KR100762091B1 - Chemical Mechanical Abrasive Slurry Composition for Copper Damasine Process - Google Patents

Abstract

The present invention relates to a chemical mechanical polishing slurry composition for performing a copper damascene process in a semiconductor manufacturing process, and more particularly, 0.5 to 12% by weight of the abrasive and gluconic acid, morpholine, taurine, alumina, based on the total weight of the slurry. For chemical mechanical polishing for copper damascene processes containing from 0.001 to 5% by weight of one or more additives selected from compounds selected from dific acid or aminoalcohol or salts thereof and free of oxidizing agents and having a pH of 2 to 12 It provides a slurry composition.

The secondary chemical mechanical polishing slurry of the copper damascene process according to the present invention does not contain an oxidizing agent and thus has excellent abrasive reproducibility, low floating etching rate, and suitable polishing rate for copper, silicon oxide film and tantalum based film. It has the advantage of easy to remove dishing or erosion generated in, excellent dispersion stability, low scratch generation is useful as a secondary polishing slurry of copper damascene process.

Description

Chemical mechanical polishing slurry composition for copper damascene process {CMP Slurry composition for copper damascene process}

The present invention relates to a chemical mechanical polishing slurry composition for performing a copper damascene process in a semiconductor manufacturing process, and more particularly, to a slurry for secondary chemical mechanical polishing of a copper damascene process.

Since IBM announced copper chips using the damascene process in 1997, there has been an increase in the use of copper instead of tungsten or aluminum as a wiring material to address the increased wiring resistance due to wiring miniaturization on the device. Doing. In the case of using copper as a metal wiring, since the etching process using plasma is impossible, a damascene process is essential and a copper CMP process is necessary. The increase in semiconductor devices employing copper interconnects has increased the importance of copper CMP slurries.

The copper damascene process includes patterning a surface of a silicon oxide film or a low dielectric material film by a conventional dry etching process to form holes and trenches for vertical and horizontal wiring, wherein the patterned surface is formed of titanium (Ti) or tantalum. Coating with an adhesion promoter film selected from (Ta), a diffusion barrier film selected from titanium nitride (TiN) or tantalum nitride (TaN) or a composite film thereof, and then coating copper on the adhesion promoter film or diffusion barrier film, Using mechanical polishing, the process proceeds to polishing not only copper but also a portion of the adhesion promoter, the diffusion barrier, and the silicon oxide film to form a circuit wiring composed of a hole and trench filled with electrically conductive copper and a dielectric such as a silicon oxide film. Done. In this case, the CMP process is generally performed in two successive stages. In the first polishing, in order to stop polishing in the diffusion barrier after removing the copper layer, the polishing rate of copper is high and the polishing selectivity of the copper layer to the diffusion barrier is very high ( For example, slurries of 100: 1 or more are used, and in secondary polishing, a slurry is generally preferred, which has low polishing selectivity for each film and has an appropriate relative polishing rate. In secondary polishing, the film to be polished, specifically, a Cu film, a TaN / Ta film, a silicon oxide film (or a low dielectric film), or the like is polished, so that the polishing rate of three or more kinds of films must be appropriate for dishing produced during the first polishing process. Finally, a smooth polished surface can be obtained by removing the dishing or erosion. Dicing refers to a phenomenon in which a central portion of a metal wiring such as copper is excessively removed, and erosion refers to an unnecessary recess in a polishing surface generated by removing a portion of the dielectric layer having a high metal wiring density. Both dishing and erosion can cause failures that degrade the electrical characteristics of the circuit.

As a slurry composition for secondary polishing of a copper film, Korean Patent Publication No. 10-0473442 discloses a tantalum-based polishing composition using fumed silica, propanoic acid, and hydrogen peroxide, and includes a first liquid containing an abrasive and an oxidizing agent. Separating and packaging with a second liquid containing, to solve the decomposition of hydrogen peroxide according to the storage period, but the separation-packed polishing composition has a disadvantage inconvenient to use. Korean Patent Publication No. 10-2003-0059070 also discloses a polishing composition containing fumed silica in a basic region using propanoic acid as an organic acid. The composition provides a slurry with improved storage stability due to the use of fumed silica. However, since the composition contains hydrogen peroxide, there is a problem in storage stability due to decomposition of hydrogen peroxide over time under basic conditions, which makes it difficult to control the polishing rate and selectivity of the copper film, and it is a fundamental disadvantage that it is difficult to secure abrasive reproducibility. There is this.

Meanwhile, Korean Laid-Open Patent Publication No. 2005-39602 discloses polishing in two steps in copper CMP with a polishing liquid containing no oxidizing agent and containing 0.1 to 5% by weight of abrasives and 0.5 to 10% by weight of citric acid and glutamic acid as organic acids. However, the polishing solution has a problem that the polishing rate of the silicon oxide film with respect to the copper film is very low, causing dishing of the copper wiring to the copper film. In addition, as a selective remover for tantalum-based membranes, Korean Laid-Open Publication No. 2004-104956 provides a slurry for removing tantalum barrier materials containing formamidine-based or guanidine-based tantalum removers, and Korean Laid-Open Publication No. 2005-43666 Although a polishing solution for removing a tantalum barrier containing an azole compound and an abrasive is provided, the polishing solution has a limitation in that the polishing rate of the copper film and the silicon oxide film is too low to be impractical, so that the composition for the second CMP of the copper damascene process is limited. Not suitable for use.

The present inventors have made an effort to solve the above problems, and as a result of repeated studies on the copper secondary polishing slurry containing no oxidizing agent in order to secure storage stability and abrasive reproducibility of the copper secondary polishing slurry, When an appropriate concentration of one or more additives selected from a compound selected from choline, morpholine, taurine, adipic acid, or aminoalcohol or salts thereof, the copper has a low floating etching rate, and the copper film, silicon oxide film and tantalum The polishing rate of the membrane can be adjusted appropriately, so that the dishing or erosion of the copper film generated in the primary polishing process can be effectively removed, and it has been found to have excellent dispersion stability, and it is also found in gluconic acid, morpholine, taurine, and adipe. At least one addition selected from compounds selected from acids, citric acid or aminoalcohols or salts thereof And in addition to nitrilotris (methylene) triphosphonic acid (NTPA), the polishing rate for the cornea forming the copper wiring was found to be appropriate, the floating etching rate of copper was low, and the dispersion stability was excellent. Thus, it was confirmed that the polishing composition of the composition is a slurry suitable for application to the secondary polishing slurry of the copper damascene process to complete the present invention.

Accordingly, it is an object of the present invention to provide a slurry composition for secondary CMP in a copper damascene process that does not contain an oxidizing agent and has excellent abrasive reproducibility and no change over time.

In addition, another object of the present invention is to provide a good flatness by having a suitable polishing rate for the copper film, silicon oxide film and tantalum-based film, and copper damascene to remove dishing or erosion occurring during the first CMP It is to provide a slurry composition for secondary CMP of the process.

In addition, another object of the present invention is to provide a slurry composition for secondary CMP of the copper damascene process in which the surface of the polished copper film is good while removing dishing and erosion.

The present invention relates to a chemical mechanical polishing slurry composition for carrying out a copper damascene process in a semiconductor manufacturing process, more specifically, containing 0.5 to 12% by weight of an abrasive and 0.001 to 5% by weight of an additive, based on the total weight of the slurry. It is characterized in that it does not contain an oxidizing agent and provides a slurry composition for CMP having a pH of 2 to 12.

In a first aspect according to the invention the additive is at least one selected from a compound selected from gluconic acid, morpholine, taurine, adipic acid or aminoalcohol or salts thereof, and in another aspect of the invention the additive is a glue A polishing composition further comprising at least one selected from a compound selected from choline, morpholine, taurine, adipic acid, citric acid or aminoalcohol or salts thereof and nitrilotris (methylene) triphosphonic acid (NTPA) or salts thereof Is initiated.

The secondary chemical mechanical polishing slurry of the copper damascene process according to the present invention does not contain an oxidizing agent and thus has excellent abrasive reproducibility, no change over time, low floating etching speed of copper, and polishing of copper, silicon oxide and tantalum-based films. It has the advantage of eliminating dishing and erosion that occurs in primary polishing due to the proper speed, and is useful as a secondary polishing slurry in the copper damascene process. In particular, the copper secondary CMP composition according to the invention contains at least one compound or salt thereof selected from gluconic acid, morpholine, taurine, adipic acid or amanoalcohol as an additive, or gluconic acid, morpholine, taurine, aurea. Advantages of significantly reducing copper surface defects such as dishing, particles and scratches by containing at least one compound selected from dific acid, citric acid or aminoalcohol or salts thereof and nitrilotris (methylene) triphosphonic acid (NTPA) or salts thereof Have

The slurry composition according to the present invention does not contain commonly used oxidizing agents such as hydrogen peroxide, potassium iodide, ammonium persulfate, potassium ferricyanide, potassium bromide, vanadium trioxide, hypochlorous acid, sodium hypochlorite, ferric nitrate, and the like. It is characterized by. In the basic pH range, oxidants such as hydrogen peroxide, which are most commonly used in semiconductor processes, change over time as the oxidant decomposes over time, thereby changing the polishing rate or polishing selectivity. Therefore, since the slurry composition according to the present invention does not contain an oxidizing agent, it is excellent in abrasive reproducibility or time stability, and the polishing rate of copper and silicon oxide films suitable for the secondary polishing of the copper damascene process by the effect of the combination of other components is achieved. Secured. In addition, if the oxidant is not used, there is no need to mix the slurry and the oxidant, thereby simplifying the slurry feeder of the CMP apparatus, thereby increasing convenience of use.

Hereinafter, the present invention will be described in more detail.

The present invention comprises 0.5 to 12% by weight of the abrasive, 0.001 to 5% by weight of the additive, and no oxidizing agent, and a slurry for the second CMP of the copper damascene process having a pH of 2 to 12, based on the total weight of the slurry. It is about. The additive contains at least one of a compound selected from gluconic acid, morpholine, taurine, adipic acid or aminoalcohol or a salt thereof, or selected from gluconic acid, morpholine, taurine, adipic acid, citric acid or aminoalcohol. At least one of the compounds or salts thereof and nitrilotris (methylene) triphosphonic acid (NTPA) or salts thereof.

The abrasive contained in the slurry according to the present invention serves to control the polishing rate of the tantalum-based film and the silicon oxide film. As the amount of the abrasive increases, the polishing rate of the tantalum-based film and the silicon oxide film increases. Examples of abrasives include fumed silica, colloidal silica and alumina. Ceria, zirconium oxide and mixtures thereof can be used. Preferred abrasives are fumed silica and colloidal silica. The smaller the content, the better the dispersibility and the scratch. However, if the content is too small, the polishing rate of the silicon oxide film and the tantalum-based film is lowered, so 0.5 to 12% by weight is preferable, and the pH is 2 to 5. The abrasive content is from 0.5 to 12% by weight and from 6 to 12% by weight at pH 8-12 is more preferred in terms of dispersibility and scratches. The average particle diameter of the abrasive is preferably 20 to 300 nm. If too small, the polishing rate is low, and if too large, scratches are easily generated.

The slurry of the first aspect according to the present invention uses at least one of a compound selected from gluconic acid, morpholine, taurine, adipic acid or aminoalcohol or a salt thereof as the additive, which is used for polishing copper and tantalum-based films. It is possible to control the speed to an appropriate level, and also to improve the dispersibility of the polishing composition, and serves to suppress the adsorption of the abrasive particles to the polishing film. As the additive, taurine, gluconic acid or a salt thereof is more preferable because the ratio of the removal rate of the thallium-based film to the copper film is high and the floating etching rate of copper is low. The content of the additive according to the first aspect is preferably contained in 0.001 to 5% by weight, more preferably 0.01 to 1.0% by weight, most preferably 0.01 to 0.4% by weight. If the content is within 0.001 to 5% by weight, the polishing rate of the copper film, tantalum-based film and silicon oxide film can be controlled appropriately, there is a good dispersion stability, if the content exceeds 5% by weight of the copper floating There is a problem that the etching rate is increased.

The slurry of the second aspect according to the present invention comprises at least one of compounds selected from gluconic acid, morpholine, taurine, adipic acid, citric acid or aminoalcohol or salts thereof and nitrilotris (methylene) triphosphonic acid (NTPA) ) Or salts thereof. In addition, when citric acid or its salt and nitrilotris (methylene) triphosphonic acid (NTPA) or its salt are used together, the polishing rate of the tantalum-based film is high, the polishing rate ratio of the tantalum-based film to the copper film is high, The floating etching speed is lower and more preferable. Among the additives contained in the slurry of the second aspect of the present invention, at least one compound selected from gluconic acid, morpholine, taurine, adipic acid, citric acid or aminoalcohol or salt thereof is preferably 0.001 to 0.5% by weight. More preferably 0.01 to 0.4% by weight, and the content of nitrilotris (methylene) triphosphonic acid (NTPA) or salt thereof is preferably 0.01 to 1.0% by weight, more preferably 0.01 to 0.4% by weight. . The additive according to the second aspect of the invention is nitrilotris (methylene) triphosphonic acid (NTPA) or a salt thereof and a compound selected from gluconic acid, morpholine, taurine, adipic acid, citric acid or aminoalcohol or salts thereof If it contains more than one, there is an advantage that the adsorption of the abrasive particles on the polishing film is suppressed, the dispersibility is good, and the polishing rate of the tantalum-based film is increased. However, if NTPA is added in an excessively large amount out of the above range, it may cause corrosion of the copper film, and the dispersion stability of the slurry is destroyed, which causes fine scratches on the copper surface. When used below the above range, the effect of adding NTPA is insignificant. In addition, one or more of the compounds selected from gluconic acid, morpholine, taurine, adipic acid, citric acid or aminoalcohol or salts thereof may cause corrosion or polishing of the copper film when used in excess of 0.5% by weight in combination with NTPA. It may be disadvantageous due to the decrease in speed, and when it is contained at less than 0.001% by weight, the adsorption of abrasive particles is high and the polishing rate of the tantalum-based film is lowered, which is not preferable.

Specific examples of the amino alcohols usable as additives for the slurry compositions according to the invention include 2-amino-2-methyl-1-propanol (AMP), 3-amino-1- Propanol (3-amino-1-propanol), 2-amino-1-propanol, 2-amino-1-propanol, 1-amino-2-propanol, 1-amino-pentane All- (1-amino-pentanol), 2- (2-aminoethylamino) ethanol (2- (2-aminoethylamino) ethanol), 2-dimethylamino-2-methyl-1-propanol, N, N-diethylethanol Amines, monoethanolamines, diethanolamines, triethanolamines, and the like, but are not necessarily limited thereto, and the compounds may be used alone or in combination. More preferred amino alcohols are monoethanolamine, 2-amino-2-methyl-1-propanol, 2-dimethylamino-2-methyl-1-propanol or mixtures thereof.

The slurry composition of the present invention has a pH of 2 to 12, more preferably 2 to 5 and 8 to 12. Any pH regulator may be used as long as it can obtain a pH in the above range as the pH regulator. In the present invention, it can be selected from the group consisting of potassium hydroxide, ammonium hydroxide, tetramethylammonium hydroxide and mixtures thereof as the basic pH adjusting agent. The acidic pH adjusting agent may be selected from nitric acid, hydrochloric acid, sulfuric acid, perchloric acid and phosphoric acid. The addition of a basic pH regulator also acts as an aid in increasing the zeta potential to improve the dispersion stability of abrasives such as fumed silica and colloidal silica. Ammonium hydroxide also functions to increase the polishing rate of copper. If it is lower than the pH range, the dispersibility of the abrasive is reduced, and if it is too low or high, there is a problem causing dissolution of copper. The range of pH 5-8 tends to weaken dispersion stability.

The slurry composition of the present invention is low in corrosiveness, but may be contained in small amounts, if necessary, without the use of a corrosion inhibitor. Corrosion inhibitors such as benzotriazole are known to cause strong problems in the copper damascene process by strongly bonding with copper to form a surface of hydrophobic copper, deteriorating the cleaning property, causing particle problems or causing scratches. Since the slurry composition of the present invention does not contain an oxidizing agent, the corrosiveness is significantly low, and thus the problem due to corrosion is not serious. Therefore, the slurry composition of the present invention may be used even if a corrosion inhibitor is not contained. This can prevent the problem. Corrosion inhibitors that may be contained may be selected from benzotriazole or tetrazole-based compounds. As a tetrazole compound, 5-amino tetrazole and 1-alkyl-5-amino tetrazole are preferable. The benzotriazole or tetrazole compound may be mixed or used alone, and the amount added is preferably 0.0001 to 0.1% by weight, more preferably 0.005% to 0.05%. When the content is more than 0.1% by weight, the copper polishing rate may be reduced. When the content is less than 0.0001% by weight, the corrosion inhibitory effect may be weak.

The slurry composition according to the present invention may further contain a surfactant to be 0.0001 to 0.01% by weight relative to the total weight of the slurry. Surfactants can improve the wettability of membranes with hydrophobic low dielectric constants or affect the polishing rate of low dielectric films. If the amount is too small, the effect of the surfactant activity does not appear, if too much there is a problem that bubbles are generated.

More preferred slurry compositions for copper damascene secondary polishing of the present invention are based on the total weight of the slurry, 6 to 12% by weight fumed silica or colloidal silica, taurine, gluconic acid, 2-amino-2-methyl-1-propanol or At least one content selected from the compounds selected from monoethanol amines or salts thereof is 0.01 to 1.0% by weight, potassium hydroxide or ammonium hydroxide to bring the pH to 8 to 12, and benzotriazole containing 0.005 to 0.05% by weight. 6-12 wt% of fumed silica or colloidal silica, at least 0.01-0.4 wt% of nitrilotris, selected from citric acid, 2-amino-2-methyl-1-propanol, monoethanol amine or salts thereof 0.01 to 0.4% by weight of methylene) triphosphonic acid (NTPA) or salts thereof, potassium or ammonium hydroxide to bring the pH to 8 to 12, and benzotri A composition containing a sol of 0.005 to 0.05% by weight.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the following Examples do not limit the scope of the present invention.

EXAMPLE

The copper wafer used for polishing was a specimen wafer in which copper was deposited by 10000 kV by PVD method, and the tantalum-based film was a specimen wafer in which a 5000 nm thick PVD tantalum nitride (TaN) thin film was deposited. As the silicon oxide film, a specimen wafer on which a 10000 mm PETEOS thin film was deposited was used. The polishing equipment used was Poli500 CE from G & P Technology. The polishing pad was subjected to a polishing test using a Rodel IC 1400. The polishing conditions were Table / Head speed of 30/30 rpm, polishing pressure of 100 g / cm ² , slurry supply flow rate of 200 ml / min, and polishing time of 60. Seconds. The thickness of the copper film and the tantalum nitride thin film was calculated by converting the thickness after measuring sheet resistance using a four probe surface resistance probe (Four Point Probe) of Changmin Tech. PETEOS thin film thickness was measured with K-mac's Spectra Thick 4000. The floating etching rate was calculated by immersing the copper wafer in the polishing liquid at room temperature for 5 minutes, then washing and measuring the thickness change. In addition, the copper surface state was evaluated by observing the copper surface with a light emitter and a scanning electron microscope (SEM) after polishing or etching to evaluate the occurrence of scratches, the degree of adsorption of abrasive particles and the occurrence of corrosion.

Example 1

As shown in Table 1, colloidal silica A (average particle diameter: 45 nm), colloidal silica B (average particle size: 80 nm), or fumed silica (surface area: 200 m ² / g) was used as an abrasive, and the additives were also shown in Table 1 The content was used and pH was adjusted using KOH.

TABLE 1

Table 1 shows the results of evaluating the polishing rate for the slurry composition. As shown in Table 1, the polishing rate is appropriate even at low pressures and slow rotational speeds, and since the composition contains no oxidizing agent, the floating etching rate is kept very low, so that the occurrence of defects due to corrosion is suppressed. It can be seen that it is suitable for use as a composition for.

In addition, when the surface of the polished copper wafer was observed, no scratches or corrosion occurred, and no corrosion was observed in the copper wafers with the floating etching rate. In general, when the oxidizing agent is added, if the corrosion inhibitor is not used sufficiently, the etching rate is high, and corrosion occurs on the copper surface even after polishing. Adding a corrosion inhibitor to suppress this is another problem, such as the occurrence of scratches, deterioration of the cleaning due to the formation of a hydrophobic organic film on the copper surface.

Example 2

A slurry composition was prepared in which 9% by weight fumed silica having a surface area of 200 m ² / g, 0.1 or 0.4% by weight of gluconic acid, 0 or 0.02% by weight of BTA, 0.03% by weight of AMP, 0.03 or 0.1% by weight of monoethanol amine and the remainder of water, pH was adjusted to 10 with KOH. Experiment No. 2-4 was added 0.03% ammonium hydroxide, and the rest was adjusted to pH 10 using KOH. Here, as shown in Table 2, the content of gluconic acid, BTA, and monoethanol were changed, and the polishing rate and etching rate for copper, tantalum nitride, and PETEOS films were compared.

TABLE 2

From the results of Experiment Nos. 2-2 and 2-3, it can be seen that when the content of gluconic acid increases from 0.1% to 0.4%, the polishing rate for TaN is relatively increased, thereby controlling the polishing rate ratio of the TaN film to the copper film. have. Also, the addition of ammonium hydroxide increased the polishing rates of both copper and TaN.

Example 3

A slurry composition of 8% by weight of colloidal silica having an average particle diameter of 45 nm, 0.2% by weight of NTPA, 0.4% of citric acid, and the remainder of water was prepared, and KOH was added so that the pH was 9.5. Here, by adjusting the content of monoethanol amine (MEA) as shown in Table 3, the polishing rate and etching rate for copper, tantalum nitride and PETEOS film was compared.

[Table 3] Polishing speed according to MEA content

As shown in Table 3, the polishing rate of each film according to the monoethanol content was in an appropriate range, and the polishing rate of TaN and PETEOS decreased at 2 wt% of monoethanol amine. It can be seen that the relative polishing rate can be controlled by the amount of monoethanol amine. In addition, when monoethanolamine was added, the degree of adsorption of silica particles, which are abrasives, on the copper surface was greatly reduced, and thus the amount of residual abrasive particles could be greatly reduced.

Example 4

 10 wt% of colloidal silica having an average particle size of 80 nm and 0.4 wt% of gluconic acid were prepared to change the pH, and the polishing rate of the cornea and the etching rate of the copper film were measured, and the state of the copper surface was observed. The same properties were investigated while changing the pH by adding 0.03% of AMP and 0.1% by weight of monoethanol amine to the composition.

TABLE 4

As shown in Table 4, when the amino alcohol was added, the abrasive particles were not adsorbed on the copper film, which showed excellent results. In the slurry to which the AMP and the monoethanol amine were added, some gelation phenomenon occurred when the pH was 5 to 8. It is more preferable that the pH range is 2 to 5 and 8 to 10.

Example 5

It contains 8% by weight of fumed silica having a surface area of 200 m ² / g, 0.03% by weight of AMP, and the pH was adjusted to 10 by adding KOH, and by adjusting the composition and content of the additive as shown in Table 5 below, copper and tantalum nitride And the polishing rate and the etching rate for the PETEOS film was compared, and the surface state of copper was observed.

TABLE 5

As shown in Table 5, in the case of taurine or gluconic acid, the TaN film had a high polishing rate, which was more suitable for use as a copper secondary polishing composition, and the polishing rate ratio of TaN to Cu could be adjusted according to the additive content. Do. As the taurine content was increased, the polishing rate for the PETEOS film was increased. In the case of morpholine, it showed stable characteristics without changing the polishing rate according to the concentration, and showed the lowest floating etching rate for copper film.

Example 6 Time Change

As described in Table 6, the slurry compositions prepared in Examples 1 to 5 were measured for particle size and pH at the beginning of preparation and 20 days and 2 months after preparation to evaluate the change characteristics over time for the slurry composition. Average particle size is shown in Table 6 below the results measured using a Horiba particle size distribution analyzer. Experiment No. 6-1 composition was the same as Experiment No. 5-3 except that 0.2% NTPA and 0.4% citric acid were used instead of 0.4% of gluconic acid.

TABLE 6

As shown in Table 6, the rest of the additives were excellent in dispersion stability and pH aging stability since the average particle size and pH were hardly changed even after 60 days. Since the polishing composition according to the present invention does not contain an oxidizing agent, the pot life time is equal to the shelf life time, and thus the pot life is very long.

Example 7 Evaluation of Dicing Removal

SKW's SKW 6-3 patterned wafers were used to evaluate the removal ability of dishing. The pattern wafer used in the present embodiment was formed by sequentially forming a thermal oxide film of 3,000 Å, silicon nitride 1,000 E and PETEOS 5,000 상 에 on a bare Si wafer, and then trench pattern having a depth of 5,000 에 on PETEOS. After the formation, Ta / TaN was formed to be 250 mW / 250 mV, copper seed nucleus (Cu Seed) 1,000 mV and electroplating Cu 15,000 mV. The pattern was composed of copper wiring and PETEOS insulated lines, and the width of the copper wiring was changed in the range of 10 to 100 μm. The dish was measured from the following formula by measuring the profile with the KLA-Tencor Alpha step equipment.

[formula]

 Dishing value = height of PETEOS line area-height of Cu line wiring recess

The pattern wafer used was a pattern wafer polished with a primary CMP slurry of a conventional copper damascene process. The slurry of Example 3 (Experiment No. 3-2) was used as the secondary CMP slurry, and a time of 0 seconds in Table 6 was measured after the completion of the first CMP process. In this case, the dishing value means that the first process is generated. In addition, the meaning of “50 μm / 1 μm” of the wiring width (Cu / PETEOS) in Table 5 is that the copper wiring width is 50 μm and the adjacent PETEOS wiring width is 1 μm. it means.

[Table 7] Change of dishing value according to grinding time

From the results of Table 7, it can be seen that the dishing value generated after the first CMP tends to decrease with the progress of the second CMP, and excellent flatness can be obtained.

The present invention relates to a slurry composition for the second CMP of the copper damascene process does not contain an oxidizing agent, the slurry composition according to the present invention does not contain an oxidizing agent causing a change in polishing characteristics due to the aging of the oxidant concentration over time Not even polishing properties can be maintained for a long time, and corrosion caused by the oxidant does not occur, so that the occurrence of defects in the copper film is suppressed. In addition, the slurry composition according to the present invention has the advantage that the polishing rate of the copper film, tantalum film and silicon oxide film is appropriate to obtain excellent flatness and to remove dishing and erosion due to the first CMP process. In addition, it is excellent in aging stability and dispersion stability to suppress the generation of large particles due to long-term storage has the advantage that the copper polishing surface due to the low scratch and low corrosion caused by the large particles is very good.

Claims (14)

Based on the total weight of the slurry, it contains 0.5 to 12% by weight of an abrasive and 0.001 to 5% by weight of at least one additive selected from a compound selected from gluconic acid, morpholine, taurine, or aminoalcohol or a salt thereof, and contains no oxidizing agent. A slurry composition for chemical mechanical polishing, wherein the copper damascene process has a pH of 2 to 12. 0.5 to 12% by weight of the abrasive, from 0.001 to 0.5% by weight of at least one selected from a compound selected from gluconic acid, morpholine, taurine, adipic acid, citric acid or aminoalcohol or salts thereof and nitrilotris (Methylene) triphosphonic acid (NTPA) or a salt composition for chemical mechanical polishing for the copper damascene process containing an additive consisting of 0.01 to 1.0% by weight thereof and containing no oxidizing agent and having a pH of 2 to 12 . The method according to claim 1 or 2, The amino alcohol is 2-amino-2-methyl-1-propanol, 3-amino-1-propanol, 2-amino-1-propanol, 1-amino-2-propanol, 1-amino-pentanol, 2- ( 2-aminoethylamino) ethanol, 2-dimethylamino-2-methyl-1-propanol, N, N-diethylethanolamine, monoethanolamine, diethanolamine, triethanolamine and mixtures thereof Chemical mechanical polishing slurry composition for copper damascene process. The method of claim 3, wherein Aminoalcohol is a chemical mechanical polishing slurry for copper damascene process characterized in that it is selected from monoethanolamine, 2-amino-2-methyl-1-propanol, 2-dimethylamino-2-methyl-1-propanol or mixtures thereof. Composition. The method of claim 1, The additive is at least one selected from a compound selected from taurine, gluconic acid, 2-amino-2-methyl-1-propanol or monoethanol amine or a salt thereof, and the copper content is 0.01 to 1.0% by weight. Chemical mechanical polishing slurry composition for damascene process. The method of claim 2, The additive is at least 0.01 to 0.4% by weight selected from citric acid, 2-amino-2-methyl-1-propanol, monoethanol amine or salts thereof and nitrilotris (methylene) triphosphonic acid (NTPA) or salts thereof Chemical mechanical polishing slurry composition for copper damascene process, characterized in that consisting of 0.01 to 0.4% by weight. The method of claim 3, wherein Wherein said abrasive is selected from the group consisting of fumed silica, colloidal silica, alumina, ceria, zirconium oxide, and mixtures thereof. The method of claim 7, wherein The abrasive is fumed silica or colloidal silica, the abrasive content is 0.5 to 12% by weight at pH 2 to 5, 6 to 12% by weight at the pH 8 to 12 chemical mechanical polishing slurry for copper damascene process Composition. The method of claim 3, wherein The pH of the copper damascene process chemistry, characterized in that the pH is adjusted with a pH adjuster selected from the group consisting of potassium hydroxide, ammonium hydroxide, tetramethylammonium hydroxide, nitric acid, hydrochloric acid, sulfuric acid, perchloric acid, phosphoric acid and mixtures thereof. Mechanical polishing slurry composition. The method of claim 9, Benzotriazole, 5-aminotetrazole, 1-alkyl-5-aminotetrazole, 5-hydroxy-tetrazole, 1-alkyl-5-hydroxy-tetrazole, tetrazol-5thiol, imidazole and these A chemical mechanical polishing slurry composition for copper damascene process further comprising a corrosion inhibitor selected from the group consisting of a mixture of 0.0001 to 0.1% by weight relative to the total weight of the slurry. The method of claim 10, The corrosion inhibitor is a chemical mechanical polishing slurry composition for copper damascene process, characterized in that benzotriazole. The method of claim 11, 6-12 wt% fumed silica or colloidal silica, 0.01-1.0 wt% of one or more additives selected from compounds selected from taurine, gluconic acid, 2-amino-2-methyl-1-propanol or monoethanol amine or salts thereof, A chemical mechanical polishing slurry composition for a copper damascene process containing potassium hydroxide or ammonium hydroxide to bring the pH to 8-12, and 0.005 to 0.05% by weight of benzotriazole. The method of claim 11, 6-12% by weight of fumed silica or colloidal silica; 0.01 to 0.4% by weight of at least one selected from citric acid, 2-amino-2-methyl-1-propanol, monoethanol amine or salts thereof and 0.01 to 0.4 wt% of nitrilotris (methylene) triphosphonic acid (NTPA) or salts thereof 0.4 wt%; potassium hydroxide or ammonium hydroxide to bring the pH to 8-12; And 0.005 to 0.05% by weight of benzotriazole. A method for manufacturing a semiconductor device, characterized in that the secondary chemical mechanical polishing of the copper damascene process is performed using the slurry composition of claim 1.