KR20150010570A - CMP composition for polishing an organic layer and method of forming a semiconductor device using the composition - Google Patents

Abstract

Provided in the present invention are a CMP slurry composition for polishing an organic layer and a method for manufacturing a semiconductor device using the same. The CMP slurry composition includes a 0.001-5 wt% of oxide polished particles; 0.1-5 wt% of an oxidation agent; 0-5 wt% of a polish controlling agent; 0-3 wt% of a surfactant; 0-3 wt% of a pH controlling agent; and 79-99.889 wt% of deionized water. The CMP slurry composition can polish an organic layer that does not include silicone in an excellent selecting ratio of 6:1 or more for an oxidized layer.

Description

TECHNICAL FIELD The present invention relates to a CMP slurry composition for polishing an organic film and a method for manufacturing a semiconductor device using the same,

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

As the semiconductor device is highly integrated, formation of a finer pattern and a circuit of a multilayer structure are required. For this purpose, films of various materials with different etch selectivity characteristics are required. Among these various materials, the hydrocarbon-based organic film has good etch selectivity characteristics with respect to other silicon-containing films and can be used as a mask film or a sacrificial film. It is required to perform a chemical mechanical polishing process on an organic film in a semiconductor manufacturing process. However, a CMP slurry composition that can be used to effectively chemically and mechanically polish an organic film has not yet been developed.

Accordingly, an object of the present invention is to provide a CMP slurry composition capable of effectively polishing an organic film.

Another object of the present invention is to provide a semiconductor manufacturing process using the composition.

In order to achieve the above object, the CMP slurry composition according to the present invention is used for polishing an organic film containing no silicon. The CMP slurry composition contains 0.001 to 5% by weight of oxide abrasive grains; 0.1 to 5% by weight of an oxidizing agent; 0 to 5% by weight of an abrasive modifier; 0 to 3% by weight of surfactant; 0 to 3% by weight of a pH adjusting agent; And 79 to 99.889% by weight of deionized water.

The abrasive particles may be at least one selected from the group consisting of silica (SiO ₂ ), ceria (CeO ₂ ) and alumina (Al ₂ O ₃ ).

The particle size of the abrasive particles may be 30 to 120 nm.

The oxidizing agent may be at least one selected from the group consisting of hydrogen peroxide, superoxide, dioxygenyl, ozone, ozone, peroxide, fluorine, chlorine, Chlorite, Chlorate, Perchlorate, Halogen Compounds, Nitric acid, Nitrate, Hypochlorite, Hypohalite, Chromium Trioxide (Chlorite), Chlorate, Perchlorate, Chromium trioxide, Pyridinium chlorochromate, Chromate, Dichromate, Chromium Compound, Potassium permanganate, Permanganate, Sodium perborate Sodium perborate, nitrous oxide, 2,2'-dipyridisulfide, lead dioxide (PbO ₂ ), manganese dioxide (MnO ₂ ), copper oxide (CuO), ferric chloride ₃ ), perchloric acid (HClO ₄ ), iron nitrate (Fe (NO) ₃ ), sulfate sodium sulfate and potassium persulfate (K ₂ S ₂ O ₈ ).

The polishing regulator may be selected from the group consisting of organic acid, inorganic acid, nitric acid, nitrate, sulfuric acid, peroxydisulfuric acid, peroxymonosulfuric acid, It is preferable to use one or more of sulfonic acid, acetic acid, citric acid, formic acid, gluconic acid, lactic acid, oxalic acid, tartaric acid, It is also possible to use carboxylic acid, chloric acid, chlorous acid, hypochlorous acid, perchloric acid, halogenooxoacid, ascorbic acid, At least one selected from the group consisting of carboxylic acid (Vinylogous carboxylic acid), amino acid, histidine, glycine, arginine, hydrochloric acid, hydrofluoric acid and phosphoric acid.

The surfactant may be anionic or nonionic. Specifically, the surfactant may be selected from the group consisting of lauryl myristyl alcohol series, methyl-oxirane polymer series having a hydrophile lipophile balance (HLB) value of 12 or more, ethylenediamine, And selected from the ethoxylated and propoxylated alcohol series, 2-methyloxirane, oxirane series, polyethylene glycol, or polysorbate series. At least one.

The surfactant may be selected from the group consisting of benzalkonium chloride, Alkyl Benzene Sulfonate, Phemerol chloride, ammonium lauryl sulfate, sodium lauryl ether sulfate sodium lauryl ether sulfate, sodium myreth sulfate, dioctyl sodium sulfosuccinate, perfluorooctanesulfonate, perfluorobutanesulfonate, linear alkylsulfosuccinate, But are not limited to, linear alkylbenzene sulfonate, sodium stearate, sodium lauroyl sarcosinate, cetyl trimethylammonium bromide, cetyl trimethylammonium chloride, ), Perfluorononanoate, perfluorononanoic acid, Perfluorooctanoate, octenidine dihydrochloride, 5-bromo-5-nitro-1,3-dioxane, 5-bromo- , Dimethyldioctadecylammonium chloride, Cetrimonium bromide, dioctadecyldimethylammonium bromide, octaethylene glycol monododecyl ether, glycerol, At least one selected from glyceryl laurate, or polyethoxylated tallow amine.

The pH adjusting agent may be at least one acid selected from the group consisting of polyacrylic acid, carboxylic acid, nitric acid, sulfuric acid and sulfonic acid, or may be an acid selected from the group consisting of potassium hydroxide, sodium hydroxide, aqueous ammonia, tetramethylammonium At least one base selected from the group consisting of Tetramethylammonium hydroxide, Tetraethylammonium hydroxide and Tetrabutylammonium hydroxide may be used.

The composition may preferably have a pH of 2.0 to 5.0.

According to another aspect of the present invention, there is provided a method of manufacturing a semiconductor device, including: forming a first structure including a first recessed region on a substrate; Forming an organic film not containing silicon on the first structure to fill the first recess region; And exposing a top surface of the first structure to a CMP process using the CMP slurry composition of claim 1 for the organic layer.

In one example, the first recess region may be a first hole that exposes the substrate, the method further comprising: after performing a CMP process on the organic film, Forming a second structure including a second hole exposing the second structure; Removing the organic film through the second hole; Forming active pillars covering at least sidewalls of the first holes and the second holes; And forming a conductive line in a portion of the first structure and the second structure.

The first structure and the second structure may have a structure in which a plurality of layers of insulating films and sacrificial layers are alternately stacked, and the forming of the conductive lines in the first structure and the second structure may include: Selectively removing the sacrificial layers; And forming the conductive line in an area where the sacrificial films are removed.

In another example, the structure may include a film to be etched disposed on the substrate, first mask patterns disposed on the etch target film in the form of a plurality of parallel lines, A second mask layer that conformally covers a surface of the first structure, and exposing the top surface of the first structure may expose an upper surface of the second mask layer.

Specifically, the gap between the first mask patterns may be about three times the thickness of the second mask film, and the organic film may be disposed between the first mask patterns.

The method may further include a step of performing an anisotropic etching process to remove the exposed second mask film and form a second mask pattern under the organic film.

An oxide film is disposed on the top of the first structure, and the CMP slurry composition can polish the organic film with a selectivity of 6: 1 or more with respect to the oxide film.

The CMP slurry composition according to an example of the present invention can polish an organic film that does not contain silicon with a good selectivity ratio of 6: 1 or more to the oxide film. Further, when the polishing process is performed using the CMP slurry composition, the etching selectivity of the organic film to the oxide film can be variously varied from about 6: 1 to about 430: 1. A CMP composition can be applied by selecting an appropriate composition according to the structure of a semiconductor device to be manufactured. In addition, the CMP slurry composition does not cause peeling or delamination of the structure. Thereby, the semiconductor device can be manufactured without defects.

FIGS. 1, 2A and 2B are cross-sectional views illustrating a process of manufacturing a semiconductor device according to an embodiment of the present invention.
3 to 10 are cross-sectional views illustrating a process of fabricating a semiconductor device according to an embodiment of the present invention.
11 to 17 are cross-sectional views illustrating a process of manufacturing a semiconductor device according to another example of the present invention.
18 is a schematic block diagram illustrating an example of a memory system including a semiconductor device manufactured in accordance with embodiments of the present invention.
19 is a schematic block diagram showing an example of a memory card having a semiconductor device manufactured according to the embodiments of the present invention.
20 is a schematic block diagram showing an example of an information processing system for mounting a semiconductor device manufactured according to the embodiments of the present invention.

BRIEF DESCRIPTION OF THE DRAWINGS The advantages and features of the present invention, and how to accomplish them, will become apparent by reference to the embodiments described in detail below with reference to the accompanying drawings. The present invention may, however, be embodied in many different forms and should not be construed as being limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the concept of the invention to those skilled in the art. Is provided to fully convey the scope of the invention to those skilled in the art, and the invention is only defined by the scope of the claims. Like reference numerals refer to like elements throughout the specification.

The terminology used herein is for the purpose of illustrating embodiments and is not intended to be limiting of the present invention. In the present specification, the singular form includes plural forms unless otherwise specified in the specification. As used herein, the terms 'comprises' and / or 'comprising' mean that the stated element, step, operation and / or element does not imply the presence of one or more other elements, steps, operations and / Or additions. Also, in this specification, when it is mentioned that a film is on another film or substrate, it means that it may be formed directly on another film or substrate, or a third film may be interposed therebetween.

In addition, the embodiments described herein will be described with reference to cross-sectional views and / or plan views, which are ideal illustrations of the present invention. In the drawings, the thicknesses of the films and regions are exaggerated for an effective description of the technical content. Thus, the shape of the illustrations may be modified by manufacturing techniques and / or tolerances. Accordingly, the embodiments of the present invention are not limited to the specific forms shown, but also include changes in the shapes that are generated according to the manufacturing process. For example, the etched area shown at right angles may be rounded or may have a shape with a certain curvature. Thus, the regions illustrated in the figures have schematic attributes, and the shapes of the regions illustrated in the figures are intended to illustrate specific types of regions of the elements and are not intended to limit the scope of the invention.

Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings. A nonvolatile memory device according to embodiments of the present invention has a structure of a three-dimensional semiconductor device of a three-dimensional structure.

FIGS. 1, 2A and 2B are cross-sectional views illustrating a process of manufacturing a semiconductor device according to an embodiment of the present invention.

Referring to FIG. 1, a structure 110 including a recessed region 115 is formed on a substrate 100. At least the upper portion of the structure 110 may be formed of an oxide. An organic layer 120 is formed on the structure 110. The organic layer 120 may also be referred to as a spin on carbon layer or a spin on hardmask layer. The organic film 120 is an organic film not containing silicon. The process of forming the organic layer 120 may include spin coating, drying, or baking. The organic film 120 is formed to fill the recessed region 115.

Referring to FIGS. 2A and 2B, a polishing process is performed to polish the organic film 120 to remove at least a portion of the organic film 120 on the structure 110. The polishing process may be CMP (chemical mechanical polishing). 2A, the organic film pattern 120a having a predetermined thickness is formed on the structure 110 or the polishing process is continued to expose the upper surface of the structure 110 as shown in FIG. 2B, The organic film pattern 120b may remain in the organic layer 115. [ The CMP slurry composition used in the CMP process may contain 0.001 to 5% by weight of oxide abrasive grains; 0.1 to 5% by weight of an oxidizing agent; 0 to 5% by weight of an abrasive modifier; 0 to 3% by weight of surfactant; 0 to 3% by weight of a pH adjusting agent; And 79 to 99.889% by weight of deionized water.

The abrasive particles may be at least one selected from the group consisting of silica (SiO ₂ ), ceria (CeO ₂ ) and alumina (Al ₂ O ₃ ). The particle size of the abrasive grains may be 10 to 100 nm, preferably 30 to 120 nm.

The oxidizing agent induces oxidation of the organic film to secure a polishing rate. The oxidizing agent may be selected from the group consisting of peroxide such as hydrogen peroxide, superoxide, dioxygenyl, ozone and ozone, fluorine or chlorine, Halogen series, Halogen Compounds series such as Chlorite, Chlorate and Perchlorate, Nitrate series including Nitric acid, Hypo including household cleaner, Chromium compounds such as Hypochlorite series, Hypohalite series, Chromium trioxide, Pyridinium chlorochromate, Chromate, and Dichromate. ) based, gold, such as potassium permanganate (potassium permanganate) permanganate (permanganate) series, lead dioxide (PbO _2), manganese dioxide (MnO _2), cuprous oxide (CuO) and ferric chloride (FeCl _3), such as A high oxidation state compound, a thio sulfate Potassium _{(Potassium persulfate, K 2 S 2} O 8) , such as sulfates (sulfate), perchloric acid (perchloric acid, HClO _4), iron nitrate (Fe (NO) _3), sodium perborate (Sodium perborate, nitrous oxide, and 2,2'-dipyridisulfide. The term " a " Of these oxidizing agents, chlorite and chlorate are most preferred.

The abrasive modifier may serve to break the carbon chain in the organic film. The polishing regulator may be an organic acid or an inorganic acid. Specifically, the polishing regulator may be selected from the group consisting of a nitrate series including nitric acid, a sulfonic acid series such as sulfuric acid, peroxydisulfuric acid and peroxymonosulfuric acid, Such as carboxylic acids such as acetic acid, citric acid, formic acid, gluconic acid, lactic acid, oxalic acid, and tartaric acid, ) Series, halogenooxoacid series such as chloric acid, chlorous acid and hypochlorous acid and perchloric acid, and vinyl groups such as ascorbic acid, Amino acids such as histidine, glycine and arginine, and inorganic acids such as hydrochloric acid, hydrofluoric acid and phosphoric acid. The carboxylic acid series may be most preferred as the polishing regulator.

The surfactant may improve the wettability of the CMP slurry composition on the surface of the organic layer to improve the polishing rate. The surfactant may be anionic or nonionic. Specifically, the surfactant is selected from the group consisting of lauryl myristyl alcohol series, methyl-oxirane polymer series having a hydrophile lipophile balance (HLB) value of 12 or more, ethylenediamine, 16 ethoxylated and propoxylated alcohol series, 2-methyloxirane, oxirane series, polyethylene glycol, or polysorbate series. Lt; / RTI >

The surfactant may be selected from the group consisting of benzalkonium chloride, Alkyl Benzene Sulfonate, Phemerol chloride, ammonium lauryl sulfate, sodium lauryl ether sulfate sodium lauryl ether sulfate, sodium myreth sulfate, dioctyl sodium sulfosuccinate, perfluorooctanesulfonate, perfluorobutanesulfonate, linear alkylsulfosuccinate, But are not limited to, linear alkylbenzene sulfonate, sodium stearate, sodium lauroyl sarcosinate, cetyl trimethylammonium bromide, cetyl trimethylammonium chloride, ), Perfluorononanoate, perfluorononanoic acid, Perfluorooctanoate, octenidine dihydrochloride, 5-bromo-5-nitro-1,3-dioxane, 5-bromo- , Dimethyldioctadecylammonium chloride, Cetrimonium bromide, dioctadecyldimethylammonium bromide, octaethylene glycol monododecyl ether, glycerol, At least one selected from glyceryl laurate, or polyethoxylated tallow amine.

The pH adjusting agent functions to adjust the pH of the CMP slurry composition. Since it contains the polishing control system acid, it can act as a kind of pH controlling agent. The pH adjusting agent may be acidic or basic. Specifically, the pH adjusting agent may be an acid such as polyacrylic acid, carboxylic acid, nitric acid, sulfuric acid and sulfonic acid, or may be an acid such as potassium hydroxide, sodium hydroxide, aqueous ammonia, tetramethylammonium hydroxide ), Tetraethylammonium hydroxide, and tetrabutylammonium hydroxide. ≪ Desc / Clms Page number 7 >

The composition may preferably have a pH of 2.0 to 5.0.

The organic film can be effectively polished by using such a CMP slurry composition.

Experimental examples of the CMP slurry composition of the present invention will be described below.

EXPERIMENTAL EXAMPLE 1:

Eight wafers were prepared, an organic film not containing silicon was formed on each of the four wafers, and a TEOS (tetraethoxysilane) film was formed on each of the remaining four wafers. The oxidizing agent is changed to peroxide series, chlorate, nitrate series and high oxidizing compound respectively, wherein the oxidizing agent is changed to peroxide series, chlorate, nitrate series and high oxidizing compound, To 1 wt%, respectively, to prepare CMP slurry compositions. At this time, hydrogen peroxide was used as the peroxide-based oxidant. Perchloric acid (HClO ₄ ) was used as the chlorate-based oxidant. Iron nitrate (Fe (NO) ₃ ) was used as the nitrate-based oxidant. The high-oxidation compound refers to a high-oxidation compound of a metal such as lead dioxide (PbO ₂ ), manganese dioxide (MnO ₂ ), copper oxide (CuO), and iron chloride (FeCl ₃ ). In the Experimental Example 1, the oxidizing agent used as the high-oxidation compound was iron chloride (FeCl ₃ ). The average particle size of the silica was about 60 nm. The CMP slurry compositions were subjected to a CMP process on the two types of wafers, and the polishing rate and selectivity were examined and recorded in Table 1 below.

Oxidant type The polishing rate (Å / min) Organic film / TEOS selection ratio Organic film TEOS One Peroxide series 1250 115 10.9 2 Chlorate series 1530 95 16.1 3 Nitrate series 920 89 10.3 4 High-oxidation compound 870 112 7.8

In Table 1, the chlorate series exhibited the best polishing rate and selectivity. However, it is understood that other peroxide series or nitrate series exhibits a high selectivity ratio of 6: 1 or more, which is suitable as an oxidizing agent for organic film polishing of the present invention.

≪ Experimental Example 2: Abrasive Particles and Oxidant Content >

In Experimental Example 2, polishing characteristics according to the content of silica used as a chlorate-based oxidizer and abrasive grains showing the best characteristics in Experimental Example 1 will be examined. First, 34 wafers were prepared, an organic film not containing silicon was formed on each of 17 wafers, and a TEOS (tetraethoxysilane) film was formed on each of the remaining 17 wafers. Next, as shown in Table 2, the CMP process was performed on each of the wafers while varying the content of the chlorate-based oxidizer in the CMP slurry composition from 0.1 to 3.0 wt% and the content of the silica abrasive grains in the range of 0.01 to 1.0 wt% I looked at the characteristics. In Experimental Example 2, perchloric acid (HClO ₄ ) was used as a chlorate-based oxidant. The average particle size of the silica was about 60 nm.

Oxidant content (% by weight) Abrasive grain content (% by weight) The polishing rate (Å / min) Organic film / TEOS selection ratio Organic film TEOS One 1.2 0.4 1650 45 36.7 2 1.0 0.4 1620 40 40.5 3 0.7 0.4 1510 42 35.9 4 0.5 0.4 1400 40 35.0 5 1.0 0.7 1630 89 18.3 6 1.0 0.5 1620 62 26.1 7 1.0 0.3 1590 42 37.8 8 0.3 1.0 1158 121 9.6 9 0.2 1.0 941 124 7.6 10 0.1 1.0 804 129 6.2 11 3 0.01 1987 5 397.4 12 3 0.05 2100 6 350 13 3 0.1 2230 28 79.6 14 3 0.2 2480 48 51.7 15 3 0.5 2670 77 34.7 16 One 0.05 1505 8 188.1 17 One 0.1 1600 31 51.6

In Table 2, it can be seen that the selection ratio is the highest at 397.4 when the content of the chlorate-based oxidizer is 3% by weight and the concentration of the silica abrasive grains is 0.01% by weight. In addition, the selection ratio of the remaining contents is as high as 6 or more, which is suitable as the composition for polishing an organic film of the present invention.

<Experimental Example 3-1: Types of polishing modifiers>

In Experimental Example 3-1, the kind and content of the polishing agent were changed in the CMP slurry composition which retained the 1.0% by weight of chlorate-based oxidizer and 0.4% by weight of silica used as the abrasive grains, And to investigate the polishing characteristics. First, 18 wafers were prepared, an organic film not containing silicon was formed on each of nine wafers, and a plasma-enhanced tetraethoxysilane (PETEOS) film was formed on each of the remaining nine wafers. Next, as shown in Table 3, the carboxylic acid was changed to 0.1 to 1.0% by weight as a polishing regulator, or was changed to sulfonic acid, amino acid, inorganic acid, and nitric acid instead of carboxylic acid, and each wafer was subjected to a CMP process, . In Experimental Example 3-1, perchloric acid (HClO ₄ ) was used as the chlorate-based oxidant. Formic acid was used as the carboxylic acid. Histidine was used as the amino acid. Hydrochloric acid was used as the inorganic acid. The average particle size of the silica was about 60 nm.

Type of abrasive modifier Abrasive modifier content (% by weight) The polishing rate (Å / min) Organic film / PETEOS selection ratio Organic film PETEOS One Carboxylic acid 0.5 2010 48 41.9 2 Carboxylic acid 0.3 1990 42 47.4 3 Carboxylic acid 0.1 1820 41 44.4 4 Carboxylic acid 0.7 2580 45 57.3 5 Carboxylic acid 1.0 3340 42 79.5 6 Sulfonic acid 0.3 1800 47 38.3 7 amino acid 0.3 1710 45 38.0 8 Inorganic acid 0.3 1690 43 39.3 9 nitric acid 0.3 1720 43 40.0

In Table 3, the CMP slurry composition was prepared as follows: 1.0% by weight of a chlorate-based oxidizer and 0.4% by weight of silica used as abrasive grains, 1.0% by weight of carboxylic acid as a polishing regulator and the balance being deionized water Showed the best selectivity ratio of 79.5. In addition, the results of the other experiments show that the selectivity is as high as 38 or more, which is suitable for the organic film polishing composition of the present invention.

&Lt; Experimental Example 3-2: Types of polishing modifiers &

In Experimental Example 3-2, the kind and content of the polishing regulator were varied in a CMP slurry composition holding 1.0 wt% of a chlorate-based oxidizer and 0.2 wt% of silica used as abrasive grains, and the abrasive characteristics thereof were examined . First, six wafers were prepared, an organic film not containing silicon was formed on each of the three wafers, and a plasma-enhanced tetraethoxysilane (PETEOS) film was formed on each of the remaining three wafers. Next, as shown in Table 4, the polishing characteristics of the respective wafers were measured by changing the carboxylic acid to 0.7 to 1.3 wt% by the CMP process. In Experimental Example 3-1, perchloric acid (HClO ₄ ) was used as the chlorate-based oxidant. Formic acid was used as the carboxylic acid. The average particle size of the silica was about 60 nm.

Type of abrasive modifier Abrasive modifier content (% by weight) The polishing rate (Å / min) Organic film / PETEOS selection ratio Organic film PETEOS One Carboxylic acid 0.7 2600 24 108.3 2 Carboxylic acid 1.0 3500 22 159.1 3 Carboxylic acid 1.3 4410 21 210.0

In Table 4, the selectivity ratio is as high as 108.3 to 210.0 when 1.0% by weight of chlorate-based oxidizer and 0.2% by weight of silica used as abrasive particles are contained and the carboxylic acid is adjusted to 0.7 to 1.3% by weight as a polishing regulator Could know.

<Experimental Example 4: Types of Surfactants>

In Experimental Example 4, a surfactant was added to a CMP slurry composition containing 1.0% by weight of a chlorate-based oxidizer, 0.4% by weight of silica abrasive grains and 0.3% by weight of carboxylic acid as cationic, anionic and non- Ion system, and then the polishing characteristics are investigated. For this purpose, six wafers were prepared, an organic film not containing silicon was formed on each of the three wafers, and a plasma-enhanced tetraethoxysilane (PETEOS) film was formed on each of the remaining three wafers. Next, CMP slurry compositions for varying the surfactant were prepared as described above. At this time, the added amount of each kind of surfactant added was 0.5% by weight based on the weight of the total composition. As the cationic surfactant, benzalkonium chloride was used. Alkyl benzene sulfonate was used as the anionic surfactant. As the nonionic surfactant, polyethylene glycol was used. Perchloric acid (HClO ₄ ) was used as the chlorate-based oxidant. Formic acid was used as the carboxylic acid. The average particle size of the silica was about 60 nm. CMP process was performed on each wafer using the above CMP slurry compositions and the polishing characteristics were investigated and recorded in Table 5.

Type of surfactant Surfactant Content (wt%) Organic film / PETEOS selection ratio One Cationic system 0.5 56 2 Anion system 0.5 73 3 Nonionic system 0.5 102

In Table 5, it can be seen that the addition ratio of the nonionic surfactant exhibits the best selection ratio of 102. [ Regardless of the type of surfactant, the selectivity ratio was 56 or more by adding only surfactant. The anionic surfactant was superior to the nonionic surfactant. In addition, when the surfactant was added, peeling of the surface of the organic film was remarkably improved as compared with the case where no surfactant was added. It can be inferred that the CMP composition of the present invention increases the wettability at the surface of the organic film by the surfactant, and the polishing effect uniformly acts on the entire surface.

<Experimental Example 5-1>

In Experimental Example 5-1, how the polishing characteristics vary depending on the pH of the CMP composition of the present invention was examined. First, silica particles having a particle size of about 60 nm were added at 0.5 wt%, and perchloric acid was added at 1.0 wt% as a chlorate-based oxidant. At this time, the pH was about 2.1. These same compositions were prepared in 8 samples. The pH was adjusted by adding a pH adjusting agent to 7 of 8 samples. At this time, the added pH adjusting agent was added in an amount of 3% by weight or less of the total composition. Two of the seven samples were added with small amounts of nitric acid as pH adjusters to lower the pH to 1.8 and 2.0, respectively, to lower the pH. In the other five samples, potassium hydroxide (KOH) was slightly added as a pH regulator to raise the pH to 2.2-3.0. Using the samples, the CMP process was performed on the organic film containing no silicon and the TEOS film as the oxide film, and the polishing characteristics were investigated and recorded in Table 6.

Experiment number Composition pH The polishing rate (Å / min) Organic film / TEOS selection ratio Abrasive grain stability Organic film TEOS One 1.8 1403 55 25.5 Poor 2 2.0 1470 57 25.8 Poor 3 2.1 1580 60 26.3 good 4 2.2 1620 62 26.1 good 5 2.4 1610 60 26.8 good 6 2.6 1520 61 24.9 good 7 2.8 1480 59 25.1 Poor 8 3.0 1420 58 24.5 Poor

In Table 6 above, it was shown to have an excellent selectivity of at least 24.5 regardless of the pH of the composition. However, when the particle stability is indicated as 'poor' in Table 6, it means that the problems such as sinking of silica particles in the composition and change of color occur. If the stability of the abrasive grains is not good, it is impossible to exhibit uniform surface polishing characteristics in the polishing process. From Table 6, it can be seen that when the CMP composition of Experimental Example 5-1 contains 0.5% by weight of silica particles and 1.0% by weight of perchloric acid as a chlorate-based oxidizing agent, the pH is preferably about 2.1 to 2.6.

<Experimental Example 5-2>

In Experimental Example 5-2, how the stability of the abrasive grains varies according to the pH of the CMP composition of the present invention was examined. First, silica particles having a particle size of about 60 nm were added in an amount of 0.5% by weight, and 0.3% by weight of potassium persulfate (K ₂ S ₂ O ₈ ) was added as an oxidizing agent based on a sulfate. At this time, the pH was about 4.2. Three composition samples having such compositions were made. The pH was adjusted by adding a pH adjusting agent to two of the three samples. At this time, the added pH adjusting agent was added in an amount of 3% by weight or less of the total composition. In one of the three samples, sulfuric acid was added little by little as a pH regulator to lower the pH, and the pH was measured to visually observe the abrasive grain stability. At this time, when the pH was lowered to less than 3.5, the abrasive grain stability deteriorated. In one of the three samples, potassium hydroxide (KOH) was added little by little as a pH regulator to increase the pH, and the pH of the sample was measured to visually observe the stability of the abrasive particles. At this time, when the pH exceeded 5.0, the abrasive grain stability deteriorated. As a result, when the CMP composition of Experimental Example 5-2 contains 0.5% by weight of silica particles and 0.3% by weight of potassium persulfate (K ₂ S ₂ O ₈ ) 5.0. &Lt; / RTI &gt;

<Experimental Example 5-3>

In Experimental Example 5-2, how the stability of the abrasive grains varies according to the pH of the CMP composition of the present invention was examined. First, ceria particles having a particle size of about 60 nm were added in an amount of 0.5 wt%, and iron nitrate (Fe (NO) ₃ ) was added in an amount of 0.3 wt% as a nitrate-based oxidizing agent. At this time, the pH was about 2.1. Three composition samples having such compositions were made. The pH was adjusted by adding a pH adjusting agent to two of the three samples. At this time, the added pH adjusting agent was added in an amount of 3% by weight or less of the total composition. In one of the three samples, nitric acid was added little by little as a pH regulator to lower the pH, and the pH was measured to visually observe the abrasive grain stability. At this time, when the pH was lowered to less than 2.0, the abrasive grain stability deteriorated. In one of the three samples, potassium hydroxide (KOH) was added little by little as a pH regulator to increase the pH, and the pH of the sample was measured to visually observe the stability of the abrasive particles. At this time, when the pH exceeded 2.8, the abrasive grain stability deteriorated. Thus, when the CMP composition of Experimental Example 5-3 contains 0.5% by weight of ceria particles and 0.3% by weight of iron nitrate (Fe (NO) ₃ ), the preferable pH is about 2.0 to 2.8.

<Experimental Example 6>

In Experimental Example 6, how the polishing characteristics vary depending on the size of the silica abrasive particles of the present invention was examined. The silica abrasive grains were added in an amount of 0.5 wt% and perchloric acid was added as a chlorate-based oxidizing agent in an amount of 1.0 wt%. Then, four composition samples each having a size of silica abrasive of about 30 nm, 60 nm, 80 nm and 120 nm were prepared. Using the samples, the CMP process was performed on the organic film which does not contain silicon and the TEOS film which is an oxide film, and the polishing characteristics were investigated and recorded in Table 7.

Experiment number Silica particle size (nm) The polishing rate (Å / min) Organic film / TEOS selection ratio Organic film TEOS One 30 1550 50 31 2 60 1620 62 26.1 3 80 2100 88 23.9 4 120 2430 101 24.1

Referring to Table 7, when the silica particle size is 120 nm or less, the selectivity is as high as 23.9 or more.

<Experimental Example 7>

In Experimental Example 7, ceria was used as the oxide abrasive grains of the present invention. We also investigated how the polishing characteristics vary with the size of ceria abrasive grains. Ceria abrasive grains were added in an amount of 0.05 wt% and iron nitrate was added in an amount of 3.0 wt% as an oxidizing agent. And three composition samples having ceria abrasive sizes of about 30 nm, 60 nm and 80 nm, respectively. Using the samples, the CMP process was performed on the organic film which does not contain silicon and the TEOS film which is an oxide film, and the polishing characteristics were investigated and recorded in Table 7.

Experiment number Celia
Particle Size (nm) The polishing rate (Å / min) Organic film / TEOS selection ratio Organic film TEOS One 30 1720 4 430 2 60 2100 6 350 3 80 2450 12 204

Referring to Table 8, when the ceria is used as the oxide abrasive grains, the selection ratio is remarkably improved to 204 ~ 430. Also, it can be seen that the selectivity ratio increases with decreasing ceria particle size.

The etch selectivity ratio of the organic layer to the oxide layer can be variously varied from about 6: 1 to about 430: 1 through various experimental examples. A CMP composition can be applied by selecting an appropriate composition according to the structure of a semiconductor device to be manufactured.

Hereinafter, a manufacturing process of a specific semiconductor device to which the CMP composition of the present invention can be applied will be described.

3 to 10 are cross-sectional views illustrating a process of fabricating a semiconductor device according to an embodiment of the present invention.

Referring to FIG. 3, first gate interlayer insulating films 3 and first sacrificial films 5 are alternately stacked on a substrate 1 to form a first structure 10. The first sacrificial layers 5 may be formed of a material having an etch selectivity with respect to the first inter-gate insulating films 3. The first inter-gate insulating films 3 may be, for example, a silicon oxide film, and the first sacrificial films 5 may be a silicon nitride film. The first sacrificial layers 5 and the first gate dielectric interlayers 3 are sequentially etched to form a first hole 12 exposing the substrate 1. [

Referring to FIG. 4, an organic layer 14 not containing silicon is formed on the first structure 10 to fill the first holes 12.

Referring to FIG. 5, a CMP process is performed on the organic layer 14 using the CMP composition to remove the organic layer 14 on the first structure 10, (3). At this time, since the CMP composition has an excellent polishing selectivity to the oxide film and exhibits a high polishing rate with respect to the organic film, the CMP process can proceed quickly without fail. As a result, the organic film pattern 14a remains in the first hole 12.

Referring to FIG. 6, second gate interlayer insulating films 23 and second sacrificial films 25 are alternately stacked on the first structure 10 to form a second structure 20. The second sacrificial layers 25 may be the same as the first sacrificial layers 5. The second inter-gate insulating films 23 may be the same as the first inter-gate insulating films 3. The second sacrificial layers 25 and the second gate interlayer insulating films 23 are sequentially etched to form a second hole 22 exposing the organic film pattern 14a. At this time, the organic film pattern 14a protects the first hole 12 and the substrate 1 on the bottom.

In this example, two layers of structures 10 and 20 are formed, but the number of layers of the structures may be three or more.

Referring to FIG. 7, the organic film pattern 14a exposed through the second hole 22 is selectively removed by performing an ashing process using oxygen or the like. This allows the substrate 1 to be exposed at the bottom of the first hole 12.

8, a polysilicon film is formed on the front surface of the substrate 1, a first buried insulating film is formed to fill the holes 12 and 22, and then planarization etching is applied to the holes 12 and 22 The active pillars 27 covering the side walls and the bottom thereof and the first buried insulation film pattern 29 filling them are formed. Then, the common drain region 31 may be formed on the active pillars 27 by performing the ion implantation process.

Referring to FIG. 9, grooves 32 for exposing the substrate 1 are formed by patterning the structures 20 and 10 spaced apart from the active pillars 27. And the sacrificial films 5 and 25 are removed through the groove 32. A gate insulating film 34 is formed in a cone shape in a region where the sacrificial films 5 and 25 are removed and a conductive film is formed so that the regions where the sacrificial films 5 and 25 are removed and the grooves 32 Fill it. The gate insulating layer 34 may include a tunnel insulating layer, a charge trap layer, and a blocking insulating layer. The conductive film may be an impurity-doped polysilicon or a metal-containing film. The conductive layers in the groove 32 are removed to expose the substrate 1 and a lower selection line LSL and word lines WL0 to WL3 are formed between the gate insulating layers 3 and 23. [ And upper select lines USL0 and USL1.

Referring to FIG. 10, an ion implantation process is performed to form a common source line (CSL) under the groove 32. After the groove 32 is filled with the second buried insulating film, the second buried insulating film pattern 34 is left in the groove 32 by planarizing and etching. A plurality of bit lines BL which are in contact with the common drain region 31 and are spaced apart from each other are formed on the second gate interlayer insulating film 23 of the uppermost layer.

FIGS. 3 to 10 illustrate the application of the CMP composition of the present invention to the vertical NAND memory device.

11 to 17 are cross-sectional views illustrating a process of manufacturing a semiconductor device according to another embodiment of the present invention.

Referring to FIG. 11, a film 53 to be etched is formed on a substrate 51. The etching target film 53 may be, for example, a silicon oxide film, a silicon nitride film, a polysilicon film, or the like. A first mask film 55 is formed on the etching target film 53. The first mask layer 55 may be an organic layer having an etch selectivity with the etch target layer 53, for example, silicon-free. A second mask pattern 57 is formed on the first mask film 55. The second mask pattern 57 may be formed of a material having an etch selectivity with the first mask layer 55. The width W1 of the second mask pattern 57 may correspond to a minimum line width that can be implemented in the photolithography process. The distance W2 between the second mask patterns 57 may be greater than the width W1 of the second mask pattern 57. [ For example, the width W1 versus the spacing W2 may be about 3: 5. Spacers 59 are formed to cover sidewalls of the second mask pattern 57. The width W3 of the spacers 59 may correspond to about one-third of the width W1 of the second mask pattern 57.

Referring to FIG. 12, the second mask pattern 57 is removed. The first mask patterns 55 are etched using the spacers 59 as an etch mask to form the first mask patterns 55a. At this time, the interval between the first mask patterns 55a may be substantially equal to the width W1 of the second mask pattern 57.

Referring to FIG. 13, a third mask layer 61 that conformally covers the upper surface and the side walls of the first mask patterns 55 is formed. The third mask film 61 may be, for example, a silicon oxide film. The thickness T1 of the third mask layer 61 may be equal to the width W3 of the spacer 59. [

Referring to FIG. 14, an organic layer 63 is formed on the third mask layer 61. The organic layer 63 may be formed of an organic layer containing no silicon. The organic layer 63 is formed to fill the spaces between the first mask patterns 55a.

Referring to FIG. 15, the organic film 63 is subjected to a CMP process using the CMP composition. The organic film 63 on the uppermost surface of the third mask film 61 is removed to expose the uppermost surface of the third mask film 61 and the organic film patterns 61a are formed between the first mask patterns 55a, (63a).

16, an anisotropic etching process is performed on the exposed third mask film 61 to remove the third mask film 61 between the organic film patterns 63a, Thereby exposing the openings 55a. At this time, the third mask patterns 61a are left under the organic film patterns 63a. At this time, the gap between the first mask pattern 55a and the organic film pattern 63a may be the same as the width W3 of the spacer 59.

Referring to FIG. 17, the etching target film 53 is etched using the first mask pattern 55a and the organic film pattern 63a as an etching mask to form etching target film patterns 53a. Then, the first and third mask patterns 55a and 61a and the organic film pattern 63a are removed. This makes it possible to form a pattern having a line width smaller than the minimum line width that can be realized by the photolithography process.

The method described with reference to FIGS. 11 to 17 can be applied to the process of forming word lines or bit lines of a DRAM device.

18 is a schematic block diagram illustrating an example of a memory system including a semiconductor device manufactured in accordance with embodiments of the present invention.

18, the memory system 1100 may be a personal digital assistant (PDA), a portable computer, a web tablet, a wireless phone, a mobile phone, a digital music player, A memory card, or any device capable of transmitting and / or receiving information in a wireless environment.

The memory system 1100 includes an input / output device 1120 such as a controller 1110, a keypad, a keyboard and a display, a memory 1130, an interface 1140, and a bus 1150. Memory 1130 and interface 1140 are in communication with one another via bus 1150.

The controller 1110 includes at least one microprocessor, digital signal processor, microcontroller, or other similar process device. Memory 1130 may be used to store instructions executed by the controller. The input / output device 1120 may receive data or signals from outside the system 1100, or may output data or signals outside the system 1100. For example, the input / output device 1120 may include a keyboard, a keypad, or a display device.

Memory 1130 includes a non-volatile memory device in accordance with embodiments of the present invention. Memory 1130 may also include other types of memory, volatile memory that may be accessed at any time, and various other types of memory.

The interface 1140 serves to transmit data to and receive data from the communication network.

19 is a schematic block diagram showing an example of a memory card having a semiconductor device manufactured according to the embodiments of the present invention.

Referring to FIG. 19, a memory card 1200 for supporting a high capacity data storage capability mounts a flash memory device 1210 according to the present invention. The memory card 1200 according to the present invention includes a memory controller 1220 that controls the exchange of all data between the host and the flash memory device 1210.

The SRAM 1221 is used as the operating memory of the processing unit 1222. The host interface 1223 has a data exchange protocol of a host connected to the memory card 1200. Error correction block 1224 detects and corrects errors contained in data read from multi-bit flash memory device 1210. The memory interface 1225 interfaces with the flash memory device 1210 of the present invention. The processing unit 1222 performs all control operations for data exchange of the memory controller 1220. Although it is not shown in the drawing, the memory card 1200 according to the present invention may be further provided with a ROM (not shown) or the like for storing code data for interfacing with a host, To those who have learned.

According to the above flash memory device and memory card or memory system of the present invention, it is possible to provide a reliable memory system through the flash memory device 1210 with the erase characteristics of the dummy cells improved. In particular, the flash memory device of the present invention can be provided in a memory system such as a solid state disk (SSD) device which is actively in progress. In this case, a reliable memory system can be implemented by blocking read errors caused by dummy cells.

20 is a schematic block diagram showing an example of an information processing system for mounting a semiconductor device manufactured according to the embodiments of the present invention.

Referring to FIG. 20, the flash memory system 1310 of the present invention is installed in an information processing system such as a mobile device or a desktop computer. The information processing system 1300 according to the present invention includes a flash memory system 1310 and a modem 1320, a central processing unit 1330, a RAM 1340, a user interface 1350, . The flash memory system 1310 will be configured substantially the same as the memory system or flash memory system mentioned above. The flash memory system 1310 stores data processed by the central processing unit 1330 or externally input data. In this case, the above-described flash memory system 1310 may be configured as a semiconductor disk device (SSD), in which case the information processing system 1300 can stably store a large amount of data in the flash memory system 1310. As the reliability increases, the flash memory system 1310 can save resources required for error correction and provide a high-speed data exchange function to the information processing system 1300. Although not shown, the information processing system 1300 according to the present invention can be provided with an application chipset, a camera image processor (CIS), an input / output device, and the like. It is clear to those who have learned.

Further, the flash memory device or memory system according to the present invention can be mounted in various types of packages. For example, the flash memory device or the memory system according to the present invention may be implemented as a package on package (PoP), ball grid arrays (BGAs), chip scale packages (CSPs), plastic leaded chip carriers (PDIP), Die in Waffle Pack, Die in Wafer Form, Chip On Board (COB), Ceramic Dual In-Line Package (CERDIP), Plastic Metric Quad Flat Pack (MQFP), Thin Quad Flatpack (TQFP) SOIC), Shrink Small Outline Package (SSOP), Thin Small Outline (TSOP), Thin Quad Flatpack (TQFP), System In Package (SIP), Multi Chip Package (MCP), Wafer-level Fabricated Package Level Processed Stack Package (WSP) or the like.

While the present invention has been described in connection with what is presently considered to be practical exemplary embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, It will be understood. It is therefore to be understood that the above-described embodiments are illustrative and not restrictive in every respect.

1, 51, 100: substrate
3, and 23: a gate interlayer insulating film
5, 25: sacrificial membrane
10, 20 110: Structure
14, 14a, 63, 63a, 120, 120a,
12, 22: Hall
32: Groove
115: recessed area
29, 34: buried insulating film
31: common drain region
34: Gate insulating film
LSL: lower select line
WL0, WL1, WL2, WL3: word line
USL0, USL1: upper select line
BL: bit line
CSL: common source line
53: etching target film
55, 55a, 57, 61, 61a: mask film
59: Spacer

Claims (19)

1. A chemical mechanical polishing (CMP) slurry composition for use in polishing an organic film not containing silicon,
0.001 to 5% by weight of oxide abrasive grains;
0.1 to 5% by weight of an oxidizing agent;
0 to 5% by weight of an abrasive modifier;
0 to 3% by weight of surfactant;
0 to 3% by weight of a pH adjusting agent; And
CMP slurry composition comprising deionized water at 79 to 99.889 wt%. The method according to claim 1,
The abrasive particles include silica (SiO _2), ceria (CeO ₂₎ and alumina (Al ₂ O ₃₎ at least one of the CMP slurry composition is selected in. The method according to claim 1,
And the particle size of the abrasive grains is 30 to 120 nm. The method according to claim 1,
The oxidizing agent may be at least one selected from the group consisting of hydrogen peroxide, superoxide, dioxygenyl, ozone, ozone, peroxide, fluorine, chlorine, Chlorite, Chlorate, Perchlorate, Halogen Compounds, Nitric acid, Nitrate, Hypochlorite, Hypohalite, Chromium Trioxide (Chlorite), Chlorate, Perchlorate, Chromium trioxide, Pyridinium chlorochromate, Chromate, Dichromate, Chromium Compound, Potassium permanganate, Permanganate, Sodium perborate Sodium perborate, nitrous oxide, 2,2'-dipyridisulfide, lead dioxide (PbO ₂ ), manganese dioxide (MnO ₂ ), copper oxide (CuO), ferric chloride ₃ ), perchloric acid (HClO ₄ ), iron nitrate (Fe (NO) ₃ ), sulfate at least one material selected from the group consisting of sulfate and potassium persulfate (K ₂ S ₂ O ₈ ). The method according to claim 1,
The polishing regulator may be selected from the group consisting of organic acid, inorganic acid, nitric acid, nitrate, sulfuric acid, peroxydisulfuric acid, peroxymonosulfuric acid, It is possible to use a carboxylic acid such as sulfonic acid, acetic acid, citric acid, formic acid, gluconic acid, lactic acid, oxalic acid, tartaric acid, It is also possible to use carboxylic acid, chloric acid, chlorous acid, hypochlorous acid, perchloric acid, halogenooxoacid, ascorbic acid, Wherein the composition is at least one selected from the group consisting of Vinylogous carboxylic acid, amino acid, histidine, glycine, arginine, hydrochloric acid, hydrofluoric acid and phosphoric acid. The method according to claim 1,
Wherein the surfactant is an anionic or nonionic surfactant. The method according to claim 1,
The surfactant may be selected from the group consisting of lauryl myristyl alcohol series, methyl-oxirane polymer series having a hydrophile lipophile balance (HLB) value of 12 or more, ethylenediamine, ethoxylated propoxy At least one selected from the group consisting of ethoxylated and propoxylated alcohol series, 2-methyloxirane, oxirane series, polyethylene glycol, and polysorbate series. CMP slurry composition. The method according to claim 1,
The surfactant may be selected from the group consisting of benzalkonium chloride, alkyl benzene sulfonate, phemerol chloride, ammonium lauryl sulfate, sodium lauryl ether sulfate, ether sulfate, sodium myreth sulfate, dioctyl sodium sulfosuccinate, perfluorooctanesulfonate, perfluorobutanesulfonate, linear alkylbenzene sulfonates, But are not limited to, linear alkylbenzene sulfonate, sodium stearate, sodium lauroyl sarcosinate, cetyl trimethylammonium bromide, cetyl trimethylammonium chloride, Perfluorononanoate, perfluorooctanoate, But are not limited to, perfluorooctanoate, octenidine dihydrochloride, 5-bromo-5-nitro-1,3-dioxane, dimethyl But are not limited to, dimethyldioctadecylammonium chloride, Cetrimonium bromide, dioctadecyldimethylammonium bromide, octaethylene glycol monododecyl ether, glyceryllaurammonium bromide, Wherein the CMP slurry composition is at least one selected from the group consisting of glyceryl laurate, or polyethoxylated tallow amine. The method of claim 1, wherein
The pH adjusting agent may be at least one acid selected from the group consisting of polyacrylic acid, carboxylic acid, sulfuric acid and sulfonic acid, or may be at least one acid selected from the group consisting of potassium hydroxide, sodium hydroxide, ammonia water, tetramethylammonium hydroxide Wherein the at least one base is selected from the group consisting of Tetramethylammonium hydroxide, Tetraethylammonium hydroxide and Tetrabutylammonium hydroxide. The method according to claim 1,
Wherein the composition has a pH of from 2.0 to 5.0. Forming a first structure on the substrate, the first structure including a first recessed region;
Forming an organic film not containing silicon on the first structure to fill the first recess region; And
And performing a CMP process on the organic film using the CMP slurry composition of claim 1 to remove at least a part of the organic film. 12. The method of claim 11,
Wherein removing at least a portion of the organic film exposes an upper surface of the first structure. 13. The method of claim 12,
The first recess region is a first hole exposing the substrate,
After the organic film is subjected to a CMP process,
Forming a second structure including a second hole exposing an upper surface of the organic layer on the first structure;
Removing the organic film through the second hole;
Forming active pillars covering at least sidewalls of the first holes and the second holes; And
And forming a conductive line in the first structure and a part of the second structure. 14. The method of claim 13,
The first structure and the second structure each have a structure in which a plurality of insulating films and sacrificial films are alternately stacked,
Forming a conductive line in the first structure and a portion of the second structure,
Selectively removing the sacrificial layers; And
And forming the conductive line in a region where the sacrificial films are removed. 12. The method of claim 11,
Wherein the first structure comprises a film to be etched disposed on the substrate, first mask patterns arranged on the film to be etched and having a plurality of parallel lines, And a second mask film that covers the substrate,
Wherein exposing the top surface of the first structure exposes the top surface of the second mask film. 16. The method of claim 15,
Wherein an interval between the first mask patterns is three times the thickness of the second mask film,
Wherein the organic film is disposed between the first mask patterns. 16. The method of claim 15,
Further comprising performing an anisotropic etching process to remove the exposed second mask film and form a second mask pattern below the organic film. 13. The method of claim 12,
An oxide film is disposed on an upper end of the first structure,
Wherein the CMP slurry composition polishes the organic film with a selectivity of 6: 1 or more with respect to the oxide film. 12. The method of claim 11,
Wherein removing at least a portion of the organic film does not expose an upper surface of the first structure.

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