and Ta-based oxides; semiconductor films such as silicon, amorphous silicon, SiC, SiGe, Ge, GaN, GaP, GaAs, and organic semiconductors; GeSbTe Phase change film; inorganic conductive film such as ITO; polymer resin film such as polyimide, polybenzoxazole, acrylic, epoxy, and phenol.

  The polishing agent, the polishing agent set, and the polishing method according to the present embodiment are not only film-like objects to be polished, but also various types composed of glass, silicon, SiC, SiGe, Ge, GaN, GaP, GaAs, sapphire, plastic, or the like. It can also be applied to substrates.

  The polishing agent, the polishing agent set, and the polishing method according to the present embodiment are not only for manufacturing semiconductor elements, but also for image display devices such as TFTs and organic ELs; optical parts such as photomasks, lenses, prisms, optical fibers, and single crystal scintillators Optical elements such as optical switching elements and optical waveguides; light emitting elements such as solid lasers and blue laser LEDs; and magnetic storage devices such as magnetic disks and magnetic heads.

  EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example, this invention is not limited to this.

<Synthesis of tetravalent metal element hydroxide particles>
350 g of Ce (NH ₄ ) ₂ (NO ₃ ) ₆ 50% by mass aqueous solution (manufactured by Nippon Chemical Industry Co., Ltd., product name: CAN50 solution) was dissolved in 7825 g of pure water to obtain a solution. Next, while stirring this solution, 750 g of an imidazole aqueous solution (10% by mass aqueous solution) was dropped at a rate of 5 mL / min to obtain a precipitate of particles containing cerium hydroxide.

The obtained precipitate containing cerium hydroxide was centrifuged (4000 min ⁻¹ , 5 minutes), and then the liquid phase was removed by decantation to perform solid-liquid separation. Also, 10 g of the obtained particles and 990 g of water are mixed, and the particles are dispersed in water using an ultrasonic cleaner to prepare a cerium hydroxide slurry storage liquid (particle content: 1.0 mass%). did.

  It was 25 nm when the average particle diameter (Z-average Size) of the particle | grains in the stock solution for cerium hydroxide slurries was measured using the product name Zetasizer 3000HSA made from Malvern Instruments. The measuring method is as follows. First, about 1 mL of a measurement sample containing 1.0% by mass of particles was placed in a 1 cm square cell, and the cell was placed in the Zetasizer 3000HSA. The refractive index of the measurement sample was 1.33, the viscosity of the measurement sample was 0.887 mPa · s, measurement was performed at 25 ° C., and the value displayed as Z-average Size was read.

  An appropriate amount of the cerium hydroxide slurry storage solution was collected and diluted with water so that the particle content was 0.0065% by mass to obtain a measurement sample (aqueous dispersion). About 4 mL of the measurement sample was placed in a 1 cm square cell, and the cell was installed in a spectrophotometer (device name: U3310) manufactured by Hitachi, Ltd. Absorbance was measured in the wavelength range of 200 to 600 nm, and the absorbance to light having a wavelength of 290 nm and the absorbance to light having a wavelength of 450 to 600 nm were measured. Absorbance with respect to light having a wavelength of 290 nm was 1.192, and absorbance with respect to light having a wavelength of 450 to 600 nm was less than 0.010.

  About 4 mL of cerium hydroxide slurry storage solution (particle content: 1.0 mass%) is placed in a 1 cm square cell, and the cell is installed in a spectrophotometer (device name: U3310) manufactured by Hitachi, Ltd. did. Absorbance was measured in the wavelength range of 200 to 600 nm, and the absorbance with respect to light with a wavelength of 400 nm and the light transmittance with respect to light with a wavelength of 500 nm were measured. Absorbance with respect to light with a wavelength of 400 nm was 2.25, and light transmittance with respect to light with a wavelength of 500 nm was 92% / cm.

An appropriate amount of cerium hydroxide slurry stock was collected, vacuum dried to isolate the abrasive grains, and the sample obtained by washing thoroughly with pure water was measured by FT-IR ATR method. In addition to the peak based on, a peak based on the NO ₃ group was observed. Further, when XPS (N-XPS) measurement was performed on the sample, a peak based on NH ₄ was not observed, and a peak based on NO ₃ was observed. From these results, it was confirmed that the abrasive grains contained in the cerium hydroxide slurry storage liquid contain at least a part of particles having NO ₃ groups bonded to the cerium element.

<Preparation of abrasive for CMP>
The polishing slurry for CMP used in Examples 1 to 16 and Comparative Examples 1 to 3 shows 0.05% by mass of particles containing the cerium hydroxide as abrasive grains based on the total mass of the polishing slurry for CMP. (B) 0-0.5% by mass of EOPO adduct, (C) 0-0.3% by mass of polyvinylpyrrolidone, (D) 0-0.1% by mass of glycerin compound, 0 as imidazole as pH adjuster. It was prepared so that 0.005 mass% and pure water was contained in the balance.

  Specifically, water was added to the cerium hydroxide slurry storage solution and diluted 5 to 10 times to obtain a slurry containing particles containing cerium hydroxide as abrasive grains. Next, components other than abrasive grains were dissolved in pure water to obtain an additive solution. Next, the slurry and the additive solution were mixed and stirred to prepare an abrasive for CMP.

<Liquid property evaluation>
The pH of these CMP abrasives and the average particle size of abrasive grains in the CMP abrasive were evaluated under the following conditions.
(PH)
Measurement temperature: 25 ± 5 ° C
Measuring device: manufactured by Electrochemical Instrument Co., Ltd., model number PHL-40
Measurement method: After calibrating two points using a standard buffer (phthalate pH buffer, pH: 4.01 (25 ° C.); neutral phosphate pH buffer, pH 6.86 (25 ° C.)), The electrode was placed in a CMP abrasive and the pH after the passage of 2 minutes or more and stabilized was measured with the measuring device.

(Average grain size of abrasive grains)
The average particle size (Z-average Size) of the abrasive grains in the CMP abrasive was measured using a product name Zeta Sizer 3000HSA manufactured by Malvern Instruments. The measuring method is as follows. First, about 1 mL of the polishing slurry for CMP was placed in a 1 cm square cell, and the cell was placed in the Zetasizer 3000HSA. The refractive index of the measurement sample was adjusted to 1.33, the viscosity of the measurement sample was adjusted to 0.887 mPa · s, the measurement was performed at 25 ° C., and the value displayed as Z-average Size was read. The average particle size of the abrasive grains was 25 nm in any of the polishing abrasives for CMP of Examples 1 to 16 and Comparative Examples 1 to 3.

<CMP evaluation>
The silicon oxide film and the polysilicon film were polished under the following polishing conditions using the CMP abrasives of Examples 1 to 16 and Comparative Examples 1 to 3. Further, the silicon nitride film was polished under the following polishing conditions using the CMP polishing slurry of Example 11 and Comparative Example 1.

(CMP polishing conditions)
Polishing equipment: Reflexion (manufactured by APPLIED MATERIALS)
Polishing agent flow rate for CMP: 200 mL / min Substrate to be polished: (a) A substrate in which a silicon oxide film having a thickness of 1 μm is formed on a silicon substrate by a plasma CVD method, (b) A polysilicon film having a thickness of 0.15 μm is formed by silicon A substrate formed on a substrate, and (c) a substrate in which a silicon nitride film having a thickness of 0.5 μm is formed on a silicon substrate.
Polishing pad: Foam polyurethane resin with closed cells (Rohm and Haas Japan, model number IC1000)
Polishing pressure: 14.7 kPa (2 psi)
Relative speed between substrate and polishing platen: 85 m / min Polishing time: 1 minute Cleaning: After CMP treatment, cleaning with ultrasonic water was performed and then drying with a spin dryer.

(Abrasive product evaluation items)
For the substrate to be polished and cleaned under the above conditions, the polishing rate of the silicon oxide film (SiO ₂ RR), the polishing rate of the polysilicon film (p-SiRR), and the polishing rate of the silicon nitride film (SiNRR) are I asked more. Note that the difference in film thickness between the silicon oxide film, the polysilicon film, and the silicon nitride film before and after polishing was determined using an optical interference film thickness apparatus (manufactured by Filmetrics, product name: F80).
(Polishing rate: RR) = (Difference in thickness of silicon oxide film, polysilicon film or silicon nitride film before and after polishing (nm)) / (Polishing time (min))

Tables 1 and 2 show the pH of the polishing slurry for CMP, the polishing rate of the silicon oxide film (SiO ₂ RR), the polishing rate of the polysilicon film (p-SiRR), the polishing rate of the silicon nitride film (SiNRR), and the like. Show.

  Further, the substrate to be polished (blanket wafer) polished and cleaned under the above conditions was immersed in an aqueous solution of 0.5% by mass of hydrogen fluoride for 15 seconds, and then washed with water for 60 seconds. Subsequently, the surface of the film to be polished was washed with a PVA brush for 1 minute while supplying water, and then dried. A defect of 0.2 μm or more on the surface of the film to be polished was detected using Applied Materials Complus. Furthermore, when the surface of the film to be polished was observed using the defect detection coordinates obtained by Complus and SEM Vision made by Applied Materials, the number of polishing scratches of 0.2 μm or more on the surface of the film to be polished was found to be 1 to 16 and Comparative Examples 1 to 3 were about 0 to 3 (pieces / wafer), and the occurrence of polishing flaws was sufficiently suppressed.

  In addition, each compound described in Table 1 is as follows.

(EOPO adduct)
TR-304: manufactured by ADEKA, ethylenediaminetetrapolyoxyethylenepolyoxypropylene, the compound of the above formula (Ia), the total molecular weight of the oxypropylene part: about 750, the mass ratio of the entire oxyethylene part: 40%
TR-702: manufactured by ADEKA, ethylenediaminetetrapolyoxyethylenepolyoxypropylene, the compound of the above formula (Ia), the total molecular weight of the oxypropylene part: about 2800, the mass ratio of the whole oxyethylene part: 20%
TR-704: manufactured by ADEKA, ethylenediaminetetrapolyoxyethylenepolyoxypropylene, the compound of the above formula (Ia), the total molecular weight of the oxypropylene part: about 2800, the mass ratio of the entire oxyethylene part: 40%
TR-913R: manufactured by ADEKA, ethylenediaminetetrapolyoxypropylenepolyoxyethylene, the compound of the above formula (IIa), the total molecular weight of the oxypropylene part: about 4500, the mass ratio of the whole oxyethylene part: about 30%

(Polyvinylpyrrolidone)
PVP K15: manufactured by Nippon Shokubai, weight average molecular weight: 10,000 PVP K30: manufactured by Nippon Shokubai, weight average molecular weight: 45,000 PVP K90: manufactured by Nippon Shokubai, weight average molecular weight: 360,000

(Glycerin compound)
Polyglycerin tetramer: Sakamoto Pharmaceutical Co., Ltd., weight average molecular weight: 300
Polyglycerin 10mer: Sakamoto Pharmaceutical Co., Ltd., weight average molecular weight: 680
Polyglycerin 20mer: Sakamoto Pharmaceutical Co., Ltd., weight average molecular weight: 1300
SC-E2000: Sakamoto Pharmaceutical Co., Ltd., diglycerin polyether (polyoxyethylene diglyceryl ether), weight average molecular weight: 2000
SC-P1000: manufactured by Sakamoto Pharmaceutical Co., Ltd., diglycerin polyether (polyoxypropylene diglyceryl ether, weight average molecular weight: 1000
# 310-EO60: manufactured by Sakamoto Pharmaceutical Co., Ltd., polyoxyethylene polyglyceryl ether, average degree of polymerization of polyglycerin skeleton: 4, weight average molecular weight: 3000

  Hereinafter, the results shown in Tables 1 and 2 will be described in detail.

  In Example 1, 0.5 mass% of TR-304 was used in the production of the polishing slurry for CMP. The polishing selectivity of the insulating film with respect to the polysilicon film of Example 1 was 35, which was higher than Comparative Examples 1 to 3.

  In Example 2, 0.5% by mass of TR-702 was used in the production of the polishing slurry for CMP. The polishing selectivity of the insulating film to the polysilicon film of Example 2 was 32, which was higher than those of Comparative Examples 1 to 3.

  In Example 3, 0.5 mass% of TR-704 was used in the production of the polishing slurry for CMP. The polishing selectivity of the insulating film to the polysilicon film of Example 3 was 40, which was higher than those of Comparative Examples 1 to 3.

  In Example 4, 0.5% by mass of TR-913R was used in the production of the CMP abrasive. The polishing selectivity of the insulating film with respect to the polysilicon film of Example 4 was 53, which was higher than those of Comparative Examples 1 to 3.

  In Example 5, 0.5% by mass of TR-704 and 0.1% by mass of PVP K30 were used in the production of the polishing slurry for CMP. The polishing selectivity of the insulating film with respect to the polysilicon film of Example 5 was 78, which was higher than those of Comparative Examples 1 to 3.

  In Example 6, in the production of the polishing slurry for CMP, 0.5% by mass of TR-704 and 0.3% by mass of PVP K30 were used. The polishing selectivity of the insulating film with respect to the polysilicon film of Example 6 was 70, which was higher than those of Comparative Examples 1 to 3.

  In Example 7, 0.5% by mass of TR-913R and 0.3% by mass of PVP K30 were used in the production of the polishing slurry for CMP. The polishing selectivity of the insulating film to the polysilicon film of Example 7 was 63, which was higher than those of Comparative Examples 1 to 3.

  In Example 8, in the production of the polishing slurry for CMP, 0.5% by mass of TR-704 and 0.1% by mass of polyglycerol 20-mer were used. The polishing selectivity of the insulating film with respect to the polysilicon film of Example 8 was 84, which was higher than those of Comparative Examples 1 to 3.

  In Example 9, 0.5 mass% TR-704, 0.3 mass% PVP K30, and 0.01 mass% polyglycerin tetramer were used in the production of the polishing slurry for CMP. The polishing selectivity of the insulating film with respect to the polysilicon film of Example 9 was 171 and was higher than Comparative Examples 1 to 3.

  In Example 10, in the preparation of the polishing slurry for CMP, 0.5 mass% TR-704, 0.3 mass% PVP K30, and 0.01 mass% polyglycerin 10-mer were used. The polishing selectivity of the insulating film to the polysilicon film of Example 10 was 222, which was higher than those of Comparative Examples 1 to 3.

  In Example 11, in the production of the polishing slurry for CMP, 0.5 mass% of TR-704, 0.3 mass% of PVP K30, and 0.01 mass% of polyglycerin 20-mer were used. The polishing selectivity of the insulating film to the polysilicon film of Example 11 was 250, which was higher than those of Comparative Examples 1 to 3. The polishing selectivity of the insulating film with respect to the silicon nitride film of Example 11 was 9, which was higher than that of Comparative Example 1.

  In Example 12, in the production of the polishing slurry for CMP, 0.5 mass% of TR-704, 0.3 mass% of PVP K15, and 0.01 mass% of polyglycerin 20-mer were used. The polishing selectivity of the insulating film with respect to the polysilicon film of Example 12 was 262, which was higher than those of Comparative Examples 1 to 3.

  In Example 13, in the production of the polishing slurry for CMP, 0.5% by mass of TR-704, 0.3% by mass of PVP K90, and 0.01% by mass of polyglycerin 20-mer were used. The polishing selectivity of the insulating film with respect to the polysilicon film of Example 13 was 194, which was higher than those of Comparative Examples 1 to 3.

  In Example 14, in the production of the polishing slurry for CMP, 0.5% by mass of TR-913R, 0.3% by mass of PVP K30, and 0.1% by mass of SC-E2000 were used. The polishing selectivity of the insulating film to the polysilicon film of Example 14 was 85, which was higher than those of Comparative Examples 1 to 3.

  In Example 15, 0.5 mass% TR-913R, 0.3 mass% PVP K30, and 0.1 mass% SC-P1000 were used in the production of the polishing slurry for CMP. The polishing selectivity of the insulating film with respect to the polysilicon film of Example 15 was 95, which was higher than those of Comparative Examples 1 to 3.

  In Example 16, in the preparation of the polishing slurry for CMP, 0.5 mass% of TR-913R, 0.3 mass% of PVP K30, and 0.1 mass% of # 310-EO60 were used. The polishing selectivity of the insulating film with respect to the polysilicon film of Example 16 was 64, which was higher than those of Comparative Examples 1 to 3.

  ADVANTAGE OF THE INVENTION According to this invention, the abrasive | polishing agent which can improve the polish selectivity of the insulating film with respect to a stopper film, an abrasive | polishing agent set, and the grinding | polishing method of a base | substrate can be provided. Further, according to the present invention, in the CMP technique for flattening the shallow trench isolation insulating film, the premetal insulating film, the interlayer insulating film, etc., it is possible to polish the insulating film at high speed and obtain a highly flat surface. According to the present invention, the insulating film can be polished at high speed, and the insulating film can be polished with low polishing scratches.

Claims (14)

  An abrasive comprising abrasive grains containing hydroxide particles of a tetravalent metal element, a compound obtained by adding at least one of oxyethylene and oxypropylene to ethylenediamine, and a liquid medium.   The abrasive | polishing agent of Claim 1 which further contains polyvinylpyrrolidone.   The abrasive | polishing agent of Claim 1 which further contains a glycerol compound.   The abrasive | polishing agent of Claim 1 which further contains polyvinylpyrrolidone and a glycerol compound.   The abrasive | polishing agent of Claim 3 or 4 whose said glycerol compound is at least 1 type selected from the group which consists of a polyglycerol, a diglycerol derivative, and a polyglycerol derivative.   The abrasive according to claim 3 or 4, wherein the glycerin compound is at least one selected from the group consisting of polyglycerin and diglycerin derivatives.   The abrasive | polishing agent of Claim 3 or 4 whose said glycerol compound is a polyglycerol.   The hydroxide particle of the tetravalent metal element is at least one selected from the group consisting of rare earth metal element hydroxide particles and zirconium hydroxide particles. The abrasive | polishing agent as described in.   The content of the compound obtained by adding at least one of oxyethylene and oxypropylene to ethylenediamine is 0.01% by mass or more and 10% by mass or less based on the total mass of the abrasive. The polishing agent according to item.   The abrasive | polishing agent as described in any one of Claims 1-9 used in order to grind | polish the to-be-polished surface containing a silicon oxide.   The constituent of the abrasive according to any one of claims 1 to 10 is stored separately in a first liquid and a second liquid, and the first liquid contains the abrasive grains and a liquid medium. And the second liquid contains the compound obtained by adding at least one of oxyethylene and oxypropylene to ethylenediamine, and a liquid medium.   The abrasive | polishing agent set of Claim 11 with which the said 2nd liquid further contains polyvinylpyrrolidone.   The abrasive | polishing agent set of Claim 11 or 12 with which the said 2nd liquid further contains a glycerol compound.   A method for polishing a substrate, comprising a step of polishing a surface to be polished of the substrate using the abrasive according to any one of claims 1 to 10.