WO2019093620A1 - Organic film cmp slurry composition and polishing method using same - Google Patents

Abstract

Provided are an organic film CMP slurry composition comprising ceria, a cerium-containing ceria activating agent, and an inorganic film surface protecting agent, and an organic film polishing method using the same.

Description

Organic film CMP slurry composition and polishing method using the same

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

Recently, the line width of the wiring pattern becomes finer and the structure becomes more and more multilayered due to the high integration and high performance of semiconductor devices. In order to improve the precision of photolithography, interlayer flatness in each process is a very important factor. The CMP process is one of the most popular planarization technologies. The CMP process is an oxide CMP process, a metal CMP process, a poly - Si CMP process, and an organic film CMP process And so on.

A semiconductor process to which a CMP process for polishing an organic film (C-SOH) is applied includes an organic film planarization process. The organic film planarization process is a process for improving the step of the SOH film by polishing an over-deposited organic film, for example, a SOH (spin on hard mask) film.

On the other hand, a titanium nitride (TiN) film formed directly in contact with the SOH film is formed at the bottom of the SOH film. CMP slurry with high SOH and TiN polishing selectivity is required for RMG (Replacement Metal Gate) process. Conventional CMP slurries containing only abrasive grains and an oxidizing agent were difficult to apply to the RMG process because the selectivity was low because the polishing rate per unit time for SOH was about 4,000 Å / min and the polishing rate per unit time for titanium nitride was about 50 Å / min.

An object of the present invention is to provide an organic film CMP slurry composition having a large organic film polishing amount relative to an inorganic film polishing amount.

Another object of the present invention is to provide an organic film CMP slurry composition excellent in polishing selectivity between an inorganic film and an organic film.

It is still another object of the present invention to provide a polishing method using the organic film CMP slurry composition.

The organic film CMP slurry composition of the present invention may comprise a ceria, a cerium containing ceria activator, and an inorganic film surface protective agent.

The present invention provides an organic film CMP slurry composition having a large amount of organic film polishing with respect to an inorganic film polishing amount.

The present invention provides an organic film CMP slurry composition excellent in polishing selectivity between an inorganic film and an organic film.

The present invention provides a polishing method using the organic film CMP slurry composition.

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

The organic film CMP slurry composition (hereinafter referred to as "CMP slurry composition") of one embodiment of the present invention may include a ceria, a ceria-containing ceria activator, and an inorganic film surface protective agent. Thus, the CMP slurry composition of the present invention has a high polishing rate per unit time of the organic film, while a relatively low polishing rate of the inorganic film per unit time can increase the polishing selectivity between the inorganic film and the organic film. Specifically, the polishing selection ratio can be expressed by the following formula 1, and can be about 150 or more. In the above range, it can be sufficiently used in a polishing process requiring a high selectivity ratio of an inorganic film and an organic film, and there can be an effect that can be used in a RMG process in particular:

<Formula 1>

Polishing selection ratio = A / B

(In the above formula 1, A represents an organic film polishing amount per unit time (unit: A / min) of the slurry composition,

B is an inorganic film polishing amount per unit time (unit: A / min) of the slurry composition.

Preferably, the polishing selectivity ratio may be at least about 200, at least about 250, at least about 300, at least about 350, at least about 400. Within this range, it is possible to reduce the polishing amount of the inorganic film and to protect the film quality of the inorganic film.

The organic film may be a carbon-based film containing carbon-hydrogen bonds, such as a carbon-spin on hardmask (C-SOH) film, an amorphous carbon layer (ACL) or a nanocarbon polymer (NCP) film. Preferably, the CMP slurry composition of the present invention has a large amount of polishing on a C-SOH film having a high carbon content and a large polishing selectivity to an inorganic film, so that a C-SOH film is preferable for polishing the present invention. The organic film will be described later in more detail.

The inorganic film may be a film formed of titanium nitride (TiN). The CMP slurry composition of the present invention has a small amount of polishing per unit time for the titanium nitride film, so that the polishing selectivity of the organic film to the inorganic film can be increased. Specifically, the polishing amount per unit time for the titanium nitride film of the CMP slurry composition of the present invention may be about 30 Å / min or less, preferably about 20 Å / min or less, more preferably about 15 Å / min or less. Within this range, a high polishing selectivity can be achieved, and the protective effect of the inorganic film underlying film can be large.

Ceria (CeO ₂ ) can be used as a metal oxide abrasive to polish an organic film having a high carbon content at a high polishing amount. In particular, scratches and the like are not generated during the polishing of the organic film to be polished according to the present invention, and the flatness of the polished surface can be increased. Ceria can increase the amount of organic film polishing without or at least very little oxidizer.

The ceria may be spherical particles with an average particle size of from about 10 nm to about 150 nm, for example from about 30 nm to about 70 nm. It is possible to obtain a sufficient amount of organic film polishing in the above range, to prevent scratches on the organic film and the inorganic film, and to improve the flatness of the organic film and the inorganic film after polishing. The " average particle diameter " means an average primary particle diameter of the ceria particles.

The ceria may be included in the CMP slurry composition at about 0.01 wt% to about 10 wt%, such as about 0.05 wt% to about 5 wt%. A sufficient polishing amount can be obtained for the organic film within the above range, scratches can be prevented from occurring, and dispersion stability can be improved. Preferably, the average particle size of the ceria is high, and by lowering the content in the slurry composition, an improved polishing amount for the organic film and a low polishing amount for the inorganic film can be realized.

The cerium containing ceria activator can activate the ceria to increase the amount of organic film polishing. The cerium containing ceria activator does not activate silica, which is an example of a metal oxide abrasive. The ceria-containing ceria activator may be included together to provide an excellent polishing amount for the organic film, and an amount of polishing of the inorganic film may be reduced to secure a good selectivity to the organic film. have.

The cerium containing ceria activator may comprise a salt containing a cerium ion (Ce ⁺ , Ce ²⁺ , or Ce ³⁺ ) and an anion or a hydrate thereof. (Eg Ce (NO ₃ ) ₃ .6H ₂ O), cerium chloride (eg CeCl ₃ ), cerium sulfate (eg, Ce (NO ₃ ) ₃ ), hydrates of cerium nitrate : Ce ₂ (SO ₄₎ may include one or more of _3). The cerium-containing ceria activator may be present in the slurry composition in the form of an ionic compound or a chelate compound. When used in this form, it is possible to provide an excellent polishing amount for the organic film, A good selection ratio can be ensured.

The cerium containing ceria activator may be included in the CMP slurry composition in an amount of from about 0.01 wt% to about 5 wt%, preferably from about 0.01 wt% to about 2 wt%, more preferably from about 0.04 wt% to about 0.4 wt%. It is possible to provide an excellent polishing amount for the organic film within the above range and to reduce the amount of polishing of the inorganic film to secure a good selectivity to the organic film in comparison with the inorganic film and to prevent scratches on the organic film due to excessive organic film polishing Can be prevented.

The inorganic film surface protective agent does not adsorb on the surface of the inorganic film but inhibits the polishing of the inorganic film by the ceria so that the polishing rate of the inorganic film and the organic film can be increased by lowering the polishing amount of the inorganic film. The inorganic film surface protective agent is not coated on the surface of the organic film, and the amount of organic film polishing can be increased.

The inorganic membrane surface protective agent preferably has a weight average molecular weight in the nonionic surfactant of from about 200 g / mol to about 10,000 g / mol, preferably from about 300 g / mol to about 8,000 g / mol, from about 400 g / mol to about 6,000 g / mol. &lt; / RTI &gt; In the above range, even when polished together with ceria, scratches and the like on the organic film are less affected and the dispersion stability of the ceria particles can be increased. The inorganic membrane surface protective agent may include at least one of polyethylene glycol and polyurethane. In one embodiment, the inorganic membrane surface protective agent may be a polyethylene glycol having a weight average molecular weight of from about 200 g / mol to about 10,000 g / mol or mixtures comprising it. In other embodiments, the inorganic membrane surface protective agent may be a polyurethane having a weight average molecular weight of from about 1,000 g / mol to about 5,000 g / mol or mixtures comprising it.

The inorganic membrane surface protective agent may be included in the CMP slurry composition in an amount of from 0.01 wt% to about 5 wt%, preferably from about 0.01 wt% to about 2 wt%, more preferably from about 0.04 wt% to about 0.4 wt%. It is possible to reduce the amount of the inorganic film to be polished in the above range, to secure a good selectivity to the organic film with respect to the inorganic film, and to prevent scratches from occurring in the inorganic film.

The CMP slurry composition may comprise water. It is preferable to use ultrapure water as the water. Water may be included as a balance in the slurry composition.

The CMP slurry composition may be acidic. In this case, the effect of realizing a high polishing selectivity of the organic film to the inorganic film can be obtained, and the amount of polishing per hour for the organic film can be increased and the flatness can be increased. Specifically, the CMP slurry composition may have a pH of about 3 to about 5, preferably about 3 to about 4.

The CMP slurry composition further comprises a pH adjusting agent, whereby the CMP slurry composition can be adjusted to a pH in the aforementioned range. The pH adjusting agent may include at least one of inorganic acids such as nitric acid and sulfuric acid. The pH adjusting agent may include, but is not necessarily limited to, at least one of an organic acid, for example, an organic acid having a pKa of about 5 or less, specifically, acetic acid, or citric acid.

The pH adjusting agent may be included in the CMP slurry composition in an amount of up to about 5 wt%, from about 0.01 wt% to about 5 wt%, preferably from about 0.01 wt% to about 2 wt%, more preferably from about 0.04 wt% to about 0.4 wt% In the above range, it is possible to provide an excellent polishing amount for the organic film with respect to the organic film, and it is possible to reduce the polishing amount of the inorganic film, thereby securing a good selectivity to the organic film with respect to the inorganic film.

The CMP slurry composition comprises a peroxide-free . When the slurry composition contains a peroxide, the polishing selectivity ratio may be lowered by interfering with the polishing of the organic film of ceria. The content of peroxide in the slurry composition is about 10 ppm or less, preferably about 5 ppm or less, and more preferably about 0 ppm. The peroxide may include hydrogen peroxide water, ammonium persulfate.

The CMP slurry composition may further comprise an oxidizing agent other than peroxide. The oxidizing agent oxidizes the surface layer of the organic film in order to facilitate the polishing of the organic carbon film having a high carbon content, thereby facilitating the polishing of the organic film. When the inorganic film is exposed by polishing, the surface of the organic film is evenly polished so that the surface roughness It can be good. In addition, the residue of the organic film existing in the inorganic film can be easily removed, so that more uniform polishing can be achieved.

The oxidizing agent may include at least one of a metal salt having a polyvalent oxidation state and a chelate compound of a transition metal. The term " multivalent " means a divalent or more, for example, three or more, for example, four or more. The metal salt having a multi-valent oxidation state can increase the polishing rate for the organic film and lower the polishing rate for the inorganic film. The metal salt may include a metal such as a transition metal or a lanthanide element, and may further include a halogen, an ammonium, a nitrate, and the like. Specifically, the metal salt may include a seric ammonium salt, a ferric halogen salt, a ferric nitrate salt, and the like, and may include, for example, ceric ammonium nitrate, ferric nitrate, ferric chloride, and cerium nitrate.

The chelate compound of the transition metal can increase the polishing rate for the organic film and lower the polishing rate for the inorganic film.

In the chelate compounds of the transition metals, the transition metals include the commonly known transition metals of group 3 to 12 of the periodic table, for example, iron, copper, manganese or chromium. The chelate may be selected from the group consisting of oxalic acid, amino-substituted carboxylic acids such as iminodiacetic acid, ethylenediamine disuccinic acid, iminodisuccinic acid, ethylenediaminetetraacetic acid, aminopolycarboxylates such as nitrilotriacetic acid, alpha-amino acids such as glycine, Amino acids), hydroxyl-substituted carboxylic acids (e.g., glycolic acid, lactic acid, and also polycarboxylic acids including hydroxyl groups such as malic acid, citric acid, and tartaric acid), phosphonocarboxylic acids, aminophosphonic acids; And combinations of these. For example, the chelate compound of the transition metal may include, but is not limited to, one or more of Mn-containing compounds including Fe-containing compounds including propylene diamine tetraacetic acid-Fe and the like, propylene diamine tetraacetic acid-Mn and the like.

The oxidizing agent may be included in the slurry composition in an amount of up to about 15 wt%, from about 0.001 wt% to about 15 wt%, such as from about 0.01 wt% to about 5 wt%, such as from about 0.05 wt% to about 3 wt% . It is possible to maintain the proper etching property for the organic film within the above range. By making the slurry composition acidic, the stability of the oxidizing agent can be improved, the amount of polishing per unit time of the organic film can be increased, the flatness of the polishing surface can be improved, and the polishing selectivity to the inorganic film can be increased.

The slurry composition may further comprise additives. For example, the slurry composition may further comprise an abrasive accelerator as an additive. By further including the polishing accelerator, the polishing rate for the inorganic film can be suppressed, and the polishing selectivity between the inorganic film and the organic film can be increased. The abrasive accelerator may include one or more of organic acids such as malic acid, formic acid, glutaric acid, oxalic acid, phthalic acid, succinic acid, tartaric acid, maleic acid and malonic acid. The abrasive accelerator may be included in the slurry composition in an amount of about 0.5% by weight or less, preferably about 0.02% by weight to about 0.5% by weight. In the above range, there may be no adverse effect on the polishing amount, dispersion stability of the slurry, and surface characteristics of the organic film.

Hereinafter, the organic film to be polished of the slurry composition of the present invention will be specifically described.

As used herein, the term "substituted" means that a hydrogen atom of the functional group is a hydroxyl 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, , A C3 to C30 cycloalkenyl group, a C6 to C30 aryl group, a C7 to C30 arylalkyl group, a C1 to C20 heteroalkyl group, a C2 to C30 heterocycloalkyl group, a C2 to C30 heterocycloalkenyl group, a C2 to C30 heteroaryl group, A C1 to C30 alkyl group, a C1 to C30 alkyl group, a C1 to C30 alkoxy group, a C6 to C30 aryloxy group, a C1 to C20 aldehyde group, a C1 to C40 alkyl ether group, a C7 to C20 arylalkylene ether group, An alkyl group, a functional group containing P, a functional group containing B, or a combination thereof.

In the present specification, the "functional group containing P" may be represented by the following formula (1), and the "functional group containing B" may be represented by the following formula (2)

&Lt; Formula 1 >

- (O) _n - (CH ₂ ) _{m -} P (= O) (R ^a ) (R ^b )

(2)

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

(In the above formulas (1) and (2), 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, a hydroxyl group, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, A substituted or unsubstituted C1 to C20 haloalkyl group, a substituted or unsubstituted C1 to C20 alkylsulfonate group, a substituted or unsubstituted C1 to C20 alkylsulfonyl group, a substituted or unsubstituted C2 C20 alkyl amide group, a substituted or unsubstituted C3 to C20 alkyl ester group, a substituted or unsubstituted C2 to C20 cyano alkyl group, a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted A C6 to C30 aryl group, a substituted or unsubstituted C6 to C30 arylalkyl group, a substituted or unsubstituted C6 to C30 aryloxy group,

R ^a and R ^b or R ^c and R ^d are connected to each other to form a substituted or unsubstituted C3 to C20 cycloalkyl group or a substituted or unsubstituted C3 to C20 heterocycloalkyl group)

Preferably, the "functional group containing P", for example with a functional group containing P and O, -P (= O) ( OH) 2, -OP (= O) (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 the B" comprises a B for example, a functional group may be a _{-B (OH) 2, -B (} H) (CH 3), -B (CH 2 CH 3) 2.

When an inorganic film is deposited on a patterned wafer, for example a silicon wafer, the organic film fills the via-holes created. The slurry composition must be able to polish the organic film with a sufficient polishing rate and planarity of the polishing surface in order to planarize the deposited film, so that the residue remaining on the inorganic film after polishing must be removed. The inorganic film may be, but is not limited to, a film formed of titanium nitride. The inorganic film may have a carbon content of less than about 1 atom%, for example, from about 0 atom% to less than about 1 atom%, or for example, about 0 atom%.

The organic film may vary greatly in polishing amount per unit time and flatness after polishing depending on the material of the organic film. The slurry composition of the present invention is a composition that simultaneously polishes an organic film having a high carbon content and an inorganic film having a low carbon content at the same time, thereby increasing the polishing rate per unit time of the organic film and polishing rate per unit time of the inorganic film. Further, the slurry composition of the present invention can increase the polishing selectivity ratio of the inorganic film and the organic film even when the thin inorganic film and the organic film having a thickness of, for example, about 10 Å to about 20 Å are simultaneously polished. 1, the slurry composition of the present invention can be applied to an inorganic film and an organic film even when an inorganic film and an organic film having a thin thickness of, for example, about 10 to about 20 are polished simultaneously after the organic film having a predetermined thickness is polished, The polishing selectivity ratio can be increased.

The organic film may have a carbon content of at least about 70 atom%, such as from about 70 atom% to about 99 atom%, or for example from about 75 atom% to about 99 atom%. In the above range, the amount of polishing during polishing to ceria is high, scratches do not occur, and the flatness of the polishing surface is high. The organic film has a film density of 0.5 g / cm ³ to 3 g / cm ³ , For example 0.5g / cm ³ to 2.5g / cm ^3, 0.5 g / cm ³ to 2 g / cm ³ , and 1 g / cm ³ to 1.5 g / cm ³ . In the above range, the amount of polishing during polishing to ceria is high, scratches do not occur, and the flatness of the polishing surface is high. The organic film has a hardness of about 0.3 GPa or more, for example, about 0.4 GPa or more to about 2 GPa or less, about 0.6 GPa or more to about 1.5 GPa or less, about 0.6 GPa or more to about 1.2 GPa or less, about 0.6 GPa or more to about 1 GPa or less . In the above range, the amount of polishing during curing with ceria is high, scratches do not occur, and the flatness of the polishing surface is high.

The organic film may have an acid value of substantially 0 mg KOH / g. There has been a problem in that when the organic film to be polished of the present invention is polished with a slurry composition for polishing an organic film including a conventional polymeric polishing compound, the polishing rate is lowered. On the other hand, the slurry composition of the present invention can secure the polishing amount per unit time of the organic film applicable to the CMP process. The " substantially " includes not only an acid value of about 0 mgKOH / g but also a slight error at about 0 mgKOH / g.

The organic film may be prepared by applying a composition for forming an organic film on an inorganic film and then baking at a high temperature, for example, from about 200 캜 to about 400 캜.

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

The above-mentioned " compound having a substituted or unsubstituted aromatic group " means a compound which is not decomposed after thermosetting so that an organic film formed from 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 includes units represented by the following formulas (3-1) to can do:

&Lt; Formula 3-1 >

(3-2)

<Formula 3-3>

<Formula 3-4>

<Formula 3-5>

<Formula 3-6>

<Formula 3-7>

<Formula 3-8>

(Formula 3-9)

<Formula 3-10>

<Formula 3-11>

(3-12)

<Formula 3-13>

<Formula 3-14>

<Formula 3-15>

<Formula 3-16>

<Formula 3-17>

<Formula 3-18>

<Formula 3-19>

<Formula 3-20>

&Lt; Formula 3-21 &

<Formula 3-22>

<Formula 3-23>

<Formula 3-24>

<Formula 3-25>

<Formula 3-26>

In formulas (3-1) to (3-26), Z ¹ to Z ¹⁸ each independently represents 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, a substituted or unsubstituted C3 to C20 cycloalkylene group, a substituted or unsubstituted C3 to C20 cycloalkenylene group, a substituted or unsubstituted C6 to C20 arylene group, a substituted or unsubstituted C2 to C20 heteroaryl 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, specific examples of the composition for forming an organic film including a compound having a substituted or unsubstituted aromatic group will be described in more detail.

In a first embodiment, the composition for forming an organic film may comprise a substance having a substituted or unsubstituted aromatic group,

&Lt; Formula 4 >

In Formula 4, a is 1? A < 190,

R ₁ represents a hydrogen atom, a hydroxyl group, a halogen atom, an allyl group, 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, a substituted or unsubstituted C2 to C30 alkynyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C2 to C30 heterocycloalkyl group, A substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C7 to C30 arylalkyl group, a substituted or unsubstituted C1 to C20 heteroalkyl group, a substituted or unsubstituted C2 to C30 hetero 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 hetero A substituted or unsubstituted C1 to C20 alkylamine group, a substituted or unsubstituted C1 to C30 alkoxy group, a substituted or 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 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 containing B, or a combination thereof,

R ₂ represents hydrogen, an amino group, a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C6 to C20 aryloxy group, a dialkylamino group (-NRR ', wherein R and R' A substituted or unsubstituted C1 to C10 alkyl group or a substituted or unsubstituted C6 to C10 aryl group), a hydroxyl group, a halogen atom, an allyl group, a thionyl group, a thiol group, a cyano group, Substituted or unsubstituted C1 to C30 cycloalkyl, substituted or unsubstituted C1 to C30 heteroalkyl, substituted or unsubstituted C2 to C30 alkenyl, substituted or unsubstituted C2 to C30 alkynyl, substituted or unsubstituted C3 to C30 cyclo A substituted or unsubstituted C2 to C30 heterocycloalkyl group, a substituted or unsubstituted C3 to C30 cycloalkenyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C7 to C30 arylalkyl group, A substituted or unsubstituted C1 to C20 heteroalkyl group, a substituted or unsubstituted C2 to C30 heterocycloalkyl group, a substituted or unsubstituted C2 to C30 heterocycloalkenyl group, a substituted or unsubstituted C2 to C30 heteroaryl group, A substituted or unsubstituted C1 to C20 alkylamine group, a substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C1 to C30 heteroalkoxy group, a substituted or unsubstituted C1 to C30 heteroaryl group, A substituted or unsubstituted C 1 to C 20 arylalkoxy group, a substituted or unsubstituted C 1 to C 20 aryloxy group, a substituted or unsubstituted C 1 to C 20 aldehyde group, a substituted or unsubstituted C 1 to C 40 alkyl ether group, a substituted or unsubstituted C 7 to C 20 arylalkylene ether group, A C30 haloalkyl group, a functional group containing P, a functional group containing B, or a combination thereof,

R &lt; ₃ &gt; is a substituted or unsubstituted,

/ RTI &gt;

For example, R ₂ may be a substituted or unsubstituted C1 to C10 alkoxy group.

The composition for forming an organic layer 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 the compound of Formula 4. About 0.1 wt.% To about 5 wt.% Of a crosslinking component, about 0.001 wt.% To about 0.05 wt.% Of an acid catalyst, and about 75 wt.% Of an organic solvent. By weight to about 98.8% by weight.

The crosslinking component may be a melamine resin (specifically N-methoxymethyl-melamine resin, N-butoxymethylmelamine resin), methylated or butylated urea resin, amino resin, glycoluril derivative of the following formula A bis-epoxy compound, and a melamine derivative represented by the following formula (7): &lt; EMI ID =

&Lt; Formula 5 >

(6)

&Lt; Formula 7 >

The acid catalyst is selected from the group consisting of p-toluenesulfonic acid monohydrate, pyridinium p-toluenesulfonate, 2,4,4,6-tetrabromocyclohexadienone, benzoinositolate, 2-nitrobenzyltosylate, alkyl Esters. &Lt; / RTI &gt; The organic solvent is not particularly limited as long as it is an organic solvent having sufficient solubility for a compound having a substituted or unsubstituted aromatic group, and examples thereof include propylene glycol monomethyl ether acetate, cyclohexanone and ethyl lactate.

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

In the second embodiment, the composition for forming an organic film may include a substance having a substituted or unsubstituted aromatic group and represented by the following formula (8)

(8)

(Wherein R ₄ to R ₉ and X ₁ to X ₆ each independently represent a hydrogen atom, a hydroxyl group, a halogen atom, an allyl group, 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, a substituted or unsubstituted C2 to C30 alkynyl group, a substituted or unsubstituted C3 to C30 A substituted or unsubstituted C2 to C30 heterocycloalkyl group, a substituted or unsubstituted C3 to C30 cycloalkenyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C7 to C30 arylalkyl group, a substituted Or a substituted or unsubstituted C2 to C30 heterocycloalkyl group, a substituted or unsubstituted C2 to C30 heterocycloalkenyl group, a substituted or unsubstituted C2 A substituted or unsubstituted C1 to C30 heteroaryl group, a substituted or unsubstituted C2 to C30 heteroarylalkyl group, a substituted or unsubstituted C1 to C20 alkylamine group, a substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C1 to C30 hetero A substituted or unsubstituted C1 to C20 alkyl 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 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 containing P, a functional group containing B, or a combination thereof

n ₁ to n ₆ are each independently in the range of 0 to 2, and 2? n ₁ + n ₂ + n ₃ + n ₄ + n ₅ + n ₆ ?

For example, each of R ₄ to R ₉ independently represents 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, An unsubstituted C3 to C20 cycloalkenyl group, a functional group containing P, or a functional group containing B, for example.

For example, each of X ₁ to X ₆ may independently be a functional group including hydrogen, a hydroxyl group, a substituted or unsubstituted C1 to C20 alkylamine group, an amino group, a functional group containing P,

The organic film composition of the second embodiment is a compound having a substituted or unsubstituted aromatic group, and the organic film composition of the first embodiment is substantially the same as the organic film composition of the first embodiment except that the substance represented by the formula . Hereinafter, only the substance represented by Formula 8 will be described.

The substance represented by the formula (8) may be a mixture of two or more compounds having different substituent positions, and may include an aromatic ring having strong absorption in a short wavelength region (e.g., 193 nm, 248 nm) The aromatic group compound of formula (8) may have an average molecular weight of about 500 to about 4,000, and it is preferable that the thickness of the organic film in the range or the thickness of the thin film Can be formed.

The material of Formula 8 can increase carbon content, film density and hardness after thermal curing of the organic film composition. The compound represented by Formula 8 can be prepared by a conventional method, for example, by reacting coronene with acetyl chloride, benzoyl chloride, naphthoyl chloride, cyclohexanecarbonyl chloride, and reducing It is not limited.

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

(i) a compound represented by the following general formula (9)

(ii) a mixture of a compound represented by the following formula (9) and a compound represented by the following formula (10)

(iii) a compound represented by the following formula (11).

&Lt; Formula 9 >

&Lt; Formula 10 >

&Lt; Formula 11 >

(B), (c), (d) and (e) are independently 1 to 750, and 2? C + d <

R &lt; ₁₀ &gt; is a substituted or unsubstituted,

, &Lt; / RTI &gt;

R ₁₁ represents a hydrogen atom, a hydroxyl 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, a substituted or unsubstituted C2 to C30 alkynyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C1 to C30 heterocycloalkyl group, A substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C7 to C30 arylalkyl group, a substituted or unsubstituted C1 to C20 heteroalkyl group, a substituted or unsubstituted C2 to C30 heterocycloalkyl group, 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 heteroaryl group A substituted or unsubstituted C1 to C20 alkylamine group, a substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C6 to C30 aryloxy group, a substituted or unsubstituted C1 to C20 aldehyde group, A substituted or unsubstituted C7 to C20 arylalkylene ether group, a substituted or unsubstituted C1 to C30 haloalkyl group, a functional group containing P, a functional group containing B, or a combination thereof ,

R &lt; ₁₂ &gt; is a substituted or unsubstituted,

, &Lt; / RTI &gt;

R &lt; ₁₃ &gt; is a substituted or unsubstituted,

, &Lt; / RTI &gt;

R ₁₄ is a substituted or unsubstituted,

, &Lt; / RTI &gt;

R ₁₅ is a substituted or unsubstituted,

, &Lt; / RTI &gt;

Each of R ₁₀ , R ₁₃ and R ₁₅ is independently selected from the group consisting of hydrogen, a hydroxyl 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, a substituted or unsubstituted C2 to C30 alkynyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C1 to C30 Substituted or unsubstituted C1 to C20 heteroalkyl groups, substituted or unsubstituted C6 to C30 aryl groups, substituted or unsubstituted C7 to C30 arylalkyl groups, substituted or unsubstituted C1 to C20 heteroalkyl groups, substituted or unsubstituted C3 to C30 cycloalkenyl groups, Or a substituted or unsubstituted C2 to C30 heterocycloalkyl group, a substituted or unsubstituted C2 to C30 heterocycloalkenyl group, a substituted or unsubstituted C2 to C30 heteroaryl group, A substituted or unsubstituted C1 to C30 alkylamine group, a substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C6 to C30 aryloxy group, a substituted or unsubstituted C1 A substituted or unsubstituted 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 containing P, Functional group or a combination thereof)

The organic film composition of the third embodiment is substantially the same as the organic film composition of the first embodiment except that the aromatic group-containing polymer is replaced by a compound having a substituted or unsubstituted aromatic group in place of the substance represented by the formula Do. Hereinafter, only the aromatic group-containing polymer will be described.

The aromatic group-containing polymer can increase the carbon content, the film density and the hardness after thermal curing of the organic film composition, and can be produced by a usual method.

In a fourth embodiment, the organic film composition is a compound having a substituted or unsubstituted aromatic group; The substance represented by the formula (8); May contain two or more kinds of aromatic group-containing polymers selected from (i), (ii) and (iii) above. The organic film composition of the fourth embodiment is substantially the same as the composition of the first embodiment except that it contains two or more compounds having a substituted or unsubstituted aromatic group.

The CMP slurry composition can increase the polishing rate of the organic film per unit time and increase the polishing selectivity between the inorganic film and the organic film. Specifically, the polishing amount of the organic film per unit time may be more than about 4,000 ANGSTROM / min, specifically about 4,200 ANGSTROM / min or more, and about 4,250 ANGSTROM / min or more. Within this range, it is possible to increase the polishing selectivity between the inorganic film and the organic film.

The organic film polishing method of the present invention includes a step of polishing an organic film having a high carbon content using an organic film CMP slurry composition and the organic film CMP slurry composition may include the organic film CMP slurry composition of the present invention example.

1 (a) shows the lamination state of the silicon wafer, the inorganic film, and the organic film before the organic film polishing, in which the silicon wafer 100 is patterned at a negative angle, The inorganic film 110 is deposited on the silicon wafer 100, the organic film 120 is coated on the inorganic film, and thermosetting is performed at 200 ° C to 400 ° C. In Fig. 1 (a), T represents a virtual abrasive stop line. The organic film CMP slurry composition is applied onto the organic film of FIG. 1 (a), and the polishing pad is provided. Thereafter, the silicon wafer 100 is polished by rotating it and polished until reaching the polishing stop line T, To the abrasive stop line T of Fig.

EXAMPLES The present invention will now be described more specifically with reference to the following examples, but the following examples are for illustrative purposes only and do not limit the scope of protection of the present invention.

Manufacturing example

Preparation of Composition for Organic Film Formation

A 2,000 ml three-necked flask equipped with a thermometer, a condenser, a mechanical stirrer, and a dropping funnel is prepared and dipped in an oil bath at 140 ° C. Heating and stirring by magnet were performed on a hot plate and the cooling water temperature of the condenser was fixed at 40 ° C. 1 mol of 1-methoxypyrrene (220 g) was added to the reactor, followed by the addition of 1.0 mol of 1,4-bismethoxymethylbenzene (138 g), followed by dissolving in 656 g of propylene glycol monomethyl ether acetate. Then, 4.6 g of 0.03 mol of diethyl sulfate was added. The temperature of the reactor was maintained at 130 캜. The molecular weight was measured at certain time intervals during the polymerization to determine the completion time of the reaction. At this time, a sample for measuring the molecular weight was prepared by taking 1 g of the reaction product and quenching it to room temperature. Then, 0.02 g of the reaction product was taken out and diluted with tetrahydrofuran as a solvent so as to have a solid content of 4% by weight. At the completion of the reaction, 0.048 mol of triethanolamine (4.48 g) as a neutralizing agent was added to the reactor to terminate the reaction and stirred. The reaction was then slowly cooled to ambient temperature. The reaction product was diluted with 500 g of propylene glycol monomethyl ether acetate. The solvent was then added to a 2000 ml separatory funnel. 4 kg of a methanol: ethylene glycol mixture of 90: 10 g / g ratio was prepared. The synthesized polymer solution was added dropwise to the alcohol mixture under vigorous stirring. The resulting polymer was collected on the bottom of the flask, and the supernatant was stored separately. After removing the supernatant, the methanol of the final reaction product was removed by rotary evaporation under reduced pressure at 60 ° C for 10 minutes.

The molecular weight and the degree of dispersion of the obtained copolymer were measured by GPC under tetrahydrofuran, and as a result, a polymer containing units having a weight average molecular weight of 4000 and a dispersion degree of 2.3 was obtained.

&Lt; Formula 12 >

(Average a = 11, Me is a methyl group)

0.8 g of the polymer prepared above, 0.2 g of the crosslinking agent (5) (Powderlink 1174, Cytec Industries Inc.) and 2 mg of pyridinium p-toluenesulfonate were dissolved in 9 g of propylene glycol monomethyl ether acetate and filtered to form an organic film A composition was prepared.

Organic film manufacturing

An inorganic film of titanium nitride (TiN) having a thickness of 10 Å was deposited on a patterned wafer having an engraved pattern on its surface, and an organic film having a thickness of 2,700 Å was formed after filling the engraved pattern formed on the surface of the titanium nitride film. The organic film was prepared by applying the composition for forming an organic film on the titanium nitride inorganic film and thermally curing at 400 占 폚.

The hardness was measured using a Nanoindentor (Hysitron TI750 Ubi) for a sample having a thickness of 5,000 to 10,000 ANGSTROM prepared by applying the organic film forming composition and thermally curing at 400 DEG C for 120 seconds. The tip of the Nanoindentor was loaded into the specimen for 5 seconds, held for 2 seconds, held and then unloaded for 5 seconds, and the hardness was 0.9 GPa. The carbon content of the same specimen was measured using an elemental analyzer (EA1112, Thermo). Specifically, the precise amount of the sample was burned under the coexistence of O ₂ to measure the carbon content, and the carbon content was 71 atom%. Film densities were measured on the same specimens using an XRR (X-RAY REFLECTIVITY) device (X'Pert PRO, PANalytical). Specifically, a diffraction pattern obtained by irradiating X-rays was compared with a known diffraction pattern, and the film density was 1.4 g / cm ³ . The acid value of the same specimen was measured and the acid value was 0 mgKOH / g.

Examples 1 to 4 and Comparative Examples 1 to 5

A CMP slurry composition containing the components (% by weight based on the total composition) and residual amounts of ultrapure water in the following Table 1 was prepared, and the patterned wafer on which the titanium nitride film and the organic film were formed was polished under the following polishing conditions.

(1) CMP slurry composition Specification of each component

① Ceria:

Colloidal ceria (SOLVAY) having an average particle diameter of 60 nm was used.

② Cerium-containing ceria activator:

Cerium nitrate (Samcheon Chemical) was used.

③ Inorganic membrane surface protection agent

Polyethylene Glycol (PEG): Polyethylene glycol having a weight average molecular weight of 200 g / mol, 1,000 g / mol, or 10,000 g / mol (Sanken Chemical Co., Ltd.) was used.

Polyurethane (PU): Polyurethane (Sigma Aldrich) having a weight average molecular weight of 2,000 g / mol was used.

④ pH regulator: Nitric acid of the pharmacopoeia of Samseongjeon was used.

⑤ Silica:

Silica having an average particle diameter of 60 nm was used.

(2) Measurement of polishing conditions, polishing rate and selection ratio

As the polishing pad, a H800 CMP pad of FUJIBO Corporation was used. Polishing was performed for 1 minute using a 200 mm MIRRA instrument from Applied Materials (AMAT) at a down pressure of 1.0 psi, a slurry flow rate of 200 mL / min, a platen speed of 100 rpm and a head speed of 90 rpm The amount of back-grinding was measured and is shown in Table 1 below. The thickness (unit: Å) of the abrasive film was measured using a thin film thickness meter (ST4000, K-MAC) for the abrasive surface after performing the polishing as described above. The abrasion amount (unit: Å / min) . The selectivity was calculated by the following equation 1 on the basis of the measured abrasive amount:

<Formula 1>

Polishing selection ratio = A / B

(In the above formula 1, A represents an organic film polishing amount per unit time (unit: A / min) of the slurry composition,

B is an inorganic film polishing amount per unit time (unit: A / min) of the slurry composition.

		Example				Comparative Example
		One	2	3	4	One	2	3	4	5
Ceria (wt%)		0.1	0.1	0.1	0.1	0.5	0.1	0.05	0.05	-
Cerium nitrate (wt%)		0.1	0.1	0.1	0.1	0.4	0.1	0.1	0.4	0.1
PEG (% by weight)	200 g / mol	0.1	-	-	-	-	-	-	-	0.1
	1,000 g / mol	-	0.1	-	-	-	-	-	-	-
	10,000 g / mol	-	-	0.1	-	-	-	-	-	-
PU (polyurethane) (% by weight)		-	-	-	0.1	-	-	-	-	-
Silica (% by weight)		-	-	-	-	-	-	-	-	0.1
pH		3.0	3.0	3.0	3.1	2.9	3.0	3.1	3.1	3.0
The organic film polishing amount per unit time (Å / minute)		4320	4270	4250	4560	4530	4380	4210	4070	360
Unit time per unit polishing amount (Å / minute)		12	11	10	11	65	52	45	48	57
The abrasive selectivity ratio of Equation 1		360	388	425	414	70	84	94	85	6

As shown in Table 1, in Examples 1 to 4 including the slurry composition of the present invention, the polishing amount per unit time for the organic film was high, while the polishing amount per unit time for the inorganic film was low, Is high.

On the other hand, in the case of Comparative Examples 1 to 4, it is confirmed that the polishing rate per unit time for the organic film is low, or the polishing rate per unit time for the inorganic film is relatively high, so that the selectivity ratio between the inorganic film and the organic film is low. In addition, in Comparative Example 5 in which silica was used without using ceria, it was confirmed that the polishing amount for the organic film was remarkably low.

It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.

Claims (16)

1. An organic film CMP slurry composition comprising ceria, a cerium containing ceria activator, and an inorganic film surface protective agent.
2. The organic film CMP slurry composition of claim 1, wherein the ceria has an average particle size of from about 10 nm to about 150 nm.
3. The organic film CMP slurry composition of claim 1, wherein the ceria is present in an amount ranging from about 0.01% to about 10% by weight of the composition.
4. The organic film CMP slurry composition according to claim 1, wherein the cerium containing ceria activator comprises at least one of cerium nitrate, hydrate of cerium nitrate, cerium chloride, and cerium sulfate.
5. The organic film CMP slurry composition of claim 1, wherein the cerium containing ceria activator comprises from about 0.01% to about 5% by weight of the composition.
6. The organic film CMP slurry composition according to claim 1, wherein the inorganic film surface protective agent has a weight average molecular weight of from about 200 g / mol to about 10,000 g / mol, and polyethylene glycol or polyurethane.
7. The organic film CMP slurry composition of claim 1, wherein the inorganic film surface protective agent is included in the composition in an amount of about 0.01 wt% to about 5 wt%.
8. The organic film CMP slurry composition of claim 1, wherein the composition has a pH of from about 3 to about 5.
9. The organic film CMP slurry composition of claim 1, wherein the composition further comprises an oxidizing agent.
10. 10. The method of claim 9, wherein the oxidant is selected from the group consisting of metal salts comprising at least one of a seric ammonium salt, a ferric halogen salt, a ferric nitrate salt, or a transition metal chelate compound comprising at least one of an Fe- Membrane CMP slurry composition.
11. The organic film CMP slurry composition according to claim 1, wherein the organic film has a carbon content of about 70 atom% or more.
12. The organic film according to claim 1, wherein the organic film has a film density of about 0.5 g / cm ³ to about 3.0 g / cm ³ , Wherein the hardness of the organic film CMP slurry composition is about 0.3 GPa or more.
13. The organic film according to claim 1, wherein the organic film has a film density of about 0.5 g / cm ³ to about 2.5 g / cm ³ , Wherein the hardness of the organic film CMP slurry composition is from about 0.4 GPa to about 2 GPa.
14. The organic film CMP slurry composition according to claim 1, wherein the inorganic film is a titanium nitride film.
15. The organic film CMP slurry composition according to claim 1, wherein the organic film CMP slurry composition has a polishing selectivity of about 150 or more according to the following formula 1:

    <Formula 1>

    Polishing selection ratio = A / B

    (In the above formula 1, A represents an organic film polishing amount per unit time (unit: A / min) of the slurry composition,

    B is an inorganic film polishing amount per unit time (unit: A / min) of the slurry composition.
16. A method for polishing an organic film, comprising the step of polishing an organic film using the organic film CMP slurry composition according to any one of claims 1 to 15.

Images