TWI619849B - Rinse solution for silica thin film, silica thin film and method of producing the same - Google Patents

Abstract

The present invention relates to a rinsing solution for a cerium oxide film, a cerium oxide film, and a method for producing the same. The rinsing solution for the cerium oxide film comprises: trimethylbenzene, diethylbenzene, indane, fluorene, tert-butyltoluene, methylnaphthalene, and an aromatic hydrocarbon having 12 or more carbons. A mixture, a mixture comprising an aliphatic hydrocarbon having 12 or more carbons, a mixture comprising a heterohydrocarbon compound containing a phenyl group and an oxygen atom, or a combination thereof. The rinsing solution for the cerium oxide film of the present invention can completely peel off the interface region of the cerium oxide film.

Description

Flushing solution for ruthenium dioxide film and production method thereof

This application claims the priority and rights of Korean Patent Application No. 10-2014-0181864 filed on December 16, 2014 in the Korea Intellectual Property Office and filed with the Korea Intellectual Property Office on June 4, 2015. The priority and the rights of the Korean Patent Application No. 10-2015-0079441, the entire contents of which are hereby incorporated by reference.

The present invention relates to a rinsing solution for a cerium oxide film, a method of forming a cerium oxide film, and a cerium oxide film.

Cerium dioxide is used as a material for coating on a substrate having a concave-convex surface, and after heating, gaps are filled in the grooves on the substrate and thereby planarize the surface. The ceria film formed from such a ceria material is widely used as an interlayer insulating layer, a planarization layer, a passivation film, and an insulating interlayer of a device such as a semiconductor device (for example, an LSI, a TFT liquid crystal display, or the like). Wait. Specifically, a ceria film is used as an insulating layer for STI, ILD, IMD layers, and the like. A shallow trench isolation (STI) layer is used to properly separate devices such as transistors in an integrated circuit (IC), and the trench is filled with an insulating material after forming a trench on the semiconductor substrate. To form. This filled trench adjusts the size and settings of the active region. In addition, the ruthenium dioxide film includes an interlayer insulating layer formed in the ILD and IMD regions. To form these STI, ILD, and IMD insulating layers, the hafnium oxide film can be formed by filling the gaps and layers in the integrated circuit (IC) with a composition of the hafnium coating. When a hafnium oxide film is formed in a semiconductor device or the like, a hafnium oxide film is usually formed by the following method. Rotating a hydrogenated polyoxazane solution on a substrate, wherein a semiconductor, a wire, an electrode, and the like are formed on the substrate as necessary, and it has a step difference or no step, and heats the coated Substrate to remove solvent, and then baked at a temperature greater than or equal to a specific temperature to convert the hydrogenated polyoxazane to a ruthenium dioxide film, and use the ruthenium dioxide film as an interlayer insulating layer, a planarization layer, a passivation film , device insulation interlayer, etc. In general, a ruthenium (Si)-containing solution is coated on a substrate by a spin coating or a slit coating method to form a ruthenium dioxide film, and in this case, beads may be formed around the substrate, or may be included The ruthenium solution is applied to the back side of the substrate. Therefore, a rinsing solution can be used to peel off the cerium oxide coated in the unintentional region, but there is a possibility that the cerium oxide at the interface is not completely removed or a small amount of cerium oxide is left around the stripped region. problem. A solution to this problem has been proposed (Korean Patent Publication No. 2004-0068989), but the step between the region in which the cerium oxide is peeled off and the other region in which the cerium oxide is not peeled off still needs to be improved.

One embodiment provides a rinsing solution for a ruthenium dioxide film that is capable of completely stripping the interface region of the ruthenium dioxide film.

Another embodiment provides a method of producing a ruthenium dioxide film using the rinsing solution for a ruthenium dioxide film.

Yet another embodiment provides a cerium oxide film produced using the rinsing solution for a cerium oxide film.

According to one embodiment, the rinsing solution for the cerium oxide film comprises trimethylbenzene, diethylbenzene, indane, indene, methylanisole, tert-butyl Tert-butyl toluene, a mixture containing aromatic hydrocarbons having 12 or more carbons, a mixture containing aliphatic hydrocarbons having 12 or more carbons, containing impurities containing phenyl and oxygen atoms a mixture of hydrocarbon compounds, or a combination thereof.

The cerium oxide film may include hydrogenated polysilazane, hydrogenated polysiloxazane, or a combination thereof.

The rinsing solution for the cerium oxide film may comprise a mixture comprising a C12 to C30 aromatic hydrocarbon, a mixture comprising a C12 to C30 aliphatic hydrocarbon, or a combination thereof.

The mixture including the heterohydrocarbon compound may include greater than or equal to about 10% by weight and less than or equal to about 70% by weight of a heterohydrocarbon compound including a phenyl group and an oxygen atom.

The structure of the hetero hydrocarbon compound containing a phenyl group and an oxygen atom may include an ether, an aldehyde, an alcohol, a ketone, or a combination thereof.

The hetero hydrocarbon compound containing a phenyl group and an oxygen atom may comprise methyl anisole, Diphenyl ether, butyl benzoate, butyl phenyl ether, allyl methyl phenol, isobutyl phenyl propionaldehyde, phenylcyclohexanone, or a combination thereof.

According to another embodiment, a method of producing a ruthenium dioxide film includes: coating a ruthenium-containing solution on a substrate; and locally spraying the ruthenium dioxide film on the substrate coated with the ruthenium-containing solution Rinse the solution.

According to still another embodiment, a ruthenium dioxide film produced using the rinsing solution for a ruthenium dioxide film is provided.

The ruthenium dioxide film may have a step (ΔT) of less than or equal to about 400 nm measured according to the following calculation formula 1.

[Calculation Formula 1] Step difference (ΔT) = (maximum thickness of the ceria film measured between one end of the ceria film and a point at 10 mm therefrom) - (at a distance from the ceria The thickness of the cerium oxide film measured at a point of 10 mm at the end of the film).

The rinsing solution for the cerium oxide film can completely peel off the interface region of the cerium oxide film by reducing the moisture and impurities contained in the rinsing solution without affecting the film characteristics.

ΔT‧‧‧ step

Figure 1 shows a method for evaluating the peeling characteristics of a rinsing solution for a cerium oxide film.

Embodiments of the invention are described in detail below. However, these embodiments are examples The invention is not limited by the scope of the invention, and the invention is defined by the scope of the appended claims.

As used herein, when a definition is not otherwise provided, the term "substituted" means selected from a halogen atom (F, Cl, Br or I), a hydroxyl group, a nitro group, a cyano group, an imino group (=NH, =NR). , R is a C1 to C10 alkyl group, an amino group (-NH ₂ , -NH(R'), -N(R")(R"'), wherein R' to R"' are independently a C1 to C10 alkyl group , fluorenyl, hydrazine or fluorenyl, carboxy, C1 to C10 alkyl, C6 to C20 aryl, C3 to C20 cycloalkyl, C1 to C10 heteroalkyl, C3 to 20 heteroaryl and C2 to C20 heterocycle At least one substituent in the alkyl group is substituted in place of one hydrogen atom in the functional group, selected from =O, =S, =NR (R is a C1 to C10 alkyl group), =PR (R is a C1 to C10 alkyl group) And at least one substituent of =SiRR' (R and R' are independently a C1 to C10 alkyl group) substituted in place of two hydrogen atoms in the functional group, or selected from the group consisting of ≡N, ≡P and ≡SiR ( R is substituted with at least one substituent in the C1 to C10 alkyl group to replace three hydrogen atoms in the functional group.

As used herein, when an element such as a layer, a film, a region or a substrate is referred to as being "on" another element, it may be directly on the other element or the intermediate element may be present.

A rinsing solution for a cerium oxide film according to one embodiment is described below.

A rinsing solution for a cerium oxide film according to an embodiment comprises trimethylbenzene, diethylbenzene, indane, hydrazine, tert-butyltoluene, methylnaphthalene, and has 12 or 12 A mixture of the above aromatic hydrocarbons of carbon, a mixture comprising aliphatic hydrocarbons having 12 or more carbons, and a mixture comprising a heterohydrocarbon compound containing a phenyl group and an oxygen atom, or a combination thereof.

The compound may have a substituted or unsubstituted structure.

Here, the term "mixture" refers to a combination of two or more than two compounds, and the two or more than two compounds may be the same or different.

The ceria film may comprise a hydrogenated polyazane, a hydrogenated polyoxazane, or a combination thereof, for example, by coating a solution containing perhydropolyazane on a substrate and curing it.

However, it is necessary to peel off the locally and unnecessarily formed ceria film from the substrate during the formation of the ceria film, and here, the rinsing solution has satisfactory dissolution and trimming of the ceria film (edge- The nature of the cutting, and thus the step between the one region where the ceria film is peeled off and the other region where the ceria film is not peeled off, is sharply reduced when applied to the ceria film.

A mixture comprising an aromatic hydrocarbon having 12 or more carbons may, for example, comprise a C12 to C30 aromatic hydrocarbon, and a mixture comprising an aliphatic hydrocarbon having 12 or more carbons may include a C12 to C30 aliphatic hydrocarbon, but not Limited to this.

The mixture including the heterohydrocarbon compound may include greater than or equal to about 10% by weight and less than or equal to about 70% by weight of a heterohydrocarbon compound including a phenyl group and an oxygen atom.

The heterohydrocarbon compound containing a phenyl group and an oxygen atom may have a structure including a phenyl group and an oxygen-containing moiety such as an ether, an aldehyde, an alcohol, a ketone, or a combination thereof.

For example, a heterohydrocarbon compound containing a phenyl group and an oxygen atom may include methyl anisole, diphenyl ether, butyl benzoate, butyl phenyl ether, allyl methyl phenol, isobutyl phenyl. Propionaldehyde, phenylcyclohexanone, or a combination thereof, but is not limited thereto.

In the rinsing solution for the cerium oxide film, based on the total amount of the rinsing solution mixture, it may be greater than or equal to about 10% by weight and less than or equal to about 70% by weight. The amount includes a heterohydrocarbon compound containing a phenyl group and an oxygen atom. In this case, the step characteristics of the ruthenium dioxide film can be improved.

According to one embodiment, the rinsing solution for the cerium oxide film is gelled at a slow rate, and thus exhibits satisfactory storage stability and minimizes the influence on the film characteristics, and thoroughly strips the cerium oxide. The interface of the film.

The rinsing solution for the cerium oxide film may have a moisture content of, for example, less than or equal to about 150 ppm, and particularly less than or equal to about 100 ppm.

According to another embodiment, a method of producing a ruthenium dioxide film includes: preparing a substrate; coating a ruthenium-containing solution on the substrate; and locally spraying the ruthenium dioxide film on the substrate coated with the ruthenium-containing solution Flushing solution.

The material of the substrate is not particularly limited, and may be, for example, a germanium wafer. In addition, the substrate is not particularly limited in shape, and may have a shape such as a plate, a film, or the like, and various surfaces such as a flat surface, a concave-convex surface, or a curved surface without being particularly limited.

The cerium-containing solution may comprise a cerium-containing compound such as a hydrogenated polyazane, a hydrogenated polyoxazane, or a combination thereof, and a solvent. The nature of the cerium-containing compound is not particularly limited, and may have, for example, a weight average molecular weight of from about 1,000 to about 200,000, an oxygen content of from about 0.2% by weight to about 3% by weight, and a ratio of SiH ₃ groups to total SiH groups of 15 moles. % to 35 mol% and a chlorine content of less than or equal to about 1 ppm.

The cerium-containing solution can be applied by any well-known method, such as spin coating, spray coating, flow coating, roller coating, dip coating, wiping. , sponge wiping, etc., but the invention is not limited thereto.

The substrate coated with the ruthenium-containing solution may be rotated at a speed of about 500 rpm to 4,000 rpm, in the region where the component to be removed the rinsing solution is present (for example, the substrate The edges and the back side are sprayed with a rinsing solution for the cerium oxide film.

According to one embodiment, a ruthenium dioxide film produced using the rinsing solution for a ruthenium dioxide film is provided. The ceria film can be used for an insulating layer, a planarization layer, a passivation layer, and a device insulating interlayer of a semiconductor device, a display device, or the like.

The ceria film has excellent peeling characteristics at its interface, and may have a step (ΔT) of less than or equal to about 400 nm measured, for example, according to the following calculation formula 1.

[Calculation Formula 1] Step difference (ΔT) = (maximum thickness of the ceria film measured between one end of the ceria film and a point at 10 mm therefrom) - (at a distance from the ceria The thickness of the ruthenium dioxide film was measured at a point at 10 mm from one end of the film).

The invention will be explained in more detail below with reference to examples. However, these examples are merely exemplary, and the invention is not limited thereto.

Synthesis example: synthesis of ruthenium containing compounds

The internal atmosphere of the reactor equipped with a 2 L stirrer and a temperature controller was replaced with dry nitrogen. 1,500 g of dry pyridine was placed in the reactor, and then the reactor was warmed at 20 °C. Then, 100 g of dichlorosilane was slowly injected thereto over one hour. Next, 70 g of ammonia was slowly injected thereto over 3 hours while stirring the reactor. Subsequently, dry nitrogen gas was injected thereto over 30 minutes, and the remaining ammonia in the reactor was removed. The obtained white-slurry-phased product was filtered through a 1 μm Teflon filter under a dry nitrogen atmosphere to obtain 1,000 g of a filtered solution. Subsequently, 1,000 g of dry xylene was added thereto, and the concentration of the mixture was adjusted to 20 wt% by substituting the solvent of the mixture from pyridine to xylene using a rotary evaporator, and Teflon was passed through a pore size of 0.03 μm. The filter was filtered to concentrate the product. The perhydropolyazane obtained had an oxygen content of 3.8%, SiH ₃ /SiH (total) of 0.22, a weight average molecular weight of 4,000, and a chlorine content of 0.9 ppm.

Examples 1 to 11 and Comparative Example 1 to Comparative Example 4: a rinsing solution for a cerium oxide film

A rinsing solution for a cerium oxide film having the composition in Table 1 below was prepared.

Assessment 1: Evaluation of residual film and step characteristics

A hydrazine-containing solution (20% by weight) was prepared by mixing a compound according to the synthesis example with a di-n-butylether solvent. A 3 cc cerium-containing solution was placed in a spin coater and coated at a center of a bare enamel wafer having an 8 inch diameter at a rotational speed of 1500 rpm for 20 seconds to form a film of about 500 nm thick. Next, each of the rinsing solutions for the cerium oxide film according to Examples 1 to 11 and Comparative Example 1 to Comparative Example 4 was sprayed at a flow rate of 10 ml/min from an upper position of about 3 mm from the outer circumference of the wafer for 5 seconds. bell. Subsequently, the coated wafer was heated on a hot plate at 150 ° C and dried for 3 minutes.

The peeling characteristics of the ceria film obtained by the above process were evaluated.

1 is a view showing a state of a ruthenium dioxide film after spraying a rinsing solution on a ruthenium dioxide film on a ruthenium wafer, and an evaluation of the delamination of the rinsing solution for a ruthenium dioxide film will be described with reference to FIG. The method of the feature.

Referring to Fig. 1, the end of the ceria film becomes convex and produces a step (ΔT), and the portion for peeling off (i.e., a film 3 mm from the outer circumferential area of the wafer) is removed to check whether there is a residual film.

Use XE300 (PARK Systems) and SEM S- 4800 (Type-2), Hitachi Ltd.) as a spectral reflection film thickness gauge and scanned from the outer circumferential area of the wafer to approximately 10 mm to measure the step (ΔT) (around ΔT) SEM) was used, and an optical microscope LV100D (Nikon Inc.) and a spectral reflection film thickness gauge ST-4000 (K-MAC) were used to check whether or not film residue was present in the portion for peeling.

Assessment 2: Gelation days

2.3 g of a ruthenium-containing solution and 23 g of each of the rinsing solutions for the cerium oxide film according to Examples 1 to 11 and Comparative Example 1 to Comparative Example 4 used in Evaluation 1 were placed in a 100 g glass bottle. They were mixed, and then allowed to stand at 22 ° C, 50% relative humidity (RH) with the cap open, and the number of days from which the mixture began to gel by the naked eye.

The results of Evaluation 1 to Evaluation 2 are provided in Table 1 below.

* D110 (Dongsung Highchem Co., Ltd.): a mixture containing greater than or equal to C12 aliphatic compound

* ISOLEC (S-oil Corp.): a mixture containing greater than or equal to C12 aromatic compounds

* K600ND (SKC Inc.): (i) a mixture of greater than or equal to the C11 aromatic compound and (ii) a compound containing a phenyl group and an ether/aldehyde. K600ND comprises greater than or equal to about 10% by weight and less than or equal to about 70% by weight of a compound comprising a phenyl group and an ether/aldehyde.

Referring to Table 1, an example of using a rinsing solution according to an embodiment of the present invention showed a reduced film step difference as compared with the comparative example, and when dicing in the outer circumferential region, there was no film residue. In addition, an example of using a rinsing solution according to an embodiment of the present invention shows excellent storage stability.

Although the present invention has been described in connection with the exemplary embodiments of the present invention, it is understood that the invention is not limited to the disclosed embodiments, but rather, the invention is intended to cover the spirit and scope of the appended claims Various modifications and equivalent configurations included.

Claims (5)

A rinsing solution for a cerium oxide film, comprising: indane, cerium, tert-butyltoluene, a mixture comprising an aliphatic hydrocarbon having 12 or more carbons, and a heterohydrocarbon compound containing a phenyl group and an oxygen atom Mixture, or a combination thereof, wherein the heterohydrocarbon compound containing a phenyl group and an oxygen atom comprises methyl anisole, diphenyl ether, butyl phenyl ether, allyl methyl phenol, isobutyl phenyl Propionaldehyde, phenylcyclohexanone or a combination thereof. The rinsing solution for a cerium oxide film according to claim 1, wherein the cerium oxide film comprises hydrogenated polyazane, hydrogenated polyoxazane or a combination thereof. The rinsing solution for a cerium oxide film according to claim 1, wherein the rinsing solution for the cerium oxide film comprises a mixture containing a C12 to C30 aromatic hydrocarbon, and a mixture containing a C12 to C30 aliphatic hydrocarbon. Or a combination thereof. A rinsing solution for a cerium oxide film according to claim 1, wherein the mixture comprising a heterohydrocarbon compound comprises greater than or equal to 10% by weight and less than or equal to 70% by weight of a phenyl group and an oxygen atom. Said heterohydrocarbon compound. A method for producing a ruthenium dioxide film, comprising: preparing a substrate; coating a ruthenium-containing solution on the substrate; and locally spraying the substrate coated with the ruthenium-containing solution as claimed in the first to A rinsing solution for a cerium oxide film according to any one of the items 4.