TECHNICAL FIELD The present invention relates to a substrate processing apparatus, and more particularly, to a substrate processing apparatus for effecting cleaning after a substrate is subjected to desired processing.
BACKGROUND ART A thermal CVD (Chemical Vapor Deposition) apparatus comprises a furnace. According to the thermal CVD apparatus, a plurality of raw material gases are mixed and allowed to flow into in the furnace, and a film is formed on a substrate. If the film is formed on the substrate, the film adheres not only to the substrate but also to an inner side of the furnace. If the film adhering to the inner side of the furnace is accumulated and becomes thicker, the film is peeled off, and this generates foreign material.
To avoid this, etching gas is allowed to flow at regular intervals, and cleaning is carried out to remove the film on the inner side of the furnace. When the film is SiN for example, DCS (SiH2Cl2: dichlorsilane) gas and non-plasma NH3gas are used as the raw material gas, and gas including F (fluorine) such as NF3and ClF3is used as the etching gas.
The film on the inner side of the furnace is removed by the cleaning, molecules including F (F component, hereinafter) adsorbs and bonds to the inner wall surface of the furnace and remains thereon immediately after the cleaning. The molecules are separated at the time of subsequent film forming operation onto the substrate and hinder the film formation, and the film forming speed is decreased. This is because that F has etching function, F reacts with Si of an SiN film formed on the substrate to form SiF4(gas), and Si is removed from the substrate. Another reason is that F reacts with reaction gas (DCS), and an amount of raw material gas is reduced.
For this reason, in the conventional thermal CVD apparatus, after the cleaning and before the film is formed on the substrate, the film is forcibly deposited on the inner side of the furnace. This is called film-preformation. With this film-preformation, F component is allowed to react with the raw material of the film or is encapsulated under the film (this is also called trap of F component) so that F component is reduced from an atmosphere in the furnace as much as possible and the film forming speed is recovered when a film is formed.
In recent years, SiN films can be formed also by an ALD (Atomic Layer Deposition) apparatus. In the ALD apparatus, DCS gas and NH3activated by plasma (also called NH3plasma or NH3radical) are used as the reaction gases, and these two reaction gases are alternately supplied and films are formed one atom layer by one atom layer. If the ALD apparatus is used, even at low temperature, it is possible to form a high quality film as high as that formed by the thermal CVD apparatus which requires high temperature process. However, even with the ALD apparatus, a film must be preformed after cleaning to remove the remaining F like the thermal CVD apparatus.
In the above-described conventional technique, elements including the cleaning gas are trapped by the film-preformation, and the elements are eliminated from an atmosphere in a reaction container as much as possible. For this purpose, it is necessary to carry out the film-preformation. Further, even if a thick film-preformation is carried out, the elements included in the cleaning gas can not effectively be eliminated from the atmosphere in the reaction container. Further, since it is necessary to add a thermal CVD film-forming nozzle in addition to a special-purpose buffer nozzle, the structure of the reaction container becomes complicated and costs thereof are increased. If the thermal CVD film-forming nozzle is added, there is a problem that foreign materials are generated due to film formation in the CVD film-forming nozzle, and this is not preferable.
Therefore, it is a main object of the present invention to provide a substrate processing apparatus capable of effectively eliminating elements included in cleaning gas.
It is another object of the invention to provide a substrate processing apparatus capable of effectively preventing foreign materials from generating from a gas supply system, and to eliminate the need of the gas supply system itself.
DISCLOSURE OF THE INVENTION According to a first aspect of the present invention, there is provided a substrate processing apparatus, comprising:
a reaction container which accommodates a substrate, to which a plurality of reaction gases are supplied, and which forms a space where said substrate is subjected to desired processing,
an exhaust port which is opened in said reaction container for exhausting gas from said reaction container, and
a gas supply system for supplying at least the plurality of reaction gases to said reaction container, wherein
said gas supply system comprises
a cleaning gas supply unit for supplying cleaning gas which removes accretion adhering to an inner side of said reaction container by subjecting said substrate to the desired processing,
a post-processing gas supply unit for supplying post-processing gas which can remove an element included in the cleaning gas remaining in said reaction container after the accretion is removed by supplying the cleaning gas, and
said post-processing gas includes all reaction gases used when said substrate is subjected to the desired processing.
According to a second aspect of the present invention, there is provided a substrate processing apparatus which supplies a plurality of reaction gases alternately and forms a thin film on a substrate, comprising:
a reaction container,
a plurality of exclusive supply nozzles for respectively and exclusively supplying the reaction gases, and
a control apparatus for controlling the substrate processing apparatus such that cleaning gas is supplied from one of the supply nozzles into said reaction container at a time of cleaning, all reaction gases used for processing a substrate are alternately supplied into said reaction container from the exclusive supply nozzles after the cleaning gas is supplied and before the substrate is processed.
BRIEF DESCRIPTION OF THE DRAWINGSFIG. 1 is a schematic transverse sectional view of a furnace constituting a vertical ALD apparatus according to an embodiment of the present invention.
FIG. 2 is a schematic vertical sectional view of a furnace constituting the vertical ALD apparatus according to the embodiment of the present invention.
FIG. 3 is a perspective view of a buffer nozzle in a reaction tube according to the embodiment of the invention.
FIGS. 4A and 4B show comparison of processing temperatures of cleaning, film-preformation, film formation when an ALD method and a thermal CVD method are employed for film-preformation.
FIG. 5 shows an outline entire structure of the vertical ALD apparatus according to the embodiment of the invention.
PREFERABLE MODE FOR CARRYING OUT THE INVENTION According to a preferable embodiment of the present invention, there is provided a first substrate processing apparatus comprising:
a reaction container which accommodates a substrate, to which a plurality of reaction gases are supplied, and which forms a space where said substrate is subjected to desired processing,
an exhaust port which is opened in said reaction container for exhausting gas from said reaction container, and
a gas supply system for supplying at least the plurality of reaction gases to said reaction container, wherein
said gas supply system comprises
a cleaning gas supply unit for supplying cleaning gas which removes accretion adhering to an inner side of said reaction container by subjecting said substrate to the desired processing,
a post-processing gas supply unit for supplying post-processing gas which can remove an element included in the cleaning gas remaining in said reaction container after the accretion is removed by supplying the cleaning gas, and
said post-processing gas includes all reaction gases used when said substrate is subjected to the desired processing.
Here, the desired processing includes a thin film formation by vapor phase epitaxy or surface reaction, processing for working or machining a substrate, such as formation of an oxide film, dispersion processing and the like.
Since the post-processing gas which can remove element included in the cleaning gas from the reaction container is supplied from the post-processing gas supply unit, the element included in the cleaning gas can be removed also from the reaction container as compared with a case in which a film is preformed in the reaction container and the element is trapped. Since the post-processing gas supply unit supplies to a substrate, as post-processing gases, all reaction gases used when said substrate is subjected to the desired processing, the reaction gases react with element included in the cleaning gas to produce volatile material, and the produced volatile material can effectively be removed from the reaction container. If the post-processing gas supply unit comprises gas supply means which supplies all reaction gases used when the substrate is subjected to desired processing, it is unnecessary to newly add a gas supply system, the structure does not become complicated. Further, foreign material from a gas supply system generated when the gas supply system is added can be prevented from being generated.
According to another preferred embodiment of the invention, in the first substrate processing apparatus, there is provided a second substrate processing apparatus, wherein said post-processing gas supply unit includes exclusive supply nozzles for independently supplying each of the reaction gases, and when the reaction gases are to be supplied as the post-processing gases, the reaction gases are alternately supplied from the exclusive supply nozzles.
In the second substrate processing apparatus, the post-processing gas supply unit can alternately supply reaction gases as post-processing gases from the exclusive supply nozzles which respectively supply a plurality of reaction gases used when a substrate is subjected to desired processing. Thus, gases supplied from the exclusive supply nozzles effectively affect elements included in the cleaning gases remaining in the exclusive supply nozzles and thus, it is possible to effectively remove the elements included in the cleaning gases remaining in the exclusive supply nozzles. In this case, examples of combination between a method in which a substrate is subjected to desired processing and a method in which the post-processing is carried out are ALD method+ALD method, and thermal CVD method+ALD method.
According to still another preferred embodiment of the invention, in the second substrate processing apparatus, there is provided a third substrate processing apparatus in which each of the reaction gases supplied from said post-processing gas supply unit remove the element remaining in said exclusive supply nozzles and said reaction container, and form a desired film in said reaction container.
In the third substrate processing apparatus, the post-processing gas supply unit can supply reaction gases for removing elements remaining in the exclusive supply nozzles and the reaction container. Thus, it is possible to effectively remove, from the reaction container, elements remaining in the exclusive supply nozzles and the reaction container. If the post-processing gas supply unit can supply reaction gases for forming a desired film, i.e., for performing a film on the reaction container, element remaining in the reaction container can be encapsulated in the preformed film. Therefore, remaining element can be eliminated from the atmosphere in the reaction container from both removal and encapsulation and thus, reduction in film forming speed caused by the remaining element can be avoided. If the reaction gases can alternately be supplied, the desired films formed in the exclusive supply nozzles and the reaction container may be thin, and the throughput is enhanced.
According to still another preferred embodiment of the invention, in the third substrate processing apparatus, there is provided a fourth substrate processing apparatus, wherein the plurality of reaction gases supplied from the exclusive supply nozzles are a gas including silicon, and ammonia gas activated by plasma.
In the fourth substrate processing apparatus, the gas including silicon can effectively eliminate element included in the cleaning gas remaining in the exclusive supply nozzle which supplies gas including silicon from the atmosphere in the reaction container. The ammonia gas activated by plasma can effectively eliminate element included in the cleaning gas remaining in the exclusive supply nozzle which supplies the ammonia gas from the atmosphere in the reaction container.
According to still another preferred embodiment of the invention, in the fourth substrate processing apparatus, there is provided a fifth substrate processing apparatus, wherein the cleaning gas is a gas including fluorine, and the gas including fluorine is supplied from the exclusive supply nozzle which supplies a gas including silicon.
In the fifth substrate processing apparatus, since a film is easily formed using gas including silicon as compared with ammonia gas, more accretions adhere to the exclusive supply nozzle which supplies gas including silicon as compared with the exclusive supply nozzle which supplies ammonia gas. Therefore, if gas including fluorine is supplied as cleaning gas from the exclusive supply nozzle which supplies gas including silicon, the accretions in the exclusive supply nozzle which supplies gas including silicon can be removed, and the exclusive supply nozzle can effectively be cleaned.
According to still another preferred embodiment of the invention, in the fourth or fifth substrate processing apparatus, there is provided a sixth substrate processing apparatus, wherein the gas including silicon is DCS (SiH2Cl2).
According to still another preferred embodiment of the invention, in the fifth substrate processing apparatus, there is provided a seventh substrate processing apparatus, wherein the gas including fluorine is NF3or ClF3.
According to still another preferred embodiment of the invention, there is provided an eighth substrate processing apparatus which supplies a plurality of reaction gases alternately and forms a thin film on a substrate, comprising:
a reaction container,
a plurality of exclusive supply nozzles for respectively and exclusively supplying the plurality of the reaction gases, and
a control apparatus for controlling the substrate processing apparatus such that cleaning gas is supplied from one of the supply nozzles into said reaction container at a time of cleaning, all reaction gases used for processing a substrate are alternately supplied into said reaction container from the exclusive supply nozzles after the cleaning gas is supplied and before the substrate is processed.
According to still another preferred embodiment of the invention, there is provided a first semiconductor device producing method for producing a semiconductor device using a substrate processing apparatus in which all reaction gases used when a substrate is processed are supplied to the reaction container after the process for cleaning the inside of the reaction container and an element included in the cleaning gas supplied into the reaction container is removed.
If a semiconductor device is produced using a substrate processing apparatus in which all reaction gases used when a substrate is processed are supplied to the reaction container after the process for cleaning the inside of the reaction container and element included in the cleaning gas supplied into the reaction container is removed, the element remaining in the reaction container can effectively be removed, reduction in film forming speed caused by the element is prevented at the time of film forming process which is carried out the cleaning process, and it is possible to produce a high quality semiconductor device in which the film forming amount is stable.
According to still another preferred embodiment of the invention, in the first semiconductor device producing method, there is provided a second semiconductor device producing method wherein the reaction gases are supplied from the respective exclusive supply nozzles to the reaction container, and the process for removing element included in the cleaning gas includes process for alternately supplies the reaction gases from the exclusive supply nozzles.
In the second semiconductor device producing method, the reaction gases are supplied from the respective exclusive supply nozzles to the reaction container, and the process for removing element included in the cleaning gas includes process for alternately supplies the reaction gases from the exclusive supply nozzles. Therefore, it is possible to remove the elements remaining in the reaction container and the exclusive supply nozzles, the reduction in film forming speed caused by the elements can further be prevented at the time of film forming process which is carried out after the cleaning process, and a high quality semiconductor device having further stable film thickness can be produced.
According to still another preferred embodiment of the invention, in the second semiconductor device producing method, there is provided a third semiconductor device producing method wherein the process for removing elements included in the cleaning gas includes the process for removing the element remaining in the exclusive supply nozzles and the reaction container, and the process for forming a desired film on a constituent surface in the reaction container.
In the third semiconductor device producing method the process for removing elements included in the cleaning gas includes the process for removing the element remaining in the exclusive supply nozzles and the reaction container, and the process for forming a desired film on a constituent surface in the reaction container. Thus, it is possible to remove the elements remaining in the reaction container and the exclusive supply nozzles, and to encapsulate the elements in the film formed in the reaction container. The reduction in film forming speed caused by the elements can further be prevented at the time of the film forming process which is carried out after the cleaning process, and a high quality semiconductor device having further stable film thickness can be produced.
According to still another preferred embodiment of the invention, in the first to third semiconductor device producing methods, there is provided a fourth semiconductor device producing method wherein the plurality of reaction gases are a gas including silicon and ammonia gas.
In the fourth semiconductor device producing method, preferably, the ammonia gas is ammonia gas activated by plasma. If the plurality of reaction gases are gas including silicon and ammonia activated by plasma, the elements remaining in the exclusive supply nozzles can be removed. The reduction in film forming speed caused by the elements remaining in the reaction container and the exclusive supply nozzles can further be prevented at the time of the film forming process which is carried out after the cleaning process, and a high quality semiconductor device having further stable film thickness can be produced.
According to still another preferred embodiment of the invention, in the fourth semiconductor device producing method, there is provided a fifth semiconductor device producing method wherein the cleaning gas is gas including fluorine, and the cleaning gas is supplied to the reaction container from the supply nozzle which supplies gas including silicon.
In the fifth semiconductor device producing method, the cleaning gas is gas including fluorine, and the cleaning gas is supplied to the reaction container from the supply nozzle which supplies gas including silicon. Therefore, it is possible to effectively remove the accretions in the exclusive supply nozzle which supplies gas including silicon which can easily form a film as compared with ammonia gas, and the inside of the exclusive supply nozzle can be cleaned effectively, and it is possible to produce a semiconductor device which suppresses affect of foreign materials.
According to still another preferred embodiment of the invention, in the fourth or fifth semiconductor device producing method, there is provided a sixth semiconductor device producing method, wherein the gas including silicon is DCS (SiH2Cl2).
According to still another preferred embodiment of the invention, in the fifth semiconductor device producing method, there is provided a seventh semiconductor device producing method, wherein the gas including fluorine is NF3or ClF3.
Next, a preferred embodiment of the present invention will be explained in more detail with reference to the drawings.
FIG. 5 shows an outline entire structure of a vertical ALD apparatus according to the embodiment of the invention. Asubstrate processing apparatus50 is provided at its front surface with a cassette delivery/receivingunit49. In thesubstrate processing apparatus50, acassette shelf51 is provided such as to be opposed to the cassette delivery/receivingunit49, and aspare cassette shelf52 is provided above the cassette delivery/receivingunit49. Acassette transfer unit53 is provided with the cassette delivery/receivingunit49 and thecassette shelf51, and asubstrate loader54 is provided behind thecassette shelf51. Aboat elevator55 is provided behind thesubstrate loader54, and avertical reaction furnace10 is provided above theboat elevator55.
The cassette delivery/receivingunit49 includes acassette stage58 on which twocassettes57 can be placed. Thecassette57 is a substrate transfer container. The cassette delivery/receivingunit49 also includes two substrate-posture aligners59 below thecassette stage58. If thecassettes57 transferred by an external transfer apparatus (not shown) are placed on thecassette stage58 in a vertical posture (i.e., wafers1 accommodated in thecassettes57 are in a vertical posture), the substrate-posture aligners59 align the postures of the wafers such that notches and orientation flats of substrates (not shown) such as wafers in thecassette57 are located at the same positions.
Thecassette stage58 is rotated through 90° to set thecassettes57 horizontally so that the cassette transfer unit can transfer thecassettes57.
Thecassette transfer unit53 includes arobot arm60 which can move forward and backward in the longitudinal direction, and therobot arm60 can move laterally and vertically. Thecassettes57 are transferred from thecassette stage58 to thecassette shelf51 or thespare cassette shelf52 by combination of longitudinal, vertical and lateral movements of therobot arm60.
Anarm61 extends from theboat elevator55. Thearm61 is provided with aseal cap17. A boat which is a substrate holder is placed on theseal cap17. Theboat2 holds the multi-stacked wafers in their horizontal postures. The wafers are brought into and out from thevertical reaction furnace10 by theboat elevator55.
Thesubstrate loader54 can rotate and vertically move, and includes awafer holder62 which can move forward and backward. Thewafer holder62 has a plurality ofwafer holding plates63, and eachwafer holding plate63 can holds a plurality of wafers collectively, or can hold one wafer.
Thesubstrate loader54 loads a plurality of wafers collectively or one by one to theboat2 which is lowered from thecassette57 of thecassette shelf51.
If the necessary number of wafers are loaded onto the, theboat2 is inserted into thevertical reaction furnace10, and the wafers are subjected to processing. The ALD method is used for this wafer processing, and a plurality kinds of raw material gases as reaction gas are used for the processing. In the processing, the raw material gases are alternately supplied onto the wafers one kind by one kind, adsorption and reaction of the gasses are repeated one atom layer by one atom layer, thereby carrying out the processing.
The processed substrates are loaded on thecassettes57 of thecassette shelf51 through a reversed operation of the above-described operation, the substrates are transferred to the cassette delivery/receivingunit49 by thecassette transfer unit53, and are transferred out by the external transfer apparatus (not shown).
FIG. 2 shows a structure of the vertical reaction furnace10 (simplyfurnace10, hereinafter) of the vertical ALD apparatus of the embodiment. Thefurnace10 includes aheater14 and a cylindricalquartz reaction tube11 as a reaction container provided inside theheater14. Areaction chamber12 which is a substrate processing region is formed in thereaction tube11. A furnace opening of thereaction tube11 is occluded air-tightly by theseal cap17. Theboat2 stands on a quartz cap7 provided on theseal cap17. Theboat2 is inserted into thereaction tube11. Theboat2 includes a plurality ofcolumns5 standing between a top plate3 and abottom plate4. Thesecolumns5 are provided withgrooves6 formed at distances from one another in the vertical direction. In theboat2, the wafers1 are held horizontally in a multi-stacked manner in thegrooves6. Theboat2 is vertically movably supported by the boat elevator55 (seeFIG. 5) and theboat2 can be brought into and out from thereaction tube11. Theboat2 is rotated around therotation shaft19 in thereaction tube11 by a rotation mechanism (not shown). Areference number18 represents a sealing O-ring.
Thereaction tube11 is provided with gas supply means70. The plurality of reaction gases are supplied from the gas supply means70 into thereaction tube11. The gas supply means70 includes a cleaning gas supply system and a post-processing gas supply system. Thereaction tube11 is provided with anexhaust port16 as an exhaust system, and it is possible to exhaust gas from thereaction tube11.
Although only one gas supply means70 is shown inFIG. 2 as a matter of convenience, there are provided a plurality of gas supply means in the actually case so that a plurality kinds of raw material gases (here, two raw material gases) can be supplied into thereaction tube11. One or a portion of the plurality kinds of raw material gases is gas which is activated by plasma and supplied, and the remainder is gas which is not activated by plasma and supplied. For example, a film to be formed on the substrate is SiN film, the raw material gases includes NH3gas which is required to be activated, and DCS gas which is not required to be activated. The gas supply means70 shown here is first gas supply means (NH3gas supply means)70A which supplies NH3gas activated by plasma. The first gas supply means70A includes an NH3gas introducing port20 provided on the one side at a lower portion of thereaction tube11, and a quartz NH3buffer nozzle34 which is connected to the NH3gas introducing port20 and provided in thereaction tube11. The NH3buffer nozzle34 equalizes the flow rate and the velocity of flow of NH3gas introduced into thereaction tube11 over the all wafers.
The NH3buffer nozzle34 extends in an axial direction of thereaction tube11 along the tubeinner wall13 from the lower portion of thereaction tube11 to a portion in the vicinity of a top of thereaction tube11 where a top of theboat2 is located. As compared with a normal nozzle whose diameter is uniformly small, the NH3buffer nozzle34 has a relatively wide nozzle space, and NH3gas is injected into thereaction tube11 through the nozzle space. The NH3buffer nozzle34 is provided with a large number of injection holes (not shown) with the same pitch as adjacent wafers1 such as to correspond to the large number of wafers1 held in the multi-stacked manner in the vertical direction.
The NH3buffer nozzle34 is provided therein with a pair of plasma electrodes27 (since the electrodes are superposed on each other, only one of them is shown in the drawing) for generating plasma, and the introduced NH3gas is activated with plasma. The pair ofplasma electrodes27 are respectively inserted into a pair ofelectrode protection tubes25 provided in the NH3buffer nozzle34.Plasma40 is formed in aplasma producing region33 sandwiched between the pair ofelectrode protection tubes25.
FIG. 1 is a sectional view taken along the line I-I inFIG. 2. There are provided the first gas supply means (NH3gas supply means)70A and a second gas supply means (DCS gas supply means)70B so that two kinds of raw material gases can individually be introduced into thereaction tube11. The first gas supply means70A and the second gas supply means70B are connected to acontrol apparatus100 and controlled by thecontrol apparatus100. The first gas supply means70A includes an NH3gas introducing tube22, an NH3gas introducing port20 connected to the NH3gas introducing tube22, and the NH3buffer nozzle34 which is in communication with the NH3gas introducing port20. The second gas supply means70B includes a DCSgas introducing tube23, a DCSgas introducing port21 connected to the DCSgas introducing tube23, and aDCS buffer nozzle44 which is in communication with the DCSgas introducing port21.
The first gas supply means70A supplies NH3gas which is one of the two kinds of raw material gases into thereaction chamber12 from the NH3buffer nozzle34 as an exclusive supply nozzle. The first gas supply means70A also supplies NH3gas or inert gas such as N2which is post-processing gas into thereaction chamber12 from the NH3buffer nozzle34. The NH3gas is activated by plasma and supplied at the time of film forming operation and at the time of post-processing.
The NH3buffer nozzle34 includes a gas introducingnozzle portion28 connected to the NH3gas introducing port20, and a plasma producingnozzle portion29 for activating gas. The gas introducingnozzle portion28 and the plasma producingnozzle portion29 are provided side by side with adivision wall26 interposed therebetween, and are brought into communication with each other through acommunication port30 provided in thedivision wall26. The plasma producingnozzle portion29 is provided with the pair ofplasma electrodes27 for generating plasma so that the introduced gas can be activated by theplasma40. The activated NH3gas42 is injected from aninjection hole45 formed in the plasma producingnozzle portion29. The pair ofplasma electrodes27 are respectively inserted into the pair ofelectrode protection tubes25 provided in the plasma producingnozzle portion29. The pair ofplasma electrodes27 are introduced out from thefurnace10 through theelectrode protection tubes25 and are connected to a high frequency power supply31 through avariable capacity aligner32.
The NH3gas introducing port20 is connected to a bifurcatedgas introducing tube22. Thegas introducing tube22 selectively supplies NH3gas or inert gas N2to the NH3buffer nozzle34 through thefirst valve35 and thesecond valve36. The gas introduced from the NH3gas introducing port20 flows into the gas introducingnozzle portion28 of the NH3buffer nozzle34, and is supplied to the plasma producingnozzle portion29 through thecommunication port30. Here, high frequency electricity is applied between theplasma electrodes27,plasma40 is generated in aplasma producing region46, and NH3gas is activated by theplasma40. The activated NH3gas is injected from theinjection hole45 of the plasma producingnozzle portion29 onto the wafers1 in thereaction chamber12.
Since the NH3buffer nozzle34 has the relatively wide nozzle space therein, radicals generated when the gas is activated very little collide against the wall of the nozzle, pressure in the vicinity of theplasma producing region46 becomes low, this ensures lifetime of the generated radicals, and NH3radicals can be sent to the reaction chamber (substrate processing region)12 as they are.
The second gas supply means70B supplies DCS gas which is one of the two kinds of raw material gases to thereaction chamber12 from theDCS buffer nozzle44 as an exclusive supply nozzle. The second gas supply means70B also supplies NF3gas which is cleaning gas, DCS gas which is post-processing gas, or inert gas to thereaction chamber12 from theDCS buffer nozzle44. The DCS gas and NF3gas are supplied without being activated unlike the NH3.
Unlike the NH3buffer nozzle34, theDCS buffer nozzle44 does not have a plasma producing nozzle portion, and has only a portion corresponding to the gas introducingnozzle portion28. Gas is injected from aninjection hole47 of theDCS buffer nozzle44 onto the wafers1 in thereaction chamber12. The g21 is connected to a trifurcatedgas introducing tube23. The trifurcatedgas introducing tube23 selectively supplies DCS gas, NF3gas or inert gas to theDCS buffer nozzle44. The trifurcatedgas introducing tube23 comprisesgas introducing tubes23A,23B and23C. Thegas introducing tube23A supplies DCS gas. Since it is preferable that the pressure in the reaction tube (this pressure is also called internal pressure of the furnace) rises to a pressure higher than that of NH3gas within a short time, the DCSgas introducing tube23A includes abuffer tank41 for storing DCS gas. Thebuffer tank41 is sandwiched between afourth valve38 and asixth valve43. When DCS gas is to be supplied to thereaction chamber12, DCS gas is previously stored in thebuffer tank41, the DCS gas stored in thebuffer tank41 is supplied from thebuffer tank41 into thereaction chamber12 at a stroke in a state in which exhausting operation from theexhaust port16 of thereaction chamber12 is stopped for example, and the plurality of wafers1 in thereaction chamber12 are exposed to the DCS gas. Since it is preferable that NF3gas and inert gas are supplied without through thebuffer tank41, thegas introducing tubes23B and23C which supplies these gases are connected to the downstream portions of thebuffer tank41.
When the gas introducing tube23B, the DCSgas introducing port21 and theDCS buffer nozzle44 form films on the wafers1, reaction by-products as accretions adhering to the inner side of thereaction tube11. A cleaninggas supply system71 supplies cleaning gas for removing the reaction by-products. After first gas supply means (NH3gas supply means)70A and second gas supply means (DCS gas supply means)70B supply cleaning gas and remove the reaction by-products, a post-processinggas supply system72 removes F components included in cleaning gas remaining in thereaction tube11.
FIG. 3 shows the NH3buffer nozzle34 and theDCS buffer nozzle44 in thereaction tube11, and is a perspective view of thereaction tube11 as viewed from the hollow arrow shown at the upper right inFIG. 1. Hole sizes of the gas injection holes45 and47 of thebuffer nozzles34 and44 are increased from upstream portions toward downstream portions of thebuffer nozzles34 and44. This is because that since the pressure in the nozzle spaces of thebuffer nozzles34 and44 are decreased from the upstream portions toward the downstream portions, the hole sizes are increased toward the downstream portions so that the injection amount of gases injected from the gas injection holes45 and47 is ensured even on the downstream side, and the flow rate is equalized from the upstream portions toward the downstream portions. As described above, the gas injection holes45 and47 are provided with the same pitch as adjacent wafers1 such as to correspond to the large number of wafers1 held in the multi-stacked manner in the vertical direction.
Next, the operation of the vertical ALD apparatus of the embodiment having the above-described structure will be explained. If the film formation (film forming process A) is repeated in thereaction tube11 of the vertical ALD apparatus, reaction by-products adhere and remain to the inner side of the furnace. Cleaning (cleaning process B) is carried out to remove the reaction by-products. After the cleaning, post-processing (post-processing process C) for eliminating elements included in the cleaning gas remaining in the furnace is carried out. After the post-processing process C, the film forming process A and the cleaning process B are repeated. These processes will be explained individually. Here, time described in the following explanation is a value from which overhead is subtracted. Here, the overhead means time required for bringing theboat2 into and out from thereaction tube11, and time required for evacuation and restoration to normal pressure in the reaction tube. That is, the overhead means time from which time during which gas is introduced into the reaction chamber is subtracted.
Film Forming Process A
This process is an actual film forming process for forming a desired film on a wafer. The boat elevator55 (FIG. 5) moves theboat2 down through theseal cap17, theboat2 holds a large number of wafers1, and theboat elevator55 inserts theboat2 into thereaction tube11. The furnace opening of thereaction tube11 is completely closed by theseal cap17 air-tightly and then, thereaction tube11 is evacuated from theexhaust port16 to exhaust gas from thereaction tube11. The interior of thereaction tube11 is heated to a predetermined temperature, e.g., 400 to 600° C. and the temperature is stabilized. While raw material gases are supplied from the twobuffer nozzles34 and44 into thereaction tube11, the gases are discharged from theexhaust port16, and films are formed on the surfaces of the wafers1.
As described above, the ALD apparatus is designed such that DCS gas and NH3plasma are alternately supplied from the exclusive supply DCS nozzle and NH3nozzle. Especially in the case of a vertical ALD apparatus which processes a large number of stacked substrates at a time, in order to equally supply gases to the stacked substrates, buffer nozzles having large nozzle spaces are used as the DCS nozzle and NH3nozzle instead of normal thin nozzles in some cases. Unlike the DCS buffer nozzle, the NH3buffer nozzle is provided therein with a having a plasma electrode, and a plasma non-producing region into which NH3gas is introduced so that NH3gas introduced into the plasma non-producing region is less prone to be activated by plasma in the plasma producing region. When DCS gas is supplied from the DCS buffer nozzle so that SiN is less prone to be formed in each buffer nozzle, inert gas such as N2is allowed to flow from the NH3buffer nozzle, and when NH3plasma is supplied from the NH3buffer nozzle, inert gas such as N2is allowed to flow from the DCS buffer nozzle.
This film forming processing is carried out by ALD film forming processing using two kinds of reaction gases, i.e., DCS and NH3, and comprises the following four steps 1) to 4).
1) High frequency electricity is not applied between theplasma electrodes27 of the NH3buffer nozzle34. To prevent DCS gas from entering into the NH3buffer nozzle34, thesecond valve36 is opened to allow a small amount of N2gas to flow. Thefourth valve38 is opened, DCS gas which was previously stored in thebuffer tank41 is supplied to theDCS buffer nozzle44, and the DCS gas is injected into thereaction chamber12 from theinjection hole47. The flow rate of the injected DCS is 0.5 slm for example, the exhausting operation of theexhaust port16 is stopped, and the internal pressure in the furnace is set to 266 to 931 Pa for example. If the wafers1 are exposed to DCS gas, DCS raw materials adsorb to the wafers1.
2) Thefourth valve38 is closes and the supply of DCS gas is stopped. Thesixth valve43 is opened, and storing operation of DCS gas into thebuffer tank41 is started. Then, theexhaust port16 is opened, thefifth valve39 is opened, and N2gas which is inert gas is introduced from the DCS buffer nozzle (second buffer nozzle)44 into thereaction tube11 to purse theDCS buffer nozzle44 and thereaction tube11, thereby eliminating DCS atmosphere from theDCS buffer nozzle44 and thereaction tube11. The DCS atmosphere may be eliminated by evacuation instead of N2purge.
3) To prevent NH3radical42 from entering into theDCS buffer nozzle44, thefifth valve39 is opened to allow a small amount of N2gas. High frequency electricity is applied between theplasma electrodes27, thefirst valve35 is opened, and NH3gas is supplied to the NH3buffer nozzle (first buffer nozzle)34. The NH3gas is introduced into the plasma producingnozzle portion29 from the gas introducingnozzle portion28 through thecommunication port30, and is activated byplasma40 generated between theplasma electrodes27. The activated NH3radical42 is injected into thereaction chamber12 from theinjection hole45. The flow rate of the injected NH3gas is 3.0 to 4.5 slm for example, and the internal pressure in the furnace is set to 40 to 60 Pa which is lower than the internal pressure when DCS gas is introduced by conductance control of theexhaust port16. If the wafers1 are exposed to the activated NH3gas, the DCS raw material and the NH3raw material adsorbed to the wafers1 are reacted with each other, and an SiN film is formed on each wafer1 by one atom layer.
4) Thefirst valve35 is closed, the supply of NH3gas is stopped, and the application of high frequency electricity between theplasma electrodes27 is stopped. Theexhaust port16 is held opened, thesecond valve36 is opened, N2gas which is inert gas is introduced into the NH3buffer nozzle34, the N2gas is introduced into thereaction tube11 from the gas introducingnozzle portion28 through the plasma producingnozzle portion29, the NH3buffer nozzle34 and thereaction tube11 are purged to eliminate NH3atmosphere from the NH3buffer nozzle34 and thereaction tube11. The NH3atmosphere may be eliminated by evacuation instead of N2purge.
The procedure is returned to the step 1), the steps 1) to 4) are repeated by desired times. If the steps 1) to 4) is defined as one cycle, the film is formed by a constant film thickness in one cycle. Thus, the film thickness can be varied depending upon the number of cycles. The film forming time depends on the film thickness, and if the film forming temperature is 550° C. and the film thickness is 300 Å, the film forming time is about 100 minutes. Although the DCS gas was supplied first and then the NH3plasma was supplied in the above steps, this supply order may be reversed, and the NH3plasma may be supplied first and then the DCS gas may be supplied.
After the film forming operation is completed in this manner, gas in thereaction tube11 is replaced by the inert gas N2, the pressure is restored to the normal pressure, theboat2 is lowered, and the wafers1 formed with films are taken out from theboat2.
However, even if inert gas is allowed to flow from the other buffer nozzle when the raw material gas is allowed to flow from one of the buffer nozzles as described above, it is inevitable that a little gas is mixed between the buffer nozzles by dispersion phenomenon. If DCS gas enters the NH3buffer nozzle in which raw material gas is activated by plasma, the nozzle becomes a generation source of foreign materials. Reasons when the nozzle becomes the generation source of foreign materials are as follows:
1) If DCS gas is mixed in the plasma producing region of the NH3buffer nozzle at the time of plasma discharge, DCS and NH3plasma react with each other dramatically, polymers are formed and a film adheres to an inner side of the NH3buffer nozzle. This generates foreign materials.
2) A film adheres to the plasma producing region by the reaction between the DCS and NH3plasma, if the film adheres thickly, NH3radicals abruptly collide against the film, the film is damaged and the film may be peeled off. This also generates foreign materials.
In the case of a vertical ALD apparatus using a plurality of exclusive supply buffer nozzles for alternately supplying a plurality of gases, it is necessary that cleaning gas enters the buffer nozzle also in a later-described cleaning process B to eliminate a film in the buffer nozzle.
Cleaning Process B
In a state in which theboat2 does not hold wafers1, theboat elevator55 inserts theboat2 into thereaction tube11. Theseal cap17 completely closes the furnace opening of thereaction tube11 air-tightly and then, thereaction tube11 is evacuated from theexhaust port16 to exhaust gas from thereaction tube11. The internal pressure in the reaction tube is set to about 610° C. for example. Thethird valve37 is opened, and NF3gas which functions as cleaning gas is injected into thereaction chamber12 from theDCS buffer nozzle44. The flow rate of the injected NF3gas is 0.25 to 1.5 slm. At that time, evacuation in thereaction tube11 is continued, and the evacuation degree is controlled such that the internal pressure in thereaction tube11 becomes equal to a predetermined pressure. NF3molecules are activated by heat in the furnace. With this, reaction by-products adhering to portions in the furnace which were in contact with the gas, i.e., an inner wall surface of theDCS buffer nozzle44, an inner wall surface of thereaction tube11, a low temperature portion of the furnace in the vicinity of thefurnace opening8 and other portions which were in contact are etched. The NF3gas also enters the NH3buffer nozzle34, and reaction by-products in the plasma producingnozzle portion29 are etched. The etched reaction by-products are discharged out from theexhaust port16. The cleaning time is varied depending upon the film thickness, but when the film thickness is 0.75 μm, the cleaning time is about two hours.
Here, the inside of the gas introducingnozzle portion28 of the NH3buffer nozzle34 is theplasma non-producing region48 other than theplasma producing region46, and if NF3gas enters the gas introducingnozzle portion28 and F component adsorbs and bonds to and remains on the inner wall surface of the nozzle, the F component can not be removed because no NH3plasma exists. Therefore, a very small amount of nitrogen N2is allowed to flow from the gas introducingnozzle portion28 at the time of cleaning so that cleaning gas is not mixed in the gas introducingnozzle portion28. A reason why the amount of nitrogen N2is very small is as follows. That is, since it is conceived that reaction by-products adhere to the inner side of the plasma producingnozzle portion29 in some degree by the dispersion of DCS gas, it is necessary to allow cleaning gas to flow into the plasma producingnozzle portion29 to remove the reaction by-products as described above. Therefore, the amount of nitrogen N2is increased, the cleaning gas does not enter the plasma producingnozzle portion29, and the reaction by-products can not be removed. Therefore, the amount of nitrogen N2is very small to avoid this case.
In this embodiment, the cleaning gas is allowed to flow not from the NH3buffer nozzle34 which supplies NH3gas but from theDCS buffer nozzle44 which supplies DCS gas. This is because of the following three reasons.
1) It is conceived that since a film can also be formed using DCS gas only, a film of reaction by-product adhering to an inner side of theDCS buffer nozzle44 is thicker than a film of reaction by-product adhering to the inner side of the NH3buffer nozzle34. Therefore, it is necessary to effectively remove the former reaction by-product.
2) If a film is formed after the cleaning, the film forming speed is decreased. This is because that film forming gas is affected by remaining F component and film formation is hindered. When reaction gas is DCS and NH3plasma, reaction probability between the remaining F and NH3plasma is higher than that between the remaining F and DCS gas, and NH3plasma is more susceptible to F. For this reason, when NH3gas is allowed to flow from the NH3buffer nozzle34, the film forming speed is more decreased as compared with a case in which NF3gas is allowed to flow from theDCS buffer nozzle44. Thus, it is preferable that gas which is less susceptible to F is allowed to flow first.
3) If cleaning gas enters the NH3buffer nozzle, F component adsorbs and bonds to the inner wall surface of the NH3buffer nozzle. If NH3is not activated by plasma, NH3does not react with fluorine F. Therefore, when NF3gas is supplied from the NH3buffer nozzle34, if F component adsorbs and bonds to and remains in theplasma non-producing region48 other than theplasma producing region46, this F component can not be removed. Thus, it is necessary to keep supplying F into thereaction chamber12 for a while after wafer processing is started, and the film forming speed is not stabilized for a while. It is necessary to avoid such a case.
Post-Processing Process C
The post-processing process is carried out after the cleaning process. The post-processing process comprises a removing process for removing element F remaining in thebuffer nozzles34 and44 and thereaction chamber12 from thereaction tube11, and a film-preformation process for forming desires films on constituent surfaces in thebuffer nozzles34 and44 and thereaction tube11. These two removing process and the film-preformation process may be independent different processes, but if the ALD method is used, both the processes can be carried out as one process. The film-preformation procedure when the two processes are carried out as one process using the ALD method is basically the same as the above-described film forming process A, and is different from the film forming process A in that the processing time is as short as about 13 minutes. If the film formation of about 40 cycles is carried out with this processing time, it is possible to stabilize the film thickness of the wafer film formation which is carried out after the post-processing.
If the post-processing process is carried out using the ALD method in which NH3radical activated by plasma and DCS gas are alternately supplied, F component on portions in the furnace which are in contact with gas are removed as in the following manner.
1) NH3Buffer Nozzle
NH3gas is supplied to the NH3buffer nozzle34 as post-processing gas. Then, since the NH3is activated by plasma, F component which adsorbs and bonds to and remained on the wall surface of the plasma producingnozzle portion29 of the NH3buffer nozzle34 reacts with H atom which is ionized from the NH3by the activation, and they become HF which is easily be discharged from the NH3buffer nozzle34. The HF gas is discharged from theexhaust port16 of thereaction tube11 from the NH3buffer nozzle34 through thereaction chamber12. Further, at the time of film-preformation, an SiN film which is a preformed film is not intentionally formed in the NH3buffer nozzle34, but since a certain amount of DCS gas flows ito the NH3buffer nozzle34 by the dispersion effect of gas when the DCS gas is supplied, it is conceived that a certain amount of preformed SiN film is formed in the NH3buffer nozzle34. Therefore, F component which adsorbs and bonds to and remains on the wall surface of the NH3buffer nozzle34 is discharged from the atmosphere in the reaction tube by the reaction with respect to these film raw materials and by encapsulation under the films. At the time of cleaning, a very small amount of nitrogen N2is allowed to flow into the gas introducingnozzle portion28 where no NH3radical is produced so that F component is mixed. Therefore, it is unnecessary to suppress the F component by removing the same by NH3radical or by film-preformation.
2) DCS Buffer Nozzle
DCS gas is supplied to theDCS buffer nozzle44 as post-processing gas. Then, since this DCS (SiH2Cl2) gas can easily form Si—F bond, F component which adheres to and remains on the wall surface of theDCS buffer nozzle44 reacts with DCS gas and they become SiF (silicon fluoride) gas. This SiF gas is discharged from theexhaust port16 of thereaction tube11 through thereaction chamber12 from theDCS buffer nozzle44. An SiN film which is a preformed film is not intentionally formed in theDCS buffer nozzle44 when the film is to be preformed, but since a small amount of DCS gas flows into theDCS buffer nozzle44 by the dispersion effect of gas when NH3radical is supplied, it is conceived that a small amount of preform SiN film is formed in theDCS buffer nozzle44. Therefore, F component which adheres to and remains on the wall surface of theDCS buffer nozzle44 is discharged from the atmosphere in the reaction tube by the reaction with respect to these film raw materials and by encapsulation under the films.
3) Low Temperature Portion of Furnace
A reaction probability between F component which adsorbs and bonds to and remains on a low temperature portion of the furnace (furnace low temperature portion, hereinafter) in thevicinity furnace opening8 and NH3radical supplied from the NH3buffer nozzle34 into thereaction chamber12 is also high. Therefore, the NH3radical especially effectively functions, the F component becomes HF and if discharged from thereaction tube11. Since the NH3radical and DCS gas are alternately supplied into thereaction tube11 from thebuffer nozzles34 and44, F component which adsorbs and bonds to and remains on the wall surface is encapsulated under the film also by the preformed film formed on the furnace low temperature portion, and the F component is discharged from the atmosphere in the reaction tube.
4) Portions Other than Those Described Above
Portions in the furnace which are in contact with gas other than portions in the furnace described above can suppress the F component which adsorbs and bonds to and remains on the wall surface by volatilization of F component due to film-preformation and reaction with respect to DCS gas or NH3gas, and can discharge the F component.
By the above-described removing effects 1) to 4), F component on the portions in the furnace which are in contact with gas can effectively be removed. Thus, even immediately after the cleaning, F component is separated and does not hinder the film formation when a film is to be formed on a substrate, and reduction in film forming speed can effectively be prevented.
According to the embodiment, as described above, the ALD method is employed instead of the thermal CVD method when the film-preformation which is the post-processing process is to be carried out, and all of raw material gases to be used for actual film formation are supplied to the post-processing process at that time. Therefore, it is possible to remove F element from the furnace by the NH3radical and DCS, and to trap F element in the furnace by the film-preformation and thus, it is possible to effectively eliminate F element from the atmosphere in the reaction tube.
When a film is to be preformed by the thermal CVD method, a thick film is required for trapping F component. That is, in the case of the thermal CVD method, the film forming speed is slow in the low temperature portion in the vicinity offurnace opening8 as compared with other portions in the furnace which are in contact with gas. Therefore, if a film is preformed for trapping the F component based on the low temperature portion, the film forming time is increased, and the thickness of a film at other portion of furnace which is in contact with gas is increased. Further, since plasma is not used in the thermal CVD method, the thermal CVD method does not have a function for discharging remaining F component from thereaction chamber12 by NH3plasma. It is necessary to encapsulate a large amount of remaining F component under the preformed film and as a result, a thick preformed film is required. On the other hand, in the case of a preformed film formed by the ALD method as in the embodiment, a thin film suffices to trap F component. That is, in the case of the ALD method, since NH3plasma effectively removes reaction chamber remaining in the vicinity of the low temperature portion, it is only necessary to preform a thin film. When the preformed film is thin, time required until reaction by-product adhering to the inner wall surface of the reaction tube starts peeling off by the subsequent substrate processing becomes long, and the number of cleaning operations can be reduced.
Therefore, as shown inFIGS. 4A and 4B, when a film is to be preformed, a thick film is required if the thermal CVD method is used as in the conventional technique, and it is necessary to increase the processing temperature to increase the film forming speed (FIG. 4B). On the other hand, since the embodiment uses the ALD method, a thin film can be preformed by the removing effect of remaining F component by NH3plasma and DCS gas. Thus, the film-preformation temperature can be the same as the film formation temperature of the actual film, and throughput can be enhanced (FIG. 4A).
Further, according to the embodiment, the NH3buffer nozzle and the DCS gas buffer nozzle which are exclusive supply nozzles are utilized as they are as post-processing gas supply system which supplies post-processing gas, and it is unnecessary to add a thermal CVD film forming nozzle in addition to the exclusive supply nozzle. Thus, the structure of the reaction tube does not become complicated, and costs are not increased. Since the thermal CVD film forming nozzle is not added, foreign materials are not generated by the film formation in the CVD film forming nozzle.
If a substrate processing apparatus which uses the above-described film forming process, cleaning process and post-processing process is used, it is possible to produce a semiconductor device which is less affected by element included in cleaning gas remaining in a reaction chamber.
Although the SiN film was formed using DCS and NH3activated by plasma as raw material gases, the kinds of gases are not limited to those. For example, the SiN film can also be formed using Si2Cl6(hexachloro disilane: HCD) and NH3(it maybe or may not be activated by plasma) as raw material gases.
Although NF3was used as cleaning gas in this embodiment, etching gas including other F (fluorine) such as ClF3may also be used.
Although the actual film forming operation and the post-processing process are carried out by the ALD method in the embodiment, the invention is not limited to this. For example, the actual film forming operation may be carried out by the thermal CVD method, and only the post-processing process may be carried out by the ALD method. Although the present invention is applied to the batch type vertical ALD apparatus in the embodiment, the invention can also be applied to a single wafer type ALD apparatus.
Although two buffer nozzles having large space capacities as compared with a normal nozzle are used and gas is activated by plasma in one of the buffer nozzles in the embodiment, the invention is not limited to this structure. For example, although the processing time of the post-processing process is increased, the present invention can also be applied to a structure in which gas is activated by plasma outside of the buffer nozzle, or a normal thin nozzle is used and gas is activated by plasma outside of the nozzle.
The entire disclosure of Japanese Patent Application No. 2002-327193 filed on Nov. 11, 2002 including specification, claims, drawings and abstract is incorporated herein by reference in its entirety.
INDUSTRIAL APPLICABILITY According to the preferred embodiment of the invention as described above, since reaction gas is used as post-processing gas carried out after the cleaning, element included in the cleaning gas can effectively be removed. If all reaction gases used when a substrate is subjected to desired processing are introduced as post-processing gases, it is unnecessary to add a gas supply system, and it is possible to prevent the structure from becoming complicated. Further, foreign material from a gas supply system generated when the gas supply system is added can be prevented from being generated.
As a result, the present invention can suitably be utilized especially for a substrate processing apparatus which forms a film on a semiconductor substrate by the ALD (Atomic Layer Deposition) also.