JP2007317491A - Method and apparatus for ionizing cluster - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method and an apparatus for ionizing clusters which ionize clusters efficiently, suppress the generation of monomer ions, and enable generation of cluster ions creating a large electric current. <P>SOLUTION: According to the method for ionizing clusters, neutral clusters generated in a cluster generation chamber 1 are led through a schemer 4 and a cluster beam adjusting chamber 5 to an ionizing chamber 6, where the neutral clusters are ionized. The ionizing chamber 6 is separated from the cluster beam adjusting chamber 5 via a partition wall, and is exhausted through an exhaust port 8 formed on the ionizing chamber 6 to keep the interior of the ionizing chamber 6 lower in pressure than the interior of the cluster beam adjusting chamber 5 to ionize the neutral clusters. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  TECHNICAL FIELD The present invention relates to a cluster ionization method and an ionization apparatus, and in particular, an ionization method and ionization of a gas cluster that is an aggregate of gaseous atoms at room temperature and a material cluster that is an aggregate of material atoms that become a film material. Relates to the device.

Electron impact ionization (EI) is one of the most commonly used ionization methods for ionizing gas sample clusters and molecules in gas cluster ion sources and mass spectrometers.
An outline of a conventional gas cluster ionization apparatus using the EI method will be described with reference to FIG.
In this apparatus, a gas cluster is introduced into an ionization chamber 31 arranged in a vacuum vessel (not shown).
Therefore, an incident hole 32 and an emission hole 33 for thermionic current are provided in a direction substantially perpendicular to the introduction direction (up and down in the drawing).
A neutral cluster incident hole 34 and a cluster ion emitting hole 35 are provided on the cluster traveling axis orthogonal to the electron flow axis L connecting the incident hole 32 and the emitting hole 33.
A filament (thermocathode) 37 for generating thermoelectrons is formed on the electron flow axis L outside the incident hole 32, and a trap electrode (for trapping the electron flow on the electron flow axis L outside the emission hole 33). 38) (also called electron collectors, targets, etc.) are placed opposite.
A pair of magnets 39 and 40 are arranged on the outer side of the filament 37 and the trap electrode 38.
In the above configuration, a heating current is supplied to the filament 37 to emit electrons, and an appropriate potential difference is generated between the filament 37 and the ionization chamber 31 or the trap electrode 38 to impart kinetic energy to the electrons. .
Further, a magnetic field is formed by the magnets 39 and 40 so that the flight direction of the electrons generated in the filament 37 is aligned with the direction of the electron flow axis L.
Thereby, the electrons generated in the filament 37 enter the ionization chamber 31 through the incident hole 32 for the thermal electron flow, and fly along the direction of the electron flow axis L toward the trap electrode 38.
When a neutral cluster is touched during the flight, electrons are ejected from the cluster to ionize the cluster.
In general, electrons are configured to come into contact with sample molecules with an energy of about 70 (eV).
The generated cluster ions are extracted by an electric field formed by an electrode (not shown) arranged outside the cluster ion emission hole 35 of the ionization chamber 31.
Then, the acceleration voltage and ion beam shape are appropriately adjusted by an acceleration electrode, an ion lens, etc. (not shown), and the substrate is irradiated.

Conventionally, as an electron impact ionization method of such a gas cluster, for example, Patent Document 1 proposes a technique for improving ionization efficiency by forming a circular elliptical ionization region by devising a filament shape or the like. .
Further, in Patent Document 2, by applying an electron acceleration voltage and a magnetic field perpendicular to the ion flight direction, particularly by maximizing the magnetic field strength of the portion overlapping the ion flight, the moving speed of the electron cyclotron motion is slowed down. A method for improving the ionization rate has been proposed.
Japanese translation of PCT publication No. 2003-520393 JP 2002-373616 A

However, in the conventional ionization method described above, a technique is adopted in which electrons are accelerated and moved in a direction orthogonal to the ion flight direction to increase the collision probability between electrons and gas clusters and gas molecules, thereby improving ionization efficiency. Therefore, it had the following problems.
As described above, electrons and gas clusters collide in a direction orthogonal to the ion flight direction, so even if the configuration is such that the electron trajectory is controlled by a magnetic field or electric field and concentrated near the center, the collision probability jumps dramatically. The ionization efficiency cannot always be increased.
Also, especially in gas clusters, neutral clusters introduced into the ionization chamber are particularly concentrated near the center of the ionization chamber, and electron beam irradiation from orthogonal directions can efficiently ionize by electron impact. difficult.
For this reason, in order to raise ionization efficiency, it was necessary to take a large electron current, and there also existed a problem of shortening the lifetime of a filament.
In addition, when ionizing gas clusters that are easily dissociated by electron beam bombardment, an electron beam bombardment with a higher energy than necessary causes not only ionization but also the dissociation of the clusters, leading to generation of unnecessary monomer ions and a reduction in cluster size. It becomes.

In addition, it is said that an impact with an electron beam of 15.7 eV or more is necessary for ionization of Ar.
However, in normal Ar gas ionization, the ionization efficiency is maximized by electron beam bombardment of about 70 eV (Japanese Patent Laid-Open No. 5-47327). Until now, the acceleration voltage of an electron beam has been 70 V to 100 V, depending on the case. A voltage higher than that was applied.
Since there is a distribution in the energy conversion efficiency and the collision state between electrons and neutral particles, electron beam bombardment with high energy is necessary to some extent, but the conditions suitable for ionization of gas clusters are not necessarily I can't say that.
In high energy electron beam bombardment, excess energy is used for ionization to dissociate clusters, resulting in a decrease in cluster size and generation of monomer ions.

In addition, gas clusters can be etched and assisted vapor deposition with various characteristics for the first time with a size in which several hundred to several thousand atoms are combined. When monomer ions are mixed with these cluster ions, the film or substrate is Various harmful effects such as damage will occur.
For this reason, although light ions such as monomer ions are excluded by a size separator or the like, it has been a big problem in improving the ionization efficiency of the gas cluster ion source and maximizing the cluster ion current value.

In addition, the conventional ionization chamber of the cluster is placed in substantially the same pressure state as the introduction part and the emission part of the cluster.
In order to extend the life of the filament, only the thermoelectron supply source may be configured to keep the pressure low, but in the case of an ion source that supplies electrons using gas discharge, a gas such as Ar is used in the discharge forming portion. To cause gas discharge. For this reason, the gas pressure in the ionization chamber was rather increased.
In such an ionization chamber, not only ionization of clusters but also ionization of gas atoms and molecules occur simultaneously, and monomer ions formed in the ionization chamber diffuse out of the ionization chamber.
At this time, since the ionization part is maintained at a high voltage for accelerating the cluster ions, the ions diffused outside the ionization chamber are accelerated by this electric field and incident on the skimmer or other electrodes to damage the electrodes. In addition, there has been a problem that the electrode is sputtered to become a contamination source.

  In view of the above problems, the present invention can efficiently ionize a cluster, suppress the generation of monomer ions, and increase the cluster ion current and ionization method. An object is to provide an apparatus.

In order to achieve the above object, the present invention provides a cluster ionization method and ionization apparatus configured as follows.
The cluster ionization method of the present invention includes a cluster generation chamber that generates a neutral cluster by injecting a gas, and a cluster beam adjustment chamber that is adjacent to the cluster generation chamber via a skimmer. The room has an ionization chamber,
The neutral cluster generated in the cluster generation chamber is introduced into the ionization chamber via a skimmer and a cluster beam adjustment chamber, and the cluster ionization method ionizes the neutral cluster,
The ionization chamber is separated from the cluster beam adjustment chamber by a partition wall, the gas in the ionization chamber is exhausted from an exhaust port provided in the ionization chamber, and maintained at a lower pressure than the cluster beam adjustment chamber, The neutral cluster is ionized.
Further, in the cluster ionization method of the present invention, the ionization chamber has a neutral cluster introduction part and a cluster ion emission part, and each of the opening diameters of the neutral cluster introduction part and the cluster ion emission part is determined by the diameter of the skimmer. It is characterized in that it is set in the range of 1 to 2 times.
The cluster ionization method of the present invention is characterized in that the pressure state in the ionization chamber is adjusted by adjusting an exhaust amount from an exhaust port provided in the ionization chamber.
The cluster ionization method according to the present invention uses an electron acceleration electrode in which electrons emitted by the electron emission means provided in the ionization chamber are parallel to the flight direction of the neutral cluster introduced into the ionization chamber. Accelerates by applying an electric field,
The neutral cluster is ionized by causing a cyclotron motion of electrons by applying a magnetic field by a magnetic field generating means.
The cluster ionization apparatus of the present invention includes a cluster generation chamber that generates a neutral cluster by injecting gas, and a cluster beam adjustment chamber that is adjacent to the cluster generation chamber via a skimmer. An ionization chamber is provided in the beam adjustment chamber,
A cluster ionization apparatus for introducing a neutral cluster generated in the cluster generation chamber into an ionization chamber through a skimmer and a cluster beam adjustment chamber, and ionizing the neutral cluster,
The ionization chamber is separated from the cluster beam adjustment chamber by a partition wall, and has an exhaust port for exhausting the ionization chamber,
It has exhaust means configured to be able to be decompressed more than the cluster beam adjustment chamber by exhausting from the exhaust port.
Further, in the cluster ionization apparatus of the present invention, the ionization chamber has a neutral cluster introduction portion for introducing the neutral cluster, and an emission portion for cluster ions ionized in the ionization chamber,
The opening diameter of the neutral cluster introduction part and the opening diameter of the cluster ion emission part are set to be 1 to 2 times the diameter of the skimmer.
In the cluster ionization apparatus of the present invention, the exhaust means is configured to be capable of adjusting an exhaust amount from an exhaust port.
In the cluster ionization apparatus according to the present invention, the ionization chamber includes:
An electron emission filament that emits electrons for ionizing the neutral clusters;
An electron accelerating electrode that accelerates electrons emitted by the electron emitting filament in parallel with the flight direction of the neutral cluster introduced into the ionization chamber;
Magnetic field generating means for causing the electrons emitted by the electron emitting filament to cause electron cyclotron motion parallel to the flight direction of the neutral cluster introduced into the ionization chamber is provided.

According to the present invention, the cluster can be efficiently ionized and the generation of monomer ions can be suppressed, and the current of the cluster ions can be increased.
This also makes it possible to realize a stable cluster ionization method and ionization apparatus.

With the above configuration, the above-described problem of the present invention can be achieved, which is based on the following knowledge of the present invention.
That is, the ionization chamber of the cluster ion source only needs to ionize a cluster that is a group of atoms such as gas, and gas molecules are not necessary in the ionization chamber. In other words, only the clusters need exist in the ionization chamber.
Neutral clusters blown out from a nozzle that is normally used and cut out by a skimmer are in a supersonic state at the time of exiting from the nozzle, and are clustered to have a large mass, so that the directionality of movement is high.

Therefore, in the present invention, the opening diameter of the neutral cluster introduction port or the ionized cluster exit port is set to be 1 to 2 times the skimmer diameter to reduce the conductance and exhaust the ionization chamber. If it is less than 1 time, the probability of the neutral cluster entering the ionization chamber is lowered, and if it is more than 2 times, the exhaust efficiency is deteriorated. By reducing the conductance by setting the opening diameter of the neutral cluster introduction port and the exit port of the ionized cluster to 1 to 2 times the skimmer diameter, the pressure inside the ionization chamber can be kept lower than the cluster generation chamber in the ionization chamber. At the same time, even if the ionization chamber is exhausted and decompressed, the existence probability of the neutral cluster does not change greatly. It is gas molecules that are easy to diffuse.
In such ionization in the ionization chamber, generation of monomer ions generated by ionization of gas molecules can be reduced. Of course, since the neutral cluster existence probability does not change, the collision probability between electrons and clusters does not change greatly, and the ionization efficiency of the clusters does not change greatly.
The monomer ions generated in this way and the monomer ions generated during the ionization process of the cluster have a low probability of diffusing outside the ionization chamber, and as a result, there is an effect of suppressing damage to the external electrode and generation of impurities due to sputtering. Since the pressure in the ionization chamber is low, the probability that the cluster breaks by collision with gas molecules is also low.
If a filament is provided in the ionization chamber maintained at the low pressure, the effect of extending the life of the filament can be obtained at the same time.
In the above configuration, the thermoelectrons emitted from the filament are accelerated toward the accelerating electrode in parallel with the flight direction of the cluster, and at the same time, perform a cyclotron motion under the influence of an external magnetic field. In particular, by adjusting the strength of the magnetic field and the acceleration voltage of the electrons so that the radius of the neutral cluster distribution density is 2 mm or less, the probability of collision between the clusters and the electrons is dramatically increased.

In order to suppress the dissociation of the cluster as much as possible, the acceleration energy of the electrons needs to be about the ionization voltage.
This is because excess energy generated in ionization is used for dissociation of clusters, but the probability of ionization becomes low at a low voltage. Therefore, efficient ionization cannot be performed.
However, since the collision probability is increased by the above-described configuration of the present invention, the acceleration voltage of electrons can be reduced to 60 V or less, and the clusters can be efficiently ionized while dissociating the clusters as much as possible.
In addition, with the above configuration, a practical ion current having a cluster size of several thousand or more can be maximized, whereby a large size cluster ion can be efficiently obtained.

The cluster ions obtained as described above are applied to a cluster-assisted film-forming method that can irradiate the surface of the thin film during thin film formation and obtain a high-quality thin film with high mechanical strength on a non-heated substrate. Can be used. Alternatively, it can be used when the substrate surface is irradiated to polish the substrate.
The material cluster can be used for wiring, thin film formation, etc. by irradiating the substrate surface.

Next, examples of the present invention will be described.
The following examples will be described with reference to limited gas species, film materials, etc., but the present invention is not limited to these examples.
[Example 1]
In Example 1, a gas cluster ionization apparatus is configured by applying the configuration of the present invention.
FIG. 1 shows a schematic diagram of a gas cluster ionization source in the present embodiment.
In FIG. 1, 1 is a cluster generation chamber, 2 is a high-pressure gas introduction part, 3 is a nozzle, 4 is a skimmer, A is a skimmer diameter, 5 is a beam adjusting chamber, 6 is an ionization chamber, 7 is a magnetic field generator, and 8 is ionization. This is a room exhaust port.
Further, 9 is a hot filament, 10 is a thermoelectron acceleration electrode, 11 is an extraction electrode, 12 is an Einzel lens, 13 is an ion inlet, and 14 is a cluster ion acceleration power source.

The cluster ions generated by the gas cluster ion source of the present embodiment are irradiated through the ion introduction port 13 to the substrate to be processed and the substrate to be etched in a vacuum chamber (not shown).
The generation of such cluster ions will be described next.
First, in the cluster generation chamber 1, the high-pressure gas injected at high speed from the nozzle 3 is adiabatically cooled to generate a cluster.
The generated cluster is introduced via the skimmer 4 into the ionization chamber 6 in the cluster beam adjusting chamber 5 adjacent to the cluster generation chamber 1 via the skimmer 4. The ionization chamber 6 is configured to be completely closed by a partition except for the cluster introduction portion and the emission portion, and the gas in the ionization chamber 6 is exhausted from the exhaust port 8 by an exhaust means (not shown) such as a pump. The pressure is always kept lower than that of the beam adjusting chamber 5.
The pressure in the ionization chamber 6 varies depending on conductance, exhaust speed, cluster beam intensity, and the like of the ionization chamber.
Although not shown in the present embodiment, the pressure in the ionization chamber can be adjusted by adjusting the conductance of the cluster introduction part and the emission part and the conductance of the exhaust port for pressure adjustment.
A hot filament 9 which is a thermoelectron emission source for ionizing the cluster is provided on the ionization chamber side of the cluster entrance.
Further, in order to accelerate the thermoelectrons emitted therefrom in parallel with the flight direction of the cluster by applying an electric field, a thermoelectron acceleration electrode 10 is provided on the cluster emission part side. Furthermore, a magnetic field generator 7 that applies a magnetic field parallel to the flight direction of the cluster is provided so as to surround the ion source.

Next, the ionization method using the gas cluster ionization apparatus of the present embodiment will be described in more detail.
Gas molecules emitted from the nozzle are accelerated and cooled in the skimmer direction at supersonic speed, and molecules are bonded to each other to generate neutral clusters.
Neutral clusters are generated efficiently near the center of the nozzle, and the probability of cluster generation decreases rapidly in the radial direction. The generated neutral clusters are introduced into the ionization chamber via the skimmer 4 while maintaining an accelerated state.
This neutral cluster consists of several thousand molecules / atoms on average, and has a very large mass, so the flight direction does not change easily in collision with other molecules / atoms, and proceeds almost linearly.
For this reason, even if the opening diameter of the introduction part of the ionization chamber 6 is the same as or slightly larger than the skimmer diameter A, the probability of penetration of the neutral clusters into the ionization chamber 6 is not greatly reduced.
Also in the ionization chamber 6, the existence probability of neutral clusters is very high near the center.
Since the ionization chamber 6 is evacuated and connected to the beam adjustment chamber 5 with only a few openings, it is easy to maintain a low pressure.
As a result, the lifetime of the filament 9 heated inside the ionization chamber 6 for thermionic emission can be maintained long.
Since the neutral cluster introduced into the ionization chamber 6 has high straightness, it is localized near the center of the ionization chamber, and is emitted from the filament 9 and ionized by accelerated thermoelectrons during the flight process.
At this time, the thermoelectrons emitted from the filament 9 are affected by the magnetic field parallel to the cluster flight direction formed by the thermoelectron accelerating electrode 10 and the magnetic field generator 7, and are parallel to the flight direction of the neutral cluster and also have a cyclotron motion. While colliding with the cluster. Thereby, the cluster is ionized.
Depending on the distribution of the magnetic field, it is possible to increase the electron density particularly near the center of the ionization chamber having a high neutral cluster density.

As described above, the electron density in the region where the existence probability of the neutral cluster is high is raised by the filament 9 for thermionic emission, the electrode 10 for thermionic electron acceleration, and the magnetic field generator 7, and the neutral cluster is caused to move while performing the cyclotron motion. Accelerate electrons parallel to the direction of flight.
As a result, the probability of collision with the cluster is dramatically increased, and the ionization efficiency can be dramatically increased.
Further, by supplementing the ionization efficiency with an increase in electron density and collision probability as in the above embodiment, cluster ions can be efficiently generated even if the acceleration voltage of the thermal electrons is 60 V or less.
In addition, from the relationship between the acceleration voltage and the cluster size, the closer to the ionization potential, the more the acceleration voltage can be ionized without causing cluster collapse, which is very effective for generating large-sized cluster ions.
Moreover, since the degree of vacuum can be kept low, the filament life can be extended, and the ion source can be operated stably for a long time.
Further, the gas pressure in the ionization chamber 6 is maintained lower than that of the beam adjustment chamber 5.
For this reason, it is possible to prevent ions of neutral gas molecules other than the clusters ionized in the ionization chamber 6 from diffusing and leaking out of the ionization chamber 6.
According to the present embodiment, as in the conventional example, ions that diffuse and leak from the cluster entrance and exit of the ionization chamber 6 are accelerated by the cluster ion acceleration voltage 14 and enter the skimmer and other electrodes. There is no problem that the electrode is destroyed or sputtered and becomes a contamination source.

[Example 2]
In the second embodiment, the gas cluster ion source is configured by further adding to the gas cluster ionization apparatus of the first embodiment a configuration that suppresses the destruction of the cluster between the skimmer and the ionization chamber.
The present embodiment is different from the first embodiment only in the configuration in which the configuration for suppressing the destruction of the cluster is added to that in the first embodiment, and the configurations of the other gas cluster ion sources are all common. Only the configuration will be described.
FIG. 2 shows a schematic diagram of a gas cluster ionization source in the present embodiment.
In FIG. 2, 21 is a skimmer and 22 is an exhaust port.

Clusters consisting of gas molecules and atoms have a low bonding force, so they will be destroyed if they collide with other gas molecules during the flight process.
For this reason, in the cluster generation process, it is necessary to increase the probability of collision with other gas molecules and atoms and to keep the probability of collision low after generation.
In the configuration of the present embodiment, as described above, since the internal pressure of the ionization chamber 6 is lower than that in the conventional configuration, the probability of destruction of the cluster can be suppressed low, and thus cluster ions can be generated efficiently.
However, in the configuration of the first embodiment, there is a possibility that cluster destruction occurs between the skimmer 4 and the ionization chamber 6. The pressure in the ionization chamber 6 is also affected by the pressure in the beam adjustment chamber 5.
For this reason, in this embodiment, as shown in FIG. 2, another skimmer 21 is provided between the skimmer 4 and the ionization chamber 6, and the space between the skimmer 4 and the skimmer 21 is exhausted from the exhaust port 22. It was configured as follows.
According to the configuration of this embodiment, it is possible to suppress the destruction of the cluster between the skimmer 4 and the ionization chamber 6, and it is possible to generate cluster ions more efficiently.

Schematic which shows the structure of the gas cluster ionization apparatus in Example 1 of this invention. Schematic which shows the structure of the gas cluster ionization apparatus in Example 2 of this invention. Schematic which shows the structure of the gas cluster ionization apparatus in a prior art example.

Explanation of symbols

1: Cluster generation chamber 2: High-pressure gas introduction unit 3: Nozzle 4: Skimmer 5: Beam adjustment chamber 6: Ionization chamber 7: Magnetic field generator 8: Ionization chamber exhaust port 9: Hot filament 10: Electron for thermoelectron acceleration 11: Extraction electrode 12: Einzel lens 13: Ion introduction port 14: Cluster ion acceleration power supply 21: Skimmer 22: Exhaust port

Claims (8)

A cluster generation chamber for generating a neutral cluster by injecting gas; a cluster beam adjustment chamber adjacent to the cluster generation chamber via a skimmer; and an ionization chamber provided in the cluster beam adjustment chamber,
The neutral cluster generated in the cluster generation chamber is introduced into the ionization chamber via a skimmer and a cluster beam adjustment chamber, and the cluster ionization method ionizes the neutral cluster,
The ionization chamber is separated from the cluster beam adjustment chamber by a partition wall, the gas in the ionization chamber is exhausted from an exhaust port provided in the ionization chamber, and maintained at a lower pressure than the cluster beam adjustment chamber,
A cluster ionization method comprising ionizing the neutral cluster.   The ionization chamber has a neutral cluster introduction part and a cluster ion emission part, and each of the opening diameters of the neutral cluster introduction part and the cluster ion emission part is set to be 1 to 2 times the diameter of the skimmer. The cluster ionization method according to claim 1.   The cluster ionization method according to claim 1 or 2, wherein the pressure state in the ionization chamber is adjusted by adjusting an exhaust amount from an exhaust port provided in the ionization chamber. Electrons emitted by the electron emission means provided in the ionization chamber,
In parallel with the flight direction of the neutral cluster introduced into the ionization chamber, the electron acceleration electrode is accelerated by applying an electric field, and the magnetic field is generated by the magnetic field generating means to generate a cyclotron motion of electrons.
A cluster ionization method comprising ionizing the neutral cluster. A cluster generation chamber for generating a neutral cluster by injecting gas; a cluster beam adjustment chamber adjacent to the cluster generation chamber via a skimmer; and an ionization chamber provided in the cluster beam adjustment chamber,
A cluster ionization apparatus for introducing a neutral cluster generated in the cluster generation chamber into an ionization chamber through a skimmer and a cluster beam adjustment chamber, and ionizing the neutral cluster,
The ionization chamber is separated from the cluster beam adjustment chamber by a partition wall, and has an exhaust port for exhausting the ionization chamber,
A cluster ionization apparatus comprising exhaust means configured to be able to be depressurized more than the cluster beam adjustment chamber by exhausting from the exhaust port. The ionization chamber has a neutral cluster introduction portion for introducing the neutral cluster, and an emission portion for cluster ions ionized in the ionization chamber,
6. The cluster ionization apparatus according to claim 5, wherein an opening diameter of the neutral cluster introduction part and an opening diameter of the cluster ion emission part are set to be not less than 1 and not more than 2 times the diameter of the skimmer. .   The cluster ionization apparatus according to claim 5, wherein the exhaust means is configured to be capable of adjusting an exhaust amount from an exhaust port. The ionization chamber is
An electron emission filament that emits electrons for ionizing the neutral clusters;
An electron accelerating electrode that accelerates electrons emitted by the electron emitting filament in parallel with the flight direction of the neutral cluster introduced into the ionization chamber;
Magnetic field generating means for causing electrons emitted by the electron-emitting filament to generate a cyclotron motion of electrons parallel to the flight direction of the neutral cluster introduced into the ionization chamber;
The cluster ionization apparatus according to any one of claims 5 to 7, further comprising:

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