JP5525319B2 - Etching method and etching apparatus - Google Patents

Description

  The present invention relates to a semiconductor substrate etching method and an etching apparatus, and more particularly, to an etching method and an etching apparatus that perform dry etching to form a high aspect ratio groove and / or hole.

  With the integration of semiconductors, chip miniaturization is progressing, such as connecting a plurality of chips in a stacked manner and consolidating them into one chip. Conventionally, a connection method using a wire has been used for connection between chips, but at present, a connection method using electrodes penetrating a plurality of chips is becoming mainstream. In order to form this through electrode, it is necessary to form a deep hole of 10 μm or more in a silicon substrate or SOI substrate.

In order to perform the above-described processing, in a dry etching method using a mixed gas such as O ₂ , Cl _2, HBr, or CF ₄ that has been used to form element isolation in a silicon substrate, contact holes, capacitors, and the like, The reaction product generated by etching such as -C and Si-Br is low in volatility, so it is easy to reattach, and has a strong deposition property (depositing property), so the etching rate of silicon is reduced and the throughput is reduced. There was a problem.

In order to solve this problem, a dry etching method using a mixed gas plasma using a mixed gas of a fluorine-containing gas such as SF ₆ gas and an oxygen-containing gas such as O ₂ gas has been proposed.

For example, SF ₆ and O ₂ gases are dissociated into S, F, and O ions and radicals, respectively, and react with the silicon substrate surface to produce reaction products such as Si—F, Si—O, and Si—O—F. Generated. Si-F is most generated when Si is etched, and Si is extracted by F, so that etching of Si proceeds.

  Etching of Si—F is more likely to proceed because of higher binding energy than Si—Cl, Si—C, Si—Br, and the like. Si-F has a high vapor pressure, a low bond energy of the substance itself, and is removed by volatilization depending on the temperature of the substrate and incident ions, so that the amount of adhesion is small.

  On the other hand, since Si—O and Si—O—F are non-volatile reaction products, they are easily reattached to the side wall, and thus are formed as a protective film for the side wall.

  From the above, it is possible to perform anisotropic and high-speed etching only in the depth direction while appropriately suppressing side etching.

Further, in this dry etching method, Si—O generated by the reaction with the silicon of the substrate is formed by a plasma of a mixed gas of SF ₆ gas and O ₂ gas. There is also an advantage that the generation of foreign matter due to peeling of the film is small and the wet cycle can be lengthened.

Further, by-products formed with SF ₆ gas and Si—O thinly formed on the inner wall of the chamber with O ₂ gas suppress the scattering of metal contaminants generated from the chamber member to the silicon substrate, and form on the substrate. There is an effect of reducing characteristic defects of semiconductor devices.

In the conventional technique using SF ₆ gas and O ₂ gas, etching by F radicals is the main, and therefore the side etching 23 tends to be large in the silicon layer 21 shown in FIG. Reference numeral 22 denotes a mask. A large amount of O ₂ is added for the purpose of reducing side etching 23 and promoting etching in the depth direction, and etching proceeds while protecting the side walls of reaction products such as Si—O and Si—O—F. To go.

However, when O _{2 as the} additive gas exceeds a certain ratio, the effect of protecting the side walls is increased and a tapered shape is obtained. Although the influence of the taper angle is small in the trench process and via process of several μm in depth, the influence of the taper angle becomes large in DT (Deep Trench) and TSV (Through-Silicon Via) of several tens of μm in depth. Controllability is important.

  As for the side wall protection method using a reaction product, it has been proposed to suppress side etching and bowing shape by cooling the silicon substrate to 0 degrees or less (see, for example, Patent Document 1). However, for trenches and vias with an aspect ratio exceeding 20 and a depth of several tens of μm, the etching time becomes long, so that the side wall protection cannot be caught up only by lowering the silicon substrate. Since the attached reactive organisms are etched, side etching or bowing is likely to occur.

  Further, when the depth of the groove or the hole is deepened in the Trench process or the Via process, the mask 22 is lost during the etching, and problems such as an increase in the size of the opening are likely to occur. When the dimension of the opening is widened due to the disappearance of the mask, the side surfaces of the Trench and Via become stepped and the side walls become rough. Depending on the purpose of formation, conductors or insulating materials are embedded in the trenches and vias.

  For example, when the trench is used for the purpose of element isolation, an insulating film such as a silicon oxide film is embedded in the trench. However, due to the presence of the side etching 23, the embedding is incomplete, and voids called voids are formed in the oxide film. As a result, there has been a problem that the yield is lowered due to an increase in leakage current and a decrease in dielectric strength. Therefore, suppressing the occurrence of the side etching 23 is an important problem in securing device characteristics.

  In order to solve this problem, it has been proposed to improve the selectivity with respect to an oxide film mask by intermittently applying a high-frequency bias (for example, see Patent Document 2). However, TSV has many masks of organic films, such as a photoresist, and the solution method is not shown about the problem with respect to this organic film.

JP 2003-37100 A JP 2007-059696 A

  An object of the present invention is to form a deep groove or hole in a silicon substrate or an SOI substrate using a fluorine-containing gas and an oxygen-containing gas, and at the same time, performs silicon etching while minimizing mask etching. An object of the present invention is to provide a dry etching method and an etching apparatus that minimize etching.

  This problem can be solved by adding a gas containing Si, which is the same as the reaction product, to the fluorine-containing gas and the oxygen-containing gas because the reaction product produced by etching alone does not provide sufficient sidewall protection. Further, with respect to the selection ratio with respect to the mask, it is possible to improve the selection ratio by adding a Si-containing gas and depositing reactive organisms on the mask after providing a time during which the RF bias is not applied at regular intervals.

The etching method of the present invention is an etching method for forming grooves and / or holes in an SOI substrate or a silicon substrate, generating a mixed gas plasma using a fluorine-containing gas, an oxygen-containing gas, and a silicon-containing gas, In the etching method in which an intermittent high-frequency bias modulated with time is applied to the SOI substrate or the silicon substrate, the fluorine-containing gas is any one of SF ₆ , S ₂ F ₁₀ , CF ₄ or two of them. The above-mentioned mixed gas, wherein the oxygen-containing gas is any one of O ₂ , CO, CO ₂ , SO ₂ , or a mixed gas thereof, and the silicon-containing gas is any one of SiF ₄ , SiCl ₄ , or a mixture thereof 2 is a temperature control part in an electrode on which the SOI substrate or silicon substrate placed in the reaction vessel is placed. Has the reason, the temperature of each part is set to different temperatures -35 ℃ ~-45 ℃, increasing the flow rate of SiF ₄ in the silicon-containing gas, further, the bias power applied per unit time The off-F time of the high-frequency bias is controlled by the period of the time modulation bias using a time modulation bias that can be fixed and time-modulated to apply and stop the bias applied to the SOI substrate or silicon substrate. characterized in that it.

The etching apparatus of the present invention is an etching apparatus for forming grooves and / or holes in an SOI substrate or a silicon substrate, and introducing a mixed gas into a reaction vessel using a fluorine-containing gas, an oxygen-containing gas, and a silicon-containing gas. and, a mixed gas plasma generation means for generating a mixed gas plasma, the intermittent high-frequency bias RF power temporally modulated, and a high frequency bias power source to be applied to the SOI substrate or a silicon substrate, wherein The fluorine-containing gas is any one of SF ₆ , S ₂ F ₁₀ , CF ₄ or a mixed gas of two or more thereof, and the oxygen-containing gas is any one of O ₂ , CO, CO ₂ , SO ₂ or these mixing a gas, 4 the silicon-containing gas is _SiF, is any or a mixture gas of these SiCl _4, set into the reaction vessel Two or more temperature control portions in the electrode on which the SOI substrate or silicon substrate is placed, and the temperature of each portion can be set to different temperatures of -35 ° C to -45 ° C, and the reaction vessel The flow rate of SiF ₄ of the silicon-containing gas of the mixed gas introduced into the substrate is increased, and the bias power applied per unit time is fixed, and the application and stop of the bias applied to the SOI substrate or the silicon substrate is performed. using time-modulated bias capable of temporally modulated, characterized that you control the high frequency bias off F times the period of said time-modulated bias.

  According to the present invention, it is possible to suppress a mask processing dimension abnormality in deep hole processing such as TSV and to reduce roughness of a side wall including side etching and to ensure stable productivity.

FIG. 1 is a cross-sectional view for explaining an outline of a reaction vessel configuration of a microwave etching apparatus used in the present invention. FIG. 2 is a cross-sectional view for explaining side etching generated in a silicon substrate by a conventional method. FIG. 3 is a diagram for explaining the structure of the silicon substrate used in the present invention. FIG. 4 is a diagram showing a comparison of waveforms of CW bias and TM bias used in the present invention. FIG. 5 is a diagram for explaining the dependency of the SiF ₄ flow rate on the side etching amount generated in the silicon substrate. FIG. 6 is a diagram for explaining the dependency of SiF ₄ flow rate on the selection ratio between the depth of Via and the mask scraping amount corresponding to this embodiment.

  Hereinafter, embodiments of the present invention will be described with reference to the drawings.

  FIG. 1 shows a plasma etching apparatus to which the etching method of the present invention is applied. This embodiment shows a microwave plasma etching apparatus using a microwave and a magnetic field as means for forming plasma.

  The plasma etching apparatus includes a cylindrical reaction vessel 1 made of aluminum, stainless steel, or the like, and a sample stage 3 on which a substrate to be processed (silicon substrate or SOI substrate) 2 is placed. The sample stage 3 is a two-refrigerant type sample stage that can independently control the temperatures of the center and outer peripheral parts of the surface of the sample stage 3.

Freon gas (fluorine-containing gas) such as SF ₆ , S ₂ F ₁₀ , NF ₃ , CF ₄ , C ₂ F ₈ , inert gas such as Ar, N ₂ , oxidation containing O ₂ , CO, CO ₂ , SO _2, etc. Gas and silicon-containing gas such as SiF ₄ and SiCl ₄ are controlled in flow rate and timing by a gas flow rate adjusting means (MFC: Mass Flow Controller) and an air valve (not shown), and the permeation of the porous structure from the gas inlet 4 It is uniformly supplied to the surface of the substrate 2 through the window 5.

  Below the reaction vessel 1, vacuum evacuation means such as a turbo molecular pump (TMP) (not shown) is disposed, and the inside of the reaction vessel 1 is predetermined by pressure adjusting means (not shown) such as an auto pressure controller (APC). Held in pressure. The treated reaction gas is discharged out of the reaction vessel 1 through a vacuum exhaust means.

  Microwaves generated by the magnetron 6 are introduced into the reaction vessel 1 through a dielectric window 8 made of quartz, sapphire, aluminum nitride, and boron nitride that can transmit electromagnetic waves through the waveguide 7.

  A solenoid coil 9 for generating a magnetic field is disposed on the outer peripheral wall of the reaction vessel 1, and electron cyclotron resonance (ECR) is generated by the interaction between the generated magnetic field and the incident microwave. However, it has a structure capable of forming high-density plasma.

  An electrostatic chuck 10 is disposed on the surface of the conductive sample stage 3, and an electrostatic adsorption force is generated by applying a DC voltage from the electrostatic adsorption power source 17, so that the substrate 2 to be processed is placed on the surface of the electrostatic chuck 10. Fixed. An insulating cover 18 made of ceramics or quartz is disposed around the substrate 2 to be processed. The structures on which the substrate 2 to be processed disposed in the center of these devices is collectively referred to as electrodes.

A groove is formed on the surface of the electrostatic chuck 10, and He, Ar, O _2, etc. are supplied from the cooling gas supply port 15 to the flow path 12 formed between the back surface of the fixed substrate 2 to be processed and the electrostatic chuck 10. A cooling gas is supplied to maintain the inside of the flow path 12 at a predetermined pressure. In addition, the refrigerant whose temperature is controlled by the chiller unit 14 is circulated in the refrigerant circulation flow path 13 embedded in the electrostatic chuck 10, and the gas heat transfer by the gas in the flow path 12 and the heat conduction by the contact surface, The substrate 2 to be processed is cooled.

  A high frequency power introduction port 16 is connected to the conductive sample stage 3 so that a 400 kHz sine wave voltage or TM high frequency bias power can be applied. As for the applied high frequency bias, the application timing and applied power of the high frequency power are controlled by a control unit of an etching apparatus (not shown). Note that a variable frequency power supply is used as the power supply for the high frequency bias, and an arbitrary frequency of 400 to 1200 kHz can be applied.

  In order to apply TM high-frequency bias power, an arbitrary waveform generator (not shown) is connected to the high-frequency power supply 11, and the applied high-frequency power can be temporally modulated and intermittently supplied to the electrostatic chuck 10. ing. The duty ratio of the intermittent high-frequency bias obtained by temporally modulating the high-frequency power, the period of application, and the like can be arbitrarily controlled according to the recipe conditions recorded in the control unit of a plasma etching apparatus (not shown). .

  In the reaction vessel 1, a quartz cylinder 20 that is easy to remove and a cover 19 in which an aluminum material is subjected to a surface treatment such as alumite are installed around the electrodes in order to improve maintenance and prevent metal contamination. Yes.

  That is, an etching apparatus according to the present invention includes a reaction vessel 1, an electrode (sample stage) 3 on which a silicon or SOI substrate provided in the reaction vessel 1 is placed, a microwave power source (magnetron) 6 for generating plasma, A magnetic field generating solenoid coil 9 provided on the outer peripheral wall of the reaction vessel 1, a processing gas supply means 4 for supplying a mixed gas of fluorine-containing gas and oxygen-containing gas into the reaction vessel 1, and an electrode Silicon or SOI to be processed, comprising cooling means (cooling gas supply means 12 and 15, refrigerant circulation path 13 and chiller unit 14) for cooling the silicon or SOI substrate, and a high frequency power source 11 for supplying a high frequency bias to the electrodes. In the etching apparatus for forming grooves and / or holes in the substrate 2, a mixed gas of fluorine-containing gas and oxygen-containing gas is supplied from the processing gas supply means, The high frequency power supply is supplied with a bias whose frequency band of intermittent high frequency is 1 kHz to 2 MHz obtained by temporally modulating the high frequency bias supplied to the electrode, and the cooling means is for the electrode on which the substrate 2 to be processed is placed. The temperature was controlled to 30 to -60 ° C.

  Furthermore, the etching apparatus of the present invention takes an aspect in which the high-frequency power source supplies a continuous high-frequency power bias and a time-modulated intermittent high-frequency power bias in the etching apparatus. In this configuration, after supplying a continuous high frequency power bias, a temporally modulated intermittent high frequency power bias is output.

In the etching apparatus of the present invention, the fluorine-containing gas supplied from the processing gas supply means in the etching apparatus is SF ₆ , S ₂ F ₁₀ , NF ₃ , CF ₄ , C ₂ F ₈ or a mixed gas thereof. The oxygen-containing gas is any one of O ₂ , CO, CO ₂ and SO ₂ or a mixed gas thereof, and the Si-containing gas is any one of SiF ₄ and SiCl ₄ or a mixed gas thereof.

Using this apparatus, the etching process of the Via process of the silicon substrate was performed. The first embodiment shows a case where etching is performed under the conditions of SF ₆ , O ₂ and SiF ₄ , and details will be described with reference to FIGS. 3 to 4. In this example, the gas flow rate shown in Table 1 was set as the central condition.

  A substrate 2 to be processed shown in FIG. 1 is a silicon substrate shown in FIG. A photoresist mask pattern 24 is formed on the surface of the substrate 2 to be processed through photolithography and etching processes. The mask pattern 24 is formed with a hole pattern having a thickness of 4.0 μm and an opening width of about 10.0 μm.

The substrate 2 to be processed is transported into the reaction container 1 by a transport mechanism (not shown) and placed on the electrostatic chuck 10. Ar gas whose flow rate is controlled to 100 to 500 CCM (cc (cm ³ ) / min) by MFC is supplied into the reaction vessel 1, and the inside of the vessel is pressurized to 0.5 to 20 Pa (Pascal = 1 N / m ² ) by APC. adjust. A 400 W microwave is supplied into the reaction vessel 1 through a waveguide to form plasma.

  By applying a DC voltage of −500 V from the electrostatic attraction power source and moving the charge through the plasma, an electrostatic attraction force is generated, and the substrate 2 to be processed is fixed on the electrostatic chuck.

  He is supplied to the flow path 12 through the cooling gas supply port 15, and the pressure in the flow path 12 is adjusted to 1-2 kPa.

  The substrate 2 to be processed is left for a predetermined time by heat transfer from the contact surface with the electrostatic chuck 10 and gas heat transfer from the flow path 12, and cooled to the central portion: -35 ° C and the outer peripheral portion: -45 ° C. After the substrate 2 to be processed is cooled to a predetermined temperature, the application of microwaves is stopped and the plasma is stopped.

  The wafer is cooled by He on the back surface of the wafer, but if there is no Ar discharge (wafer bias: 0 W) as described above, etching is started from room temperature.

  For this reason, even with the discharge under the conditions shown in Table 1, the temperature of the wafer decreases to a certain extent in about 10 seconds, but etching is performed at a temperature higher than a predetermined temperature for the first about 10 seconds.

For this reason, although SF ₆ is used at a high temperature for the first approximately 10 seconds, it causes notches and side etching directly under the mask.

In order to prevent this, a discharge of Ar (wafer bias: 0 W) is added before etching and the wafer is cooled by electrostatic adsorption.
(Actually, the wafer temperature falls to around −40 ° C. when the TCR is set at −45 ° C. and the Ar discharge time is 30 seconds.)
After stopping the supply of Ar gas, the inside of the reaction vessel 1 is once evacuated, and gases of SF ₆ : 400 CCM, O ₂ : 60 CCM and SiF ₄ : 25 CCM are supplied, and the inside of the reaction vessel 1 is replaced with an etching gas. To do. The pressure in the reaction vessel 1 is adjusted to 13.0 Pa by APC (not shown).

Microwave power: 1000 W is applied and supplied into the reaction vessel 1 to generate plasma. After confirming that the plasma has been ignited and stabilized by optical means, a 400 kHz bias modulated by an arbitrary waveform generator (not shown) is applied from the high frequency power introduction port 16.
FIG. 4 shows an example of a conventional 800 kHz CW bias waveform 24 and a 400 kHz TM bias waveform 25 used in this embodiment.

  In TM (Time Modulation) bias, it is possible to fix the bias power applied per unit time and temporally modulate the application and stop of the bias applied to the substrate 2 to be processed. Therefore, when a TM bias is applied, a high voltage bias is applied compared to the CW bias, and even when the applied power per unit time is the same, high vertical ions can be generated with a high Vpp.

  The total time for applying and stopping the high frequency is 100%, and the ratio of the applied time to the total time is called the duty ratio, and the application state of the high frequency bias is controlled by this ratio. The total time can also be arbitrarily controlled, and the period of the TM bias to be applied can be controlled in the range of 120 Hz to 2 kHz. The OFF time of the high frequency bias is controlled by the period of the TM bias, and the reaction time of the by-product and the adhesion time to the side wall can be adjusted.

  After the substrate 2 to be processed is etched for a predetermined time, the application of microwave power is stopped and the generation of plasma is stopped. After the supply of the etching gas is stopped, the reaction container 1 is evacuated and the reaction product in the container is discharged. In addition, the processing time of the to-be-processed substrate 2 is controlled according to the recipe conditions recorded on the control part of the etching apparatus which is not illustrated.

  In the course of the etching process, the attachment and detachment of reaction by-products serving as a protective film on the trench side wall are repeated. The adhesion probability can be improved by lowering the electrode temperature.

FIG. 5 shows the dependence of the amount of SiF ₄ added, and side etching can be suppressed by increasing the flow rate of SiF ₄ . This effect is obtained by adding SiF ₄ , in addition to the reaction products Si—O and Si—O—F generated from the Si surface by etching, SiF ₄ supplied into the processing chamber in the form of gas is used for etching. In addition to contributing F ions and F radicals, Si—O and Si—O—F are also generated and adhered as side wall protection, thereby suppressing side etching.

FIG. 6 also shows the dependency of the amount of SiF ₄ added, and the etching selectivity between the photoresist film and the silicon film can be improved by increasing the flow rate of SiF ₄ . This effect is due to the fact that the amount of Si—O and Si—O—F reaction products deposited on the mask increases as the flow rate of SiF ₄ increases as described above. Since the wafer bias is applied, there is an attack on the photoresist film due to incident ions, but the amount of reaction product deposited increases, so that the amount of photoresist film scraping can be reduced as a whole. It becomes.

  Further, by reducing the duty ratio with the TM bias, the time during which the RF bias is not applied can be lengthened. This means that the deposition time of the reaction product can be increased. If the reaction product is attached for a long period of time, the amount of deposition increases, so that the amount of abrasion of the photoresist film can be further reduced.

For example, the selection ratio between the mask with a SiF ₄ flow rate of 0 and silicon is 141.7, whereas when 50 CCM is added, it becomes 166.6. According to the result of this example, the selection ratio of the mask and silicon is about 160, but the selection ratio can be increased to about 300 by optimizing the gas flow rate ratio, TM bias power, TM bias application period, and the like. is there.

  In addition, since the temperature of the central portion and the outer peripheral portion of the substrate to be processed is controlled independently, a uniform and favorable processed shape can be obtained within the surface of the substrate to be processed.

  In this embodiment, a microwave plasma etching apparatus using a microwave and a magnetic field has been described as an example. However, regardless of the plasma generation method, for example, a helicon wave etching apparatus, an inductively coupled etching apparatus, a capacitively coupled etching is used. The present technology can be applied to an apparatus, a magnetic field RIE apparatus, and the like, and the same effect can be obtained.

DESCRIPTION OF SYMBOLS 1 Reaction container 2 To-be-processed object 3 Sample stand 4 Process gas inlet 5 Shower plate (porous structure quartz plate)
6 Magnetron 7 Waveguide 8 Quartz plate 9 Solenoid coil 10 Electrostatic chuck 11 High frequency power supply 12 Cooling gas flow path 13 Refrigerant circulation flow path 14 Chiller unit 15 Cooling gas supply port 16 High frequency introduction port 17 Electrostatic adsorption power supply 18 Insulating cover 19 Metal contamination reduction parts 20 Quartz cylinder 21 Silicon 22 Mask pattern 23 Side etching of silicon 24 CW bias waveform 25 TM bias waveform

Claims (2)

An etching method for forming grooves and / or holes in an SOI substrate or a silicon substrate, wherein a mixed gas is introduced into a reaction vessel using a fluorine-containing gas, an oxygen-containing gas, and a silicon-containing gas to generate a mixed gas plasma, In the etching method of applying an intermittent high frequency bias obtained by temporally modulating high frequency power to the SOI substrate or the silicon substrate ,
The fluorine-containing gas is SF ₆ , S ₂ F ₁₀ , CF ₄ , or a mixed gas of two or more thereof, and the oxygen-containing gas is any one of O ₂ , CO, CO ₂ , SO ₂ or these The silicon-containing gas is either SiF ₄ , SiCl ₄ or a mixed gas thereof,
There are two or more temperature control parts in the electrode on which the SOI substrate or silicon substrate placed in the reaction vessel is placed, and the temperature of each part is set to a different temperature of −35 ° C. to −45 ° C. ,
Increasing the flow rate of SiF ₄ of the silicon-containing gas ,
Further, the time modulation bias is fixed using a bias power applied per unit time and using a time modulation bias capable of temporally modulating the application and stop of the bias applied to the SOI substrate or silicon substrate. An etching method characterized by controlling the off-F time of the high-frequency bias according to the period . An etching apparatus for forming grooves and / or holes in an SOI substrate or a silicon substrate, wherein a mixed gas is introduced into a reaction vessel using a fluorine-containing gas, an oxygen-containing gas, and a silicon-containing gas, and mixed gas is generated. Gas plasma generating means, and a high-frequency bias power source for applying an intermittent high-frequency bias obtained by temporally modulating high-frequency power to the SOI substrate or silicon substrate,
Wherein the fluorine-containing gas is _{SF 6,} S ₂ F _10, one or a mixture gas of two or more of these C _{F 4,} wherein the oxygen-containing gas is _O 2, _CO, CO 2, either SO ₂ or a mixture of these gases, the silicon-containing gas Ri either or gas mixture der these _SiF 4, SiCl _4,
There are two or more temperature control parts in the electrode on which the SOI substrate or silicon substrate placed in the reaction vessel is placed, and the temperature of each part can be set to different temperatures from -35 ° C to -45 ° C. And
Increasing the flow rate of SiF ₄ of the silicon-containing gas of the mixed gas introduced into the reaction vessel ;
Further, the time modulation bias is fixed using a bias power applied per unit time and using a time modulation bias capable of temporally modulating the application and stop of the bias applied to the SOI substrate or silicon substrate. An etching apparatus characterized by controlling the off-F time of the high-frequency bias according to the period .

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