WO2017090889A1

WO2017090889A1 - Cmp slurry composition and organic film polishing method using same

Info

Publication number: WO2017090889A1
Application number: PCT/KR2016/011624
Authority: WO
Inventors: 강동헌; 김정희; 최정민; 유용식
Original assignee: 삼성에스디아이 주식회사
Priority date: 2015-11-26
Filing date: 2016-10-17
Publication date: 2017-06-01
Also published as: TWI641670B; CN109153907B; CN109153907A; KR20170061818A; TW201720884A; KR101922289B1

Abstract

The present invention relates to a CMP slurry composition containing: an oxidant comprising an iron component; an organic acid having one carboxyl group; and water, and to an organic film polishing method using the same.

Description

CMP slurry composition and organic film polishing method using the same

The present invention relates to a CMP slurry composition and a method for polishing an organic film using the same.

The semiconductor manufacturing method includes forming an inorganic film such as a silicon oxide film and a silicon nitride film on a patterned silicon wafer, and gap-filling via-holes formed in the inorganic film. It includes a process to make. The gap-filling process is a process for filling the via-holes with the organic film material, and after the gap-filling process, a process of removing and planarizing the excessively formed organic film should be accompanied. As a planarization technique, the current spotlight is polishing by chemical mechanical polishing (CMP).

The conventional CMP slurry composition for organic films includes polymer abrasive particles because the organic film should be polished with a high polishing amount per unit time so as not to deteriorate the surface state such as scratches. However, when polishing with a CMP slurry composition for organic films containing polymer abrasive particles, the desired polishing amount could not be obtained while increasing the flatness of the polishing surface. However, when the metal oxide abrasive grains used for polishing the metal film such as silicon are used for polishing the organic film, there is a problem that the semiconductor yield is lowered due to excessive polishing, low polishing surface flatness or scratches. .

In order to solve the above problems, by using an oxidizing agent containing a metal salt, such as a ferric halide salt or a ferric nitrate salt together with the metal oxide abrasive, a technique for improving the polishing rate and the flatness of the polishing surface for the organic film Proposed. However, since ferric halogen salts or ferric nitrate salts are unstable in aqueous solution, when the above oxidizing agent is added to the slurry composition, iron particles precipitate and precipitate in the slurry, which causes the organic film to precipitate. Not only does the polishing rate decrease, but the problem of contaminating the slurry feeder arises.

Background art of the present invention is disclosed in Korea Patent Publication No. 2007-0057009.

It is an object of the present invention to provide an organic film CMP slurry composition having excellent polishing properties for organic films without using abrasive particles.

Another object of the present invention is to suppress the precipitation of the oxidizing agent containing Fe ions in the slurry composition to maintain a stable polishing rate, it is possible to provide a CMP slurry composition for organic membranes that can prevent the slurry supply apparatus from being contaminated by iron To provide.

Still another object of the present invention is to provide a method for polishing an organic film using the CMP slurry composition for organic films according to the present invention.

In one aspect, the invention provides an oxidant comprising an iron component; Organic acids having one carboxyl group; And CMP slurry composition consisting of water.

The oxidant including the iron component may include a ferric halogen salt, a ferric nitrate salt, a ferric sulfate salt, a ferric phosphate salt, or a combination thereof.

The organic acid may include lactic acid, formic acid, acetic acid, propionic acid or a combination thereof.

The oxidant including the iron component and the organic acid having one carboxyl group may be included in a weight ratio of about 7.5: 1 to about 1.5: 1.

Preferably, the CMP slurry composition may consist of about 0.001% to about 15% by weight of an oxidizing agent comprising the iron component, about 0.02% to about 0.5% by weight of an organic acid having one carboxyl group, and a balance of water. have.

The CMP slurry composition does not contain abrasive particles.

The CMP slurry composition may be for polishing an organic film.

In another aspect, the present invention provides a method for polishing an organic film comprising polishing the organic film using the CMP slurry composition.

Since the CMP slurry composition of this invention does not contain abrasive grains, it can suppress the generation | occurrence | production of the excessive grinding | polishing and / or the scratch which generate | occur | produces by abrasive grains at the time of organic membrane polishing.

In addition, the CMP slurry composition of the present invention is a problem caused by the precipitation of iron in the slurry by stabilizing the oxidizing agent containing the iron by an organic acid containing one carboxyl group, that is, lowering the polishing rate and / or supply apparatus contamination Problems such as can be prevented from occurring, and the stability of the slurry is improved, which is advantageous for storage and transportation.

1 is a schematic diagram of an organic film polishing method according to an embodiment of the present invention.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated concretely.

CMPCMP 슬러리 조성물 Slurry composition

First, the CMP slurry composition according to the present invention will be described.

According to one embodiment, the CMP slurry composition of the present invention comprises (A) an oxidizing agent comprising an iron component, (B) an organic acid having one carboxyl group, and (C) water, and does not include abrasive particles.

In general, in the case of an organic film, unlike a metal film such as copper wiring, the surface is soft, and when abrasive particles are used, there is a problem in that scratches occur on the surface of the organic film or excessive polishing occurs by the abrasive particles. However, if the abrasive particles are not used, there is a problem that polishing is not sufficiently performed.

The inventors of the present invention have repeatedly studied to solve the above problems, and when using an oxidizing agent having an iron component and an organic acid having one carboxyl group without using abrasive particles, the present inventors have excellent polishing properties for the organic film. It has been found that problems caused by the use of abrasive particles, such as scratching, can be solved, and the present invention has been completed. Since the CMP slurry composition of the present invention does not use abrasive particles, scratches are less generated when the organic film is applied, and thus the flatness is excellent, and the polishing rate with respect to the organic film is also excellent.

Hereinafter, each component of the CMP slurry composition according to the present invention will be described in more detail.

(A) 산화제(A) oxidizing agent

The CMP slurry composition of the present invention comprises an oxidant comprising an iron component. The oxidizing agent oxidizes the surface layer of the organic film to cause polishing, and includes an iron component.

The oxidizing agent including the iron component may include, but is not limited to, for example, a ferric halogen salt, a ferric nitrate salt, a ferric sulfate salt, a ferric phosphate salt, or a combination thereof. Specifically, as an oxidizing agent containing the iron component used by this invention, ferric chloride, ferric nitrate, ferric sulfate, ferric phosphate, etc. are mentioned.

On the other hand, the oxidizing agent may be included in about 0.001% to about 15% by weight, for example about 0.01% to about 5% by weight, for example about 0.05% to about 3% by weight of the CMP slurry composition. It is possible to maintain excellent etching property to the organic film in the above range.

(B) 유기산(B) organic acid

The CMP slurry composition of this invention contains the organic acid which has one carboxy group.

The organic acid is to stabilize the oxidizing agent including the iron component to prevent the precipitation of iron in the slurry, and to improve the polishing properties of the slurry composition.

The organic acid used in the present invention has one carboxyl group, and may include, for example, lactic acid, formic acid, acetic acid, propionic acid, or a combination thereof, but is not limited thereto.

According to the researches of the present inventors, when using an organic acid that does not contain a carboxyl group or contains two or more carboxyl groups, the polishing rate for the organic film is significantly reduced, and precipitation of iron particles occurs when the organic acid is not included. It was. However, when an organic acid having one carboxyl group was used, the polishing rate for the organic film was excellent at 1000 mW / min or more, and no iron particle precipitation occurred.

In the present invention, the organic acid having one carboxyl group is from about 0.02% to about 0.5% by weight, preferably from about 0.03% to about 0.2% by weight, more preferably from about 0.04% to about 0.1 in the slurry composition. It may be included in weight percent. In this range, both polishing rate and slurry stability are excellent.

On the other hand, in the present invention, The oxidizing agent including the iron component and the organic acid having one carboxyl group may be included in a weight ratio of about 7.5: 1 to about 1.5: 1, preferably, about 5: 1 to about 2: 1, more preferably May be included in a weight ratio of about 2.5: 1 to about 2: 1. It is possible to maintain the stability of the oxidizing agent and a high organic film polishing rate in the above range.

(C) 물(C) water

The CMP slurry composition of the present invention is used by dissolving an oxidizing agent and an organic acid in water. In this case, the water may be deionized water, but is not limited thereto. The content of water is added so as to be 100% by weight in combination with the contents of the oxidizing agent and the organic acid.

유기막Organic membrane

The CMP slurry composition according to the present invention may be for polishing an organic film. EMBODIMENT OF THE INVENTION Hereinafter, the organic film which is a grinding | polishing object of this invention is demonstrated concretely.

In this specification, “substituted” means that at least one hydrogen atom of the functional group is a hydroxy group, a halogen atom, a thionyl group, a thiol group, a cyano group, an amino group, a C1 to C30 alkyl group, a C2 to C30 alkenyl group, a C2 to C30 alkynyl group, and a C3 to C3 group. C30 cycloalkyl group, C3 to C30 cycloalkenyl group, C6 to C30 aryl group, C7 to C30 arylalkyl group, C1 to C20 heteroalkyl group, C2 to C30 heterocycloalkyl group, C2 to C30 heterocycloalkenyl group, C2 to C30 heteroaryl group , C2 to C30 heteroarylalkyl group, C1 to C20 alkylamine group, C1 to C30 alkoxy group, C6 to C30 aryloxy group, C1 to C20 aldehyde group, C1 to C40 alkylether group, C7 to C20 arylalkylene ether group, C1 To C30 haloalkyl group, a functional group including P, a functional group including B, or a combination thereof.

In the present specification, "functional group including P" may be represented by the following Chemical Formula A, and "functional group including B" may be represented by the following Chemical Formula B:

*-(O) _n- (CH ₂ ) _m -P (= O) (R ^a ) (R ^b )

* -B (R ^c ) (R ^d )

In <Formula A> and <Formula B>, n is 0 or 1, m is an integer of 0 to 10, R ^a , R ^b , R ^c and R ^d are each independently hydrogen, hydroxyl, substituted or Unsubstituted C1 to C20 alkyl group, substituted or unsubstituted C2 to C20 alkenyl group, substituted or unsubstituted C3 to C20 cycloalkyl group, substituted or unsubstituted C1 to C20 haloalkyl group, substituted or unsubstituted C1 to C20 alkylsulfonate group, substituted or unsubstituted C1 to C20 alkylsulfonyl group, substituted or unsubstituted C2 to C20 alkylamide group, substituted or unsubstituted C3 to C20 alkyl ester group, substituted or Unsubstituted C2 to C20 cyanoalkyl group, substituted or unsubstituted C1 to C20 alkoxy group, substituted or unsubstituted C6 to C30 aryl group, substituted or unsubstituted C6 to C30 arylalkyl group, substituted or unsubstituted or C6 to C30 aryloxy group, or R ^a and R ^b again R ^c and R ^d are connected to each other to form a heterocycloalkyl group of the substituted or unsubstituted C3 to C20 cycloalkyl group or a substituted or unsubstituted C3 to C20.

Preferably, the "functional group containing P" is a functional group containing P and O, for example, -P (= 0) (OH) ₂ , -OP (= 0) (OH) ₂ , -P ( _{_{= O) (OCH 2 CH 3}} ) 2, -P (= O) (C 2 H 4 C 6 H 5) (OCH 2 CH 3) , and the like, the "functional group containing B 'is a B and O Examples of the functional group include -B (OH) ₂ , -B (H) (CH ₃ ), -B (CH ₂ CH ₃ ) ₂ , and the like.

When an inorganic film is deposited on a patterned wafer, for example a silicon wafer, the organic film fills the generated via-holes. In order to planarize the deposited film, the CMP slurry composition should be able to polish the organic film to a sufficient polishing rate and increase the flatness of the polished surface to remove the residues remaining in the inorganic film after polishing. The inorganic film may be a film formed of at least one of silicon oxide and silicon nitride, but is not limited thereto. The inorganic membrane may have a carbon content of about 1 atom% or less, for example 0 to about 1 atom%, or for example 0 atom%.

The organic film may have a large difference in polishing amount per unit time and flatness after polishing depending on the material of the organic film. The organic film CMP slurry composition of the present invention is a composition for polishing an organic film having a high carbon content, and may increase the polishing amount per unit time of the organic film during the polishing of the organic film and have a high selectivity to the inorganic film.

In an embodiment, the organic film can have a carbon content of at least about 90 atom%, such as from about 90 atom% to about 99 atom% or, for example, from about 95 atom% to about 99 atom%, polishing with ceria in the above range. During polishing, the polishing amount is high, no scratch occurs, and the polishing surface may have high flatness. The organic film has a film density of about 0.5 g / cm ³ To about 2.5 g / cm ³ For example, about 1.0 g / cm ³ To about 2.0g / cm ^3, for example, from about 1.2 g / cm ³ It may be from about 1.6g / cm ³ , in the above range when polishing with ceria, the polishing amount is high, the scratch does not occur and the flatness of the polishing surface may also be high. The organic film may have a hardness of about 0.4 GPa or more, for example about 1.0 GPa or more, for example about 1.3 GPa or more, for example, about 1.3 GPa to about 1.5 GPa, and when polished with ceria in the above range, The polishing amount is high, no scratch occurs, and the flatness of the polishing surface may be high.

In addition, the organic film to be polished of the present invention may have an acid value of substantially 0 mgKOH / g. When polishing an organic film, which is a polishing target of the present invention, with an organic film CMP slurry composition including a conventional polymer abrasive, there is a problem that the polishing rate is lowered. On the other hand, the CMP slurry composition of the present invention can secure the amount of polishing per unit time of the organic film applicable to the CMP process. The term “substantially” includes not only the case where the acid value is 0 mgKOH / g but also a slight error at 0 mgKOH / g.

Specifically, the organic film to be polished of the present invention may be prepared by applying a composition for forming an organic film on an inorganic film and then thermosetting (baking) at a high temperature, for example, about 200 ° C to about 400 ° C.

The organic film forming composition may include a compound having a substituted or unsubstituted aromatic group.

The "compound having a substituted or unsubstituted aromatic group" refers to a compound that does not decompose even after thermal curing, so that the organic film formed of the composition can exhibit a high carbon content. The unsubstituted aromatic group means a single or fused polycyclic aromatic group having 6 to 100 carbon atoms, for example, 6 to 50 carbon atoms, and specifically, may include units of the following Chemical Formulas 1-1 to 1-26. Can:

In Formulas 1-1 to 1-26, Z ¹ to Z ¹⁸ are each independently a single bond, a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C2 to C20 alkenylene group, a substituted or unsubstituted C2 to C20 alkynylene group, substituted or unsubstituted C3 to C20 cycloalkylene group, substituted or unsubstituted C3 to C20 cycloalkenylene group, substituted or unsubstituted C6 to C20 arylene group, substituted or unsubstituted C2 To C20 heteroarylene group,-(C = O)-, -NR ^e- , -CR ^f R ^g- , oxygen (O), sulfur (S) or a combination thereof, wherein R ^e , R ^f and R ^g Are each independently hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, a halogen atom, a substituted or unsubstituted C6 to C20 arylene group, a substituted or unsubstituted C2 to C20 heteroarylene group, or a combination thereof.

Hereinafter, the specific example of the composition for organic film formation containing the compound which has a substituted or unsubstituted aromatic group is demonstrated in detail.

In a first embodiment, the composition for forming an organic layer may include a material having a substituted or unsubstituted aromatic group, and a material including a unit represented by Formula 2 below:

In Formula 2, a is 1 ≦ a <190,

R ₁ is hydrogen, a hydroxy group, a halogen atom, an allyl group, thionyl group, a thiol group, a cyano group, a substituted or unsubstituted amino group, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C1 to C30 heteroalkyl group , Substituted or unsubstituted C2 to C30 alkenyl group, substituted or unsubstituted C2 to C30 alkynyl group, substituted or unsubstituted C3 to C30 cycloalkyl group, substituted or unsubstituted C2 to C30 heterocycloalkyl group, substituted or unsubstituted C3 to C30 cycloalkenyl group, substituted or unsubstituted C6 to C30 aryl group, substituted or unsubstituted C7 to C30 arylalkyl group, substituted or unsubstituted C2 to C30 heterocycloalkenyl group, substituted or unsubstituted C2 to C30 heteroaryl group, substituted or unsubstituted C2 to C30 heteroarylalkyl group, substituted or unsubstituted C1 to C20 alkylamine group, substituted or unsubstituted C1 to C30 alkoxy group, Or an unsubstituted C1 to C30 heteroalkoxy group, a substituted or unsubstituted C6 to C30 aryloxy group, a substituted or unsubstituted C1 to C20 aldehyde group, a substituted or unsubstituted C1 to C40 alkylether group, a substituted or unsubstituted A C7 to C20 arylalkylene ether group, a substituted or unsubstituted C1 to C30 haloalkyl group, a functional group including P, a functional group including B, or a combination thereof,

R ₂ is hydrogen, an amino group, a substituted or unsubstituted C 1 to C 20 alkoxy group, a substituted or unsubstituted C 6 to C 20 aryloxy group, a dialkylamino group (-NRR ′, where R and R ′ are independently of each other Or unsubstituted C1 to C10 alkyl group or substituted or unsubstituted C6 to C10 aryl group), hydroxy group, halogen atom, allyl group, thionyl group, thiol group, cyano group, substituted or unsubstituted amino group, substituted or Unsubstituted C1 to C30 alkyl group, substituted or unsubstituted C1 to C30 heteroalkyl group, substituted or unsubstituted C2 to C30 alkenyl group, substituted or unsubstituted C2 to C30 alkynyl group, substituted or unsubstituted C3 to C30 cycle Alkyl group, substituted or unsubstituted C2 to C30 heterocycloalkyl group, substituted or unsubstituted C3 to C30 cycloalkenyl group, substituted or unsubstituted C6 to C30 aryl group, substituted or unsubstituted C7 to C30 arylalkyl , A substituted or unsubstituted C2 to C30 heterocycloalkenyl group, a substituted or unsubstituted C2 to C30 heteroaryl group, a substituted or unsubstituted C2 to C30 heteroarylalkyl group, a substituted or unsubstituted C1 to C20 alkylamine group, Substituted or unsubstituted C1 to C30 alkoxy group, substituted or unsubstituted C1 to C30 heteroalkoxy group, substituted or unsubstituted C6 to C30 aryloxy group, substituted or unsubstituted C1 to C20 aldehyde group, substituted or unsubstituted A C1 to C40 alkyl ether group, a substituted or unsubstituted C7 to C20 arylalkylene ether group, a substituted or unsubstituted C1 to C30 haloalkyl group, a functional group including P, a functional group including B, or a combination thereof,

R ₃ is substituted or unsubstituted,

Which is either.

For example, R ₂ may be a substituted or unsubstituted C 1 to C 10 alkoxy group.

The composition for forming an organic film including Chemical Formula 2 may increase carbon content, film density, and hardness after thermosetting, and refer to Korean Patent No. 10-0866015 for a more detailed manufacturing method thereof.

The composition for forming an organic film according to the first embodiment may further include at least one of a crosslinking component, an acid catalyst, and an organic solvent, in addition to the material containing Chemical Formula 2. Specifically, about 1% to about 20% by weight of the material including the unit represented by Formula 2, about 0.1% to about 5% by weight of the crosslinking component, about 0.001% to about 0.05% by weight of the acid catalyst, and the organic solvent About 75% to about 98.8% by weight.

The crosslinking component may be a melamine resin (eg, N-methoxymethyl-melamine resin, N-butoxymethylmelamine resin), methylated or butylated urea resin, amino resin, glycoluril derivative of Formula 3, Bisepoxy compound, may include one or more of the melamine derivative of formula (5):

Acid catalysts include p-toluenesulfonic acid monohydrate, pyridinium p-toluene sulfonate, 2,4,4,6-tetrabromocyclohexadienone, benzoin tosylate, 2-nitrobenzyl tosylate, alkyl of euphonic acid It may include one or more of the esters. The organic solvent is not particularly limited as long as it is an organic solvent having sufficient solubility in a compound having a substituted or unsubstituted aromatic group, and examples thereof include propylene glycol monomethyl ether acetate, cyclohexanone, ethyl lactate and the like.

The organic film forming composition of the first embodiment may be coated with a thickness of about 500 kPa to about 4000 kPa, and thermally cured at about 200 ° C. to about 400 ° C. for about 10 seconds to about 10 minutes to form an organic film, but is not limited thereto. Do not.

In a second embodiment, the composition for forming an organic film may be a compound having a substituted or unsubstituted aromatic group and may include a material represented by the following formula (6):

In Formula 6, R ₄ to R ₉ , X ₁ to X ₆ are each independently hydrogen, hydroxy group, halogen atom, allyl group, thionyl group, thiol group, cyano group, substituted or unsubstituted amino group, substituted or Unsubstituted C1 to C30 alkyl group, substituted or unsubstituted C1 to C30 heteroalkyl group, substituted or unsubstituted C2 to C30 alkenyl group, substituted or unsubstituted C2 to C30 alkynyl group, substituted or unsubstituted C3 to C30 cycle Alkyl group, substituted or unsubstituted C2 to C30 heterocycloalkyl group, substituted or unsubstituted C3 to C30 cycloalkenyl group, substituted or unsubstituted C6 to C30 aryl group, substituted or unsubstituted C7 to C30 arylalkyl group, substituted or Unsubstituted C2 to C30 heterocycloalkenyl group, substituted or unsubstituted C2 to C30 heteroaryl group, substituted or unsubstituted C2 to C30 heteroarylalkyl group, substituted or unsubstituted C1 to C2 0 alkylamine group, substituted or unsubstituted C1 to C30 alkoxy group, substituted or unsubstituted C1 to C30 heteroalkoxy group, substituted or unsubstituted C6 to C30 aryloxy group, substituted or unsubstituted C1 to C20 aldehyde group, A substituted or unsubstituted C1 to C40 alkylether group, a substituted or unsubstituted C7 to C20 arylalkylene ether group, a substituted or unsubstituted C1 to C30 haloalkyl group, a functional group comprising P, a functional group including B or these Is a combination of

n ₁ to n ₆ are each independently in a range of 0 to 2, and 2 ≦ n ₁ + n ₂ + n ₃ + n ₄ + n ₅ + n ₆ ≦ ₆ .

For example, R ₄ to R ₉ are each independently a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C6 to C20 aryl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or It may be an unsubstituted C3 to C20 cycloalkenyl group, a functional group including P, or a functional group including B.

For example, X ₁ to X ₆ may be each independently hydrogen, a hydroxy group, a substituted or unsubstituted C 1 to C 20 alkylamine group, an amino group, a functional group including P, a functional group including B.

The compound having a substituted or unsubstituted aromatic group is substantially the same as the organic film composition of the first embodiment except for including the material represented by Chemical Formula 6 instead of the material represented by Chemical Formula 2. Therefore, hereinafter, only the substance represented by Chemical Formula 6 will be described.

The material represented by Chemical Formula 6 may be a mixture of two or more compounds having different positions of substituents, and may include an aromatic ring having strong absorption in a short wavelength region (eg, 193 nm and 248 nm), even if no special catalyst is used. Since the crosslinking reaction proceeds at a high temperature, it is possible to prevent contamination by a catalyst, especially an acid, and the aromatic group compound of Chemical Formula 6 may have an average molecular weight of about 500 to about 4000. Can be formed.

The material represented by Chemical Formula 6 may increase carbon content, film density, and hardness after thermal curing of the organic film composition. The material represented by Chemical Formula 6 may be prepared by a conventional method, for example, it may be prepared by reacting and reducing acetyl chloride, benzoyl chloride, naphthoyl chloride, cyclohexanecarbonyl chloride to coronene, but It is not limited. For more detailed manufacturing method refer to Korea Patent Registration No. 10-1311942.

In a third embodiment, the organic film composition may include an aromatic group-containing polymer selected from (i), (ii) and (iii) as a compound having a substituted or unsubstituted aromatic group:

(i) a compound comprising a unit represented by the following formula (7),

(ii) a mixture of a compound comprising a unit represented by the following formula (7) with a compound comprising a unit represented by the following formula (8),

(iii) A compound comprising a unit represented by the following formula (9).

(In the formulas 7 to 9, b, c, d and e are each independently 1 to 750, 2≤≤ c + d <1500,

R ₁₀ is substituted or unsubstituted,

Wherein any one of R is hydrogen, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C1 to C30 heteroalkyl group, a substituted or unsubstituted C2 to C30 alkenyl group, a substituted or unsubstituted C2 To C30 alkynyl group, substituted or unsubstituted C3 to C30 cycloalkyl group, substituted or unsubstituted C1 to C30 heterocycloalkyl group, substituted or unsubstituted C3 to C30 cycloalkenyl group, substituted or unsubstituted C6 to C30 aryl group , Substituted or unsubstituted C7 to C30 arylalkyl group, substituted or unsubstituted C2 to C30 heterocycloalkenyl group, substituted or unsubstituted C2 to C30 heteroaryl group, substituted or unsubstituted C2 to C30 heteroarylalkyl group, substituted Or an unsubstituted C1 to C20 alkylamine group, a substituted or unsubstituted C1 to C30 haloalkyl group, a functional group including P, a functional group including B, or a combination thereof,

R ₁₁ is hydrogen, a hydroxy group, a halogen atom, a thionyl group, a thiol group, a cyano group, a substituted or unsubstituted amino group, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C1 to C30 heteroalkyl group, a substituted or Unsubstituted C2 to C30 alkenyl group, substituted or unsubstituted C2 to C30 alkynyl group, substituted or unsubstituted C3 to C30 cycloalkyl group, substituted or unsubstituted C1 to C30 heterocycloalkyl group, substituted or unsubstituted C3 to C30 cycloalkenyl group, substituted or unsubstituted C6 to C30 aryl group, substituted or unsubstituted C7 to C30 arylalkyl group, substituted or unsubstituted C2 to C30 heterocycloalkenyl group, substituted or unsubstituted C2 to C30 heteroaryl Groups, substituted or unsubstituted C2 to C30 heteroarylalkyl group, substituted or unsubstituted C1 to C20 alkylamine group, substituted or unsubstituted C1 to C30 alkoxy group, substituted or Unsubstituted C6 to C30 aryloxy group, substituted or unsubstituted C1 to C20 aldehyde group, substituted or unsubstituted C1 to C40 alkylether group, substituted or unsubstituted C7 to C20 arylalkylene ether group, substituted or unsubstituted A C1 to C30 haloalkyl group, a functional group including P, a functional group including B, or a combination thereof,

R ₁₂ is substituted or unsubstituted,

Any one of

R ₁₃ is substituted or unsubstituted,

R ₁₄ is substituted or unsubstituted,

Any one of

R ₁₅ is substituted or unsubstituted,

R at R ₁₀ , R ₁₃ and R ₁₅ are each independently hydrogen, hydroxy group, halogen atom, thionyl group, thiol group, cyano group, substituted or unsubstituted amino group, substituted or unsubstituted C1 to C30 alkyl group, substituted or Unsubstituted C1 to C30 heteroalkyl group, substituted or unsubstituted C2 to C30 alkenyl group, substituted or unsubstituted C2 to C30 alkynyl group, substituted or unsubstituted C3 to C30 cycloalkyl group, substituted or unsubstituted C1 to C30 Heterocycloalkyl group, substituted or unsubstituted C3 to C30 cycloalkenyl group, substituted or unsubstituted C6 to C30 aryl group, substituted or unsubstituted C7 to C30 arylalkyl group, substituted or unsubstituted C2 to C30 heterocycloalkenyl group , Substituted or unsubstituted C2 to C30 heteroaryl group, substituted or unsubstituted C2 to C30 heteroarylalkyl group, substituted or unsubstituted C1 to C20 alkylamine group, substituted or unsubstituted C1 to C30 alkoxy group, substituted or unsubstituted C6 to C30 aryloxy group, substituted or unsubstituted C1 to C20 aldehyde group, substituted or unsubstituted C1 to C40 alkylether group, substituted or unsubstituted C7 to C20 arylalkyl Or a ene ether group, a substituted or unsubstituted C1 to C30 haloalkyl group, a functional group including P, a functional group including B, or a combination thereof.

The compound having a substituted or unsubstituted aromatic group is substantially the same as the organic film composition of the first embodiment except that the aromatic group-containing polymer is included in place of the material represented by Chemical Formula 2. Therefore, hereinafter, only the aromatic group-containing polymer will be described.

The aromatic group-containing polymer may increase carbon content, film density and hardness after thermal curing of the organic film composition, and may be prepared by a conventional method, and refer to Korean Patent No. 10-0908601 for more details.

In a fourth embodiment, the organic film composition is a compound having a substituted or unsubstituted aromatic group material comprising a unit represented by the formula (2); A substance represented by Chemical Formula 6; It may contain two or more of the aromatic group-containing polymers selected from the above (i), (ii) and (iii). It is substantially the same as the composition of the first embodiment except that it contains two or more kinds.

유기막Organic membrane 연마 방법 Polishing method

The organic film polishing method of the present invention includes polishing an organic film using a CMP slurry composition, wherein the CMP slurry composition is a CMP slurry composition according to the present invention, that is, an oxidizing agent containing an iron component, one carboxyl group CMP slurry composition consisting of an organic acid and water having.

Hereinafter, the organic film polishing method of the present invention will be described with reference to FIG. 1A.

FIG. 1A illustrates a stacked state of a silicon wafer, an inorganic film, and an organic film prior to polishing an organic film. The silicon wafer 100 is patterned in an intaglio to locally form recesses, and the inorganic wafer is formed on the silicon wafer 100. The film 110 is deposited, and the organic film 120 is coated on the inorganic film and thermally cured at 200 ° C to 400 ° C. In FIG. 1A, T represents an imaginary polishing stop line.

After applying the CMP slurry composition of the present invention on the organic film of FIG. 1 (a) and installing the polishing pad, polishing is performed by rotating the silicon wafer 100 and polishing until the polishing stop line T is reached. Polish to the polishing stop line T of 1 (b).

Hereinafter, the present invention will be described in more detail with reference to the following examples, but the following examples are merely illustrative and are not intended to limit the protection scope of the present invention.

제조예Production Example

A silica film having a thickness of 500 mV was deposited on the pattern wafer having the negative pattern formed on the surface thereof, and an organic film having a thickness of 1400 mV was formed to fill the negative pattern formed on the surface of the silica film. In this case, the organic film was prepared by applying the composition for forming an organic film (T4 of SDI Co., Ltd.) on a silica film and thermosetting at 400 ° C.

실시예Example 및 And 비교예Comparative example

Specifications of the components used in the Examples and Comparative Examples of the present invention are as follows.

(A) Oxidizing agent: Ferric nitrate (Samjeon Pure Chemical Co., Ltd.) was used.

(B) organic acid

(b1) Lactic acid (Samjeon Pure Chemical Co., Ltd.) was used.

(b2) Propionic acid (Samjeon Pure Chemical Co., Ltd.) was used.

(b3) Acetic acid (Samjeon Pure Chemical Co., Ltd.) was used.

(b4) Formic acid (Samjeon Pure Chemical Co., Ltd.) was used.

(b5) Citric acid (Samjeon Pure Chemical Co., Ltd.) was used.

(b6) Oxalic acid (Oxalic acid) was used.

(b7) Phosphoric acid (Samjeon Pure Chemical Co., Ltd.) was used.

(C) water

(D) Abrasive particles: Colloidal silica having an average particle diameter of 55 nm was used as Nalco DVST027.

To prepare a CMP slurry containing the components in the amounts described in Table 1 below.

The particle precipitation, the polishing rate and the degree of scratch generation of the CMP slurry prepared by the above Examples and Comparative Examples were measured by the following method. The measurement results are shown in Table 1.

(1) Particle Precipitation: After the slurry was prepared, it was visually observed whether the particles precipitated at the bottom of the vessel while maintaining 50 ° C. in the oven for 7 days.

(2) Polishing speed (unit: Å / min):

By using the CMP slurry prepared in Examples and Comparative Examples, the patterned wafer on which the silica film and the organic film prepared in Preparation Example were formed was polished under the following conditions, and then the polishing rate was measured.

At this time, FUJIBO H0800 CMP pad was used as the polishing pad. As a grinding machine, 200mm MIRRA equipment from Applied Materials (AMAT) was used, and polishing was performed for 1 minute at a lower pressure of 1 psi, a slurry flow rate of 200 mL / minute, a platen speed of 100 rpm, and a head speed of 90 rpm. Was performed.

After polishing as described above, the thickness (unit: mm) of the polishing film was measured on the polished surface using a thin film thickness meter (ST4000, K-MAC), and the polishing rate (unit: mm / min) was measured from the measured thickness. Was calculated.

(3) scratch

The number of defects on the polished surface of the wafer polished under the polishing conditions was measured using a Defect measuring instrument (Hitachi, LS6800).

As described in [Table 1], in the CMP slurry compositions of Examples 1 to 7 according to the present invention, the polishing rate for the organic film was excellent, the stability of the CMP slurry was excellent, and scratching occurred during polishing. Effectively suppressed. In contrast, in the case of the CMP slurry of Comparative Example 1 containing no organic acid, the stability of the CMP slurry was inferior. On the other hand, in Comparative Examples 2 to 4 using organic acids having two or more carboxyl groups, the polishing rate for the organic film was significantly low. In addition, in the case of Comparative Example 5 containing abrasive particles, scratch generation was significantly increased.

Claims

Oxidizing agents including iron components;

Organic acids having one carboxyl group; And

CMP slurry composition consisting of water.
The method of claim 1,

The oxidizing agent comprising the iron component is a CMP slurry composition comprising a ferric halogen salt, a ferric nitrate salt, a ferric sulfate salt, a ferric phosphate salt or a combination thereof.
The method of claim 1,

Wherein said organic acid comprises lactic acid, formic acid, acetic acid, propionic acid, or a combination thereof.
The method of claim 1,

The oxidizing agent comprising the iron component and the organic acid having one carboxyl group is included in a weight ratio of about 7.5: 1 to about 1.5: 1.
The method of claim 1,

About 0.001 to about 15% by weight of an oxidizing agent comprising the iron component,

About 0.02 to about 0.5 weight percent of an organic acid having one carboxyl group, and

CMP slurry composition consisting of residual amount of water.
The method of claim 1,

The slurry composition does not contain abrasive particles.
The method of claim 1,

The slurry composition is a CMP slurry composition for polishing an organic film.
A method for polishing an organic film comprising polishing the organic film using the CMP slurry composition of any one of claims 1 to 7.