JP2007073727A - Quantitation method of nitrogen and manufacturing method of semiconductor device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for quantitating the amount of nitrogen introduced into an insulating film in plasma nitriding treatment in the manufacturing process of a semiconductor device. <P>SOLUTION: The method for quantitating the amount of nitrogen comprises processes of: forming a silicon oxide film 12 on the entire surface of a silicon substrate 11; removing the silicon oxide film 12 in a thin-film section 30 by etching; measuring the film thickness of an insulating film at a thick-film section 20 and a thin-film section 30; nitriding the surface of the thick-film section 20 and the thin-film section 30; performing the wet oxidation of the surface of the thick-film section region 20 and the thin-film section region 30; measuring the film thickness of the insulating films 16, 17 in the thick-film section region 20 and the thin-film section region 30; and quantitating the amount of nitrogen introduced by the nitriding process, based on the measured film thickness of the insulating films 16, 17. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a method for determining the amount of nitrogen, and more particularly to a method for determining nitrogen suitable for monitoring the amount of nitrogen in a silicon oxynitride film formed in a semiconductor device. The present invention further relates to a method of manufacturing a semiconductor device including such a nitrogen determination method.

  In a semiconductor device, a silicon layer in which impurities are diffused is generally used as a gate electrode. Among the gate electrodes in which these impurities are diffused, in the p-type gate electrode in which boron is introduced as a p-type impurity, boron leaks to the Si substrate by the subsequent heat treatment, and the threshold voltage of the transistor fluctuates. There's a problem. If the boron leakage amount is constant within the wafer surface, or between wafers and lots, it is possible to design a device after taking into account the variation in threshold voltage. However, in actual semiconductor manufacturing processes, there are variations in the oxide film thickness, heat treatment amount, impurity dose amount, etc., so the amount of boron leakage varies, and even if fluctuations in the threshold voltage are taken into account, a stable threshold voltage can be obtained. Cannot be obtained.

  As a countermeasure against the boron leakage, a plasma nitridation process that has been conventionally incorporated in a semiconductor device manufacturing process forms a silicon nitride layer between a gate electrode and a gate oxide film, and boron leakage from the gate electrode to the substrate surface occurs. Is to block. This plasma nitridation process aims to prevent boron leakage without depending on variations in oxide film thickness, heat treatment amount, impurity dose amount, etc., but excessive nitridation is an increase in fixed electrification caused by elemental nitrogen. There is a concern that the interface state density may increase. For this reason, in order to control the process conditions so that the boron leakage can be prevented to some extent and the influence of fixed electrification and interface state density is minimized, the amount of nitrogen in the silicon oxynitride film is highly accurate. Quantification is required.

In the prior art, the amount of nitrogen in the silicon oxynitride film is generally measured by photoelectron spectroscopy (XPS) or secondary ion mass spectrometry (SIMS). . However, these measurement methods are not suitable for regular monitoring. Therefore, instead of these measurements, the amount of nitrogen can be quantified by measuring the amount of change in film thickness before and after plasma nitriding measured by spectroscopic ellipsometry (spectral ellipsometry) or single wavelength ellipsometry. Has been tried. The determination of the amount of nitrogen using spectroscopic ellipsometry is described in Patent Document 1, for example.
JP 2003-163213 A JP 2004-342656 A

The method of estimating the amount of nitrogen based on the film thickness fluctuation amount before and after the plasma nitriding treatment measured by spectroscopic or single-wavelength ellipsometry, employed in the prior art, has the following problems.
(1) In plasma nitriding of the oxide film surface, the amount of variation in film thickness is small, so that it is difficult to accurately determine the amount of nitrogen.
(2) When the plasma nitridation is performed directly on the surface of the Si substrate, the thin film after the plasma nitridation is a thin film having a thickness of about 2 nm. The desired measurement accuracy cannot be obtained.
(3) In the case of plasma nitridation on any surface of the oxide film and Si substrate, the surface state after plasma nitridation is unstable, so moisture and carbon in the clean room are easily taken into the film and measured. The applied film thickness increases with time. For this reason, the accuracy of determination of the amount of nitrogen is lowered.

  As described above, in the prior art, there is no known accurate means for monitoring the amount of nitrogen in the insulating film without depending on the measurement apparatus, and the plasma nitridation process is managed during the manufacture of the semiconductor device. In the future, the establishment of a method capable of quantitatively determining the amount of nitrogen introduced by plasma nitriding has become an indispensable technical problem in a steady and reproducible manner.

  In view of the above, the present invention has a high accuracy in manufacturing a semiconductor device and the amount of nitrogen that can be quantified in a silicon substrate or an insulating film by plasma nitriding without depending on a measuring device. An object is to provide a quantitative method.

  Further, the present invention provides an improved method for manufacturing a semiconductor device so that the amount of nitrogen introduced into a silicon substrate or insulating film by plasma nitriding can be quantified even during a process of manufacturing an actual product of the semiconductor device. It is also intended to provide.

In order to achieve the above object, a method for quantifying nitrogen according to the first aspect of the present invention comprises:
Nitriding the surface of silicon;
Wet oxidizing the surface of the nitrided silicon;
Measuring the thickness of the insulating film formed on the surface of the wet oxidized silicon;
And quantifying the amount of nitrogen introduced by the nitriding step based on the measured film thickness of the insulating film.

In addition, the method for quantifying nitrogen according to the second aspect of the present invention includes:
Forming an insulating film containing silicon oxide on the surface of silicon;
Measuring the thickness of the formed insulating film to obtain a first measured thickness;
Nitriding the surface of the formed insulating film;
Wet-oxidizing the surface of the nitrided insulating film;
Measuring the thickness of the wet-oxidized insulating film to obtain a second measured thickness;
And quantifying the amount of nitrogen introduced by the nitriding step based on the first measured film thickness and the second measured film thickness.

A method for manufacturing a semiconductor device according to the third aspect of the present invention includes:
Forming an insulating film containing silicon oxide on the surface of the silicon substrate;
Leaving the insulating film in the first portion of the silicon substrate and removing the insulating film from the second portion;
Measuring the thickness of the insulating film of the second portion to obtain a first measured thickness;
Nitriding the surfaces of the first portion and the second portion;
Measuring the thickness of the insulating film at the second portion to obtain a second measured thickness;
Wet oxidizing the surfaces of the first and second portions;
Measuring the thickness of the insulating film in the second portion to obtain a third measured thickness;
And sequentially quantifying the amount of nitrogen introduced into the second part by the nitriding step based on the difference between the first measured film thickness and the third measured film thickness. And

A method for manufacturing a semiconductor device according to the fourth aspect of the present invention includes:
Forming an insulating film containing silicon oxide on the surface of the silicon substrate;
Leaving the insulating film in the first portion of the silicon substrate and removing the insulating film from the second portion;
Measuring the thickness of the insulating film of the first portion to obtain a first measured thickness;
Nitriding the surfaces of the first portion and the second portion;
Measuring the thickness of the insulating film at the first portion to obtain a second measured thickness;
Wet oxidizing the surfaces of the first and second portions;
Measuring the thickness of the insulating film in the first portion to obtain a third measured thickness;
And sequentially quantifying the amount of nitrogen introduced into the first portion by the nitriding step based on a difference between the first measured film thickness and the third measured film thickness. And

  According to the method according to the first to fourth aspects of the present invention, the film thickness of the insulating film formed by the nitriding step and the wet oxidation step performed after the nitriding step, or increased by these steps. Since there is a large correlation between the film thickness of the insulating film and the amount of nitrogen introduced in the nitriding process, the measured film thickness of the insulating film before the nitriding process and the insulating film after wet oxidation By obtaining the difference from the measured film thickness, the nitrogen introduced in the nitriding step can be quantified. Here, since the required film thickness difference is a relatively large difference, the degree of dependence on the measurement apparatus is small, and the amount of nitrogen can be quantified with high accuracy.

  In the method for quantifying nitrogen and the method for manufacturing a semiconductor device of the present invention, the film thickness is preferably measured by spectroscopy or single-wavelength ellipsometry. In this case, highly accurate film thickness measurement is possible.

  Moreover, it is also a preferable aspect of the present invention that the wet oxidation step is performed under process conditions such that a silicon oxide film having a thickness of 2 to 5 nm is formed on the silicon surface. In this case, it is less affected by variations in process conditions in the wet oxidation, and the introduced nitrogen is wet without being lost so much by the wet oxidation, and the accuracy in determining the amount of nitrogen is improved.

  The amount of nitrogen suitable for quantification in the present invention is a nitrogen amount in the range of 5 to 25 atom% in the insulating film. Experiments have confirmed that it is particularly effective for quantifying the amount of nitrogen in this range.

  In a preferred aspect of the method for manufacturing a semiconductor device of the present invention, the quantified nitrogen amount is evaluated based on a difference between the first measured film thickness and the second measured film thickness. The amount of nitrogen determined by examining the difference between the first measured film thickness and the second measured film thickness because the increase in the film thickness of the insulating film varies depending on the degree of variation in process conditions in wet oxidation. It is possible to evaluate whether or not is appropriate.

  The semiconductor device manufacturing method of the present invention may further include a step of plasma nitriding the first and second portions after the step of measuring the third measured film thickness. In this case, the method for manufacturing a semiconductor device of the present invention can be carried out in conformity with the process of actually manufacturing the semiconductor device by a multi-oxide process.

  Prior to the description of the embodiments of the present invention, the principle of the present invention will be described. In order to evaluate the method for determining the amount of nitrogen according to the present invention, the following test was conducted. First, a sample that has been directly plasma-nitrided on a Si substrate is subjected to wet oxidation under the condition that a 3.4 nm silicon oxide film is formed on the silicon surface. We decided to monitor. FIG. 1 shows the measured amount of nitrogen measured by XPS (horizontal axis) and the film thickness before and after oxidation when wet oxidization was performed under the condition of 3.4 nm after direct plasma nitridation on a Si substrate. The correlation with the measured value of change (vertical axis) is shown. In the range of 5 to 20 atom% nitrogen, the amount of change in film thickness increases depending on the amount of nitrogen measured by XPS. Therefore, the method for determining the amount of nitrogen according to the present invention is at least for the amount of nitrogen in the above range. Is effective as a means for quantifying the amount of nitrogen by plasma nitriding.

  Next, the measurement accuracy in the determination of the nitrogen amount according to the present invention will be considered. In the method according to the present embodiment, the film thickness to be measured is in the vicinity of 3 nm, and the film thickness change varies from 2.9 nm to 3.4 nm while the nitrogen amount changes from 10 atom% to 20 atom%. Therefore, the fluctuation range of the film thickness due to plasma nitriding is also relatively large at 0.5 nm / 10 atom%. That is, since there is a sufficient film thickness variation when the nitrogen amount varies, it is considered that high accuracy can be obtained in terms of measurement accuracy. Therefore, it is effective as an improvement measure for the problems (1) and (2) listed as conventional problems. As for the improvement of the problem (3), since wet oxidation is performed after plasma nitriding, most of the film surface is terminated with oxygen atoms, silicon atoms, nitrogen atoms, or hydrogen atoms, so It is mentioned that the film thickness variation with time does not easily occur after oxidation.

  Although the above experiment was performed when plasma nitridation was performed directly on the surface of the silicon substrate, similar results can be obtained when plasma nitridation is performed on the surface of the silicon oxide film formed on the surface of the silicon substrate. I understood that. Therefore, the nitrogen quantification method of the present invention can be applied both when the nitriding treatment is performed directly on the silicon substrate surface and when the nitriding treatment is performed on the oxide film surface.

  Hereinafter, the configuration of the embodiment of the present invention will be described in detail. FIG. 2 is a flowchart showing processing in the nitrogen amount monitoring method according to the embodiment of the present invention. FIGS. 3A to 3D sequentially show the states of the semiconductor devices when the method is performed. It is sectional drawing shown. This embodiment is an example in which the method of the present invention is applied to the manufacture of a semiconductor device using a process of forming a plurality of gate oxide films having different thicknesses on one substrate, that is, a so-called multi-oxide process. For example, in a semiconductor memory device such as a DRAM, MOS transistors having different gate oxide films are used in the memory cell region and the peripheral circuit region. The multi-oxide process is described in Patent Document 2, for example.

  First, as shown in FIG. 3A, an oxide film 12 is formed on the Si substrate 11 by a thermal oxidation method, for example, as a first gate oxidation process (FIG. 2, step S1). Next, a photoresist film is formed on the entire surface, and the region of the Si substrate 11 is divided into two regions: a thick film portion region 20 where a thick gate oxide film is formed, and a thin film portion region 30 where a thin gate oxide film is formed. The photoresist film in the thin film portion region 30 is removed by photolithography and a wet etching process. Thereby, a patterned photoresist film 13 is formed (step S2). Next, using the photoresist film 13 as an etching mask, the oxide film 12 in the thin film portion region 30 is selectively removed to obtain the structure of FIG. 3A (step S3).

  Next, as shown in FIG. 3B, the photoresist film 13 remaining in the thick film portion region 20 is peeled off (step S4). Then, the 1st film thickness measurement which measures the film thickness of the thick film part area | region 20 and the thin film part area | region 30 is performed (step S5). Furthermore, plasma nitriding is performed on both the thick film region 20 and the thin film region 30 in a nitrogen atmosphere and at a temperature of about 100 ° C. or higher (step S6). Subsequent to the plasma nitridation process, the thickness measurement of the silicon oxynitride film 14 is performed in the thick film portion region 20, and the second thickness measurement is performed in which the thickness of the silicon nitride film 15 is measured in the thin film portion region 30. (Step S7). Thereafter, a second gate oxidation process for oxidizing the surface is performed using wet etching in both the thick film region 20 and the thin film region 30 (step S8). A third film thickness measurement is performed to measure the film thickness of the silicon oxide films (insulating films) 16 and 17 in both the thin film region 30 (step S9). The difference between the film thickness obtained by the first film thickness measurement and the film thickness obtained by the third film thickness measurement is obtained, and the amount of nitrogen introduced by the plasma nitridation process according to the same graph as shown in FIG. Is determined (step S10). The above film thickness measurements are all performed by spectroscopy or single wavelength ellipsometry.

  In addition to the steps performed in the conventional multi-oxide process, the nitrogen content determination process according to the embodiment of the present invention includes step S6 for performing plasma nitriding for monitoring, and first to third film thicknesses. Measurement steps S5, S7, and S9 are added. Further, for example, in addition to the conventional nitrogen amount monitoring process described in Patent Document 1, a wet oxidation step S8 and a third film thickness measurement step S9 are performed. In other words, the method of the present embodiment performs plasma nitridation processing under the condition to be monitored by adding a small number of steps to the conventional multi-oxide process for actually manufacturing a semiconductor device, and the amount of nitrogen introduced under that condition is reduced. Quantification is possible. In addition, the determination of the amount of nitrogen by the conventional method and the determination of the amount of nitrogen by the method of the present invention are performed on the same semiconductor device, and the amount of introduced nitrogen is continuously monitored on the product. .

  In the method of the above embodiment, the film thickness of the thin film portion region 30 measured in the third film thickness measurement in step S9 is wet oxidation (step S6) after performing the plasma nitridation process (step S6) on the Si substrate 11. Since the film thickness is after the addition of S8), the process of this embodiment performs substantially the same processing as the evaluation content shown in FIG. Further, the difference between the film thickness of the thin film portion region 30 measured in the second film thickness measurement (step S7) and the film thickness of the thin film portion region 30 measured in the first film thickness measurement (step S5) is The film thickness of the thick film portion region 20 corresponding to the amount of film increase by the plasma nitriding process (step S6) on the surface of the Si substrate 11 and measured by the first film thickness measurement (step S5), The difference from the film thickness of the thick film portion region 20 measured by the second film thickness measurement (step S7) corresponds to the amount of film increase by plasma nitriding (step S6) on the surface of the oxide film 12. Therefore, the process of FIG. 2 is performed by the conventional method of monitoring the amount of nitrogen by increasing the film thickness by plasma nitriding and the nitrogen amount by measuring the difference in film thickness before and after performing wet oxidation after plasma nitriding as proposed in the present invention. The monitor is executed on the same semiconductor device. For this reason, by continuing to perform the processing of FIG. 2 on the product, it is possible to obtain correlation data between the measurement value by the conventional method and the measurement value by the method proposed by the present invention.

  The reason why the correlation data between the measured value obtained by the conventional method and the measured value obtained by the method of the present invention is kept is as follows. That is, in the conventional method, the change in the film thickness on the oxide film before and after the plasma nitridation and the change in the film thickness on the Si substrate are measured. The film thickness changes due to oxidation are collectively measured at once. For this reason, in the method according to the present invention, when the change in film thickness due to wet oxidation varies depending on the process conditions, the amount of nitrogen to be monitored shifts due to this. Therefore, in the process of FIG. 2, the first film thickness measurement and the second film thickness measurement are always performed, so that even if the wet oxidation amount is deviated, the measurement is performed by both methods. It is possible to evaluate the quantified amount of nitrogen from the correlation data of values. 2 includes a plasma nitriding step (step S6) and first to third film thickness measuring steps (steps S5 and S7) in addition to a multi-oxide process conventionally used for manufacturing a semiconductor device product. , S9) can be easily realized, and daily management is also easy.

  When manufacturing a product, a process for executing the processing shown in FIG. 2 is executed as follows, for example. In the manufacturing process, for example, out of 25 wafers in the multi-oxide process, the 25th wafer is extracted before the second gate oxidation process, and the film thickness is measured on the wafer (step S5) and monitored. After performing the additional process of the condition plasma nitriding process (step S6) and the film thickness measurement on the wafer (step S7), the second gate oxidation process is performed by merging with the other 24 wafers (step S6). S8) The film thickness is measured again on the wafer (step S9). Thereby, the flow of FIG. 2 can be realized in the product manufacturing process.

  In the manufacturing process of the above embodiment, only the 25th wafer is subjected to the plasma nitridation process, so the 25th wafer has a different nitrogen distribution from the 1st to 24th wafers. Therefore, wet oxidation is performed to about 3 nm after the plasma nitriding treatment. As a result, the nitride layer on the surface of the Si substrate is substantially removed, and as shown in FIG. 1, the film thickness by wet oxidation after plasma nitridation is compared with the film thickness by wet oxidation when plasma nitridation is not performed. Therefore, for the 25th substrate only, the first gate oxidation film thickness is made thin in advance, and the second gate oxidation film thickness is made thick on the contrary. This makes it possible to assemble the process so that the 25th sheet has the same film thickness as the 1st to 24th sheets, and the nitrogen amount is constant on the actual product without greatly affecting the quality of the product. Monitoring becomes possible.

  In FIG. 1, when the nitrogen amount is 5 to 25 atom%, the film thickness after the second gate oxidation by wet oxidation increases by about 0.4 nm / 10 atom% as compared with that before the oxidation. . Therefore, if a film thickness difference of 0.1 nm can be detected, a variation in the amount of nitrogen of 2.5 atom% can be monitored. Considering that measurement errors of about 10% are included in SIMS and XPS measurements, the method of the present invention is more accurate than the conventional measurement methods as a simple monitor of the amount of nitrogen. Can be said to be quantitative.

  In the process of FIG. 2, the management method using the product is described for the purpose of regularly performing daily management. Instead, for example, a lattice pattern in which white patterns and black patterns are evenly arranged If a reticle that can realize (checkered pattern) is used, the same evaluation can be easily performed without using a product. The outline of the processing at this time is shown below.

  After performing oxidation corresponding to the first gate oxidation which is the first oxidation process on a new Si wafer, using the reticle having the lattice pattern, and continuously performing photolithography and oxide film etching. Thus, the thick film portion region 20 and the thin film portion region 30 are separately formed in a lattice pattern. Subsequently, the first film thickness measurement (step S5), the plasma nitridation process (step S6), the second film thickness measurement (step S7), and the second gate oxidation which is the second oxidation process are performed by wet oxidation. (Step S8) Then, the third film thickness measurement in the thin film portion region 30 is performed (Step S9). Evaluation by this process is the same as that shown in the previous example.

  The advantage of using the above simple process is that the amount of nitrogen can be easily quantified with a simple flow and that evaluation can be performed without affecting the product. Compared with daily management, it is slightly inferior. If only the same measurement as in FIG. 1 is performed, the film thickness can be measured after plasma nitriding and wet oxidation are directly performed on a new Si wafer.

  As described above, the present invention has been described based on the preferred embodiment. However, the nitrogen determination method and the semiconductor device manufacturing method of the present invention are not limited to the configuration of the above-described embodiment. Those in which various modifications and changes are made from the configuration of the embodiments are also included in the scope of the present invention.

  The method for determining the amount of nitrogen in a semiconductor device of the present invention is suitably used for manufacturing a semiconductor device such as a DRAM device employing a multi-oxide process.

The graph which shows the correlation between the film thickness of the insulating film after performing wet oxidation of 3.4 nm conditions after plasma nitridation on a Si substrate, and the nitrogen content by XPS measurement. The flowchart which shows the determination method of the nitrogen content which concerns on one Embodiment of this invention. FIG. 3 is a cross-sectional view showing a state of a semiconductor device for each process stage in the flowchart of FIG. 2.

Explanation of symbols

11: Si substrate 12: Oxide film 13: Photoresist film 14: Oxide film 15: Silicon nitride film 16, 17: Oxide film (insulating film)

Claims (12)

Nitriding the surface of silicon;
Wet oxidizing the surface of the nitrided silicon;
Measuring the thickness of the insulating film formed on the surface of the wet oxidized silicon;
And a step of quantifying the amount of nitrogen introduced by the nitriding step based on the measured film thickness of the insulating film. Forming an insulating film containing silicon oxide on the surface of silicon;
Measuring the thickness of the formed insulating film to obtain a first measured thickness;
Nitriding the surface of the formed insulating film;
Wet-oxidizing the surface of the nitrided insulating film;
Measuring the thickness of the wet-oxidized insulating film to obtain a second measured film thickness;
And a step of quantifying the amount of nitrogen introduced by the nitriding step based on the first measured film thickness and the second measured film thickness.   The method for quantifying the amount of nitrogen according to claim 1 or 2, wherein the film thickness is measured by spectroscopy or single wavelength ellipsometry.   The method for quantitatively determining nitrogen according to any one of claims 1 to 3, wherein the wet oxidation step is performed under process conditions for forming a silicon oxide film having a thickness of 2 to 5 nm on a silicon surface.   The nitrogen determination method according to claim 1, wherein the amount of nitrogen to be quantified is a nitrogen amount in the range of 5 to 25 atom% in the insulating film. Forming an insulating film containing silicon oxide on the surface of the silicon substrate;
Leaving the insulating film in the first portion of the silicon substrate and removing the insulating film from the second portion;
Measuring the thickness of the insulating film of the second portion to obtain a first measured thickness;
Nitriding the surfaces of the first portion and the second portion;
Measuring the thickness of the insulating film at the second portion to obtain a second measured thickness;
Wet oxidizing the surfaces of the first and second portions;
Measuring the thickness of the insulating film in the second portion to obtain a third measured thickness;
And sequentially quantifying the amount of nitrogen introduced into the second part by the nitriding step based on the difference between the first measured film thickness and the third measured film thickness. A method for manufacturing a semiconductor device. Forming an insulating film containing silicon oxide on the surface of the silicon substrate;
Leaving the insulating film in the first portion of the silicon substrate and removing the insulating film from the second portion;
Measuring the thickness of the insulating film of the first portion to obtain a first measured thickness;
Nitriding the surfaces of the first portion and the second portion;
Measuring the thickness of the insulating film at the first portion to obtain a second measured thickness;
Wet oxidizing the surfaces of the first and second portions;
Measuring the thickness of the insulating film in the first portion to obtain a third measured thickness;
And sequentially quantifying the amount of nitrogen introduced into the first portion by the nitriding step based on the difference between the first measured film thickness and the third measured film thickness. A method for manufacturing a semiconductor device.   The method for manufacturing a semiconductor device according to claim 6, wherein the quantified nitrogen amount is evaluated based on a difference between the first measured film thickness and the second measured film thickness.   The method for manufacturing a semiconductor device according to claim 6, further comprising a step of nitriding the first and second portions after the step of measuring the third measured film thickness.   The method for manufacturing a semiconductor device according to claim 6, wherein the film thickness measurement is performed by spectroscopy or single-wavelength ellipsometry.   The method for manufacturing a semiconductor device according to claim 6, wherein the wet oxidation step is performed under process conditions for forming a silicon oxide film having a thickness of 2 to 5 nm on a surface of a silicon substrate.   The method for manufacturing a semiconductor device according to claim 6, wherein the amount of nitrogen to be quantified is a nitrogen amount in the range of 5 to 25 atom% in the insulating film.

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