JP5693199B2 - Substrate processing apparatus and substrate processing method - Google Patents

Description

  The present invention relates to a substrate processing apparatus and a substrate processing method for processing a substrate surface with a processing liquid.

  A substrate processing apparatus is an apparatus for supplying a processing liquid to the surface of a substrate such as a semiconductor wafer or a glass substrate and processing the surface of the substrate in a manufacturing process of a semiconductor device or a liquid crystal display device. Examples of the substrate processing apparatus include a resist removal apparatus (see, for example, Patent Document 1) that removes a resist film that is no longer needed from the substrate surface, and a cleaning apparatus that cleans organic substances attached to the substrate surface.

  In the step of removing the resist film and organic matter that are no longer needed from the substrate surface, an oxidative removal process is performed in which the resist film and organic matter are oxidized and removed by dry ashing or ozone water. In this case, a metal layer such as a reflective film (for example, a transition metal such as Mo, Cr, or Ru) may be laminated on the substrate surface like a reflective mask for EUV (Extreme Ultra Violet). Also, the same oxidation removal treatment as described above is performed.

JP 2006-278509 A

  However, when the same oxidation removal treatment as described above is performed on the substrate surface having the metal layer, when removing the resist film and organic matter, the metal layer is non-uniformly about 0.1 to 1.0 nm together with them. Will be etched. For this reason, the surface of a metal layer becomes rough and the functionality of a metal layer will fall.

  This invention is made | formed in view of the above, The objective is to provide the substrate processing apparatus and substrate processing method which can suppress that the functionality of the metal layer on a board | substrate falls.

According to an embodiment of the present invention, a substrate processing apparatus includes:
A first processing liquid supply device for supplying a first processing liquid to a surface of a substrate having a metal layer formed of a transition metal;
A second processing liquid supply device for supplying a second processing liquid containing molecules having adsorption characteristics to the transition metal on the surface of the substrate;
A molecule removing unit for removing the molecules adsorbed on the metal layer;
It is to provide.

A second feature according to the embodiment of the present invention is a substrate processing method,
Supplying a first treatment liquid and a second treatment liquid containing molecules having an adsorption property to the transition metal to a surface of a substrate having a metal layer formed of a transition metal; and the first treatment liquid; After the supply of the second treatment liquid is completed, the molecules adsorbed on the metal layer are removed .

  According to this invention, it can suppress that the functionality of the metal layer on a board | substrate falls.

1 is a diagram showing a schematic configuration of a substrate processing apparatus according to a first embodiment of the present invention. It is a 1st sectional view for explaining processing liquid supply to a substrate surface which a substrate processing device shown in Drawing 1 performs. It is the 2nd sectional view for explaining processing liquid supply to the above-mentioned substrate surface. It is a flowchart which shows the flow of the substrate processing process which the substrate processing apparatus shown in FIG. 1 performs. It is a figure which shows schematic structure of the substrate processing apparatus which concerns on the 2nd Embodiment of this invention. It is a flowchart which shows a part of flow of the substrate processing process which the substrate processing apparatus shown in FIG. 5 performs. It is sectional drawing which shows schematic structure of the 1st nozzle and 2nd nozzle with which the substrate processing apparatus which concerns on the 3rd Embodiment of this invention is provided. It is sectional drawing which shows schematic structure of the 1st nozzle and 2nd nozzle with which the substrate processing apparatus which concerns on the 4th Embodiment of this invention is provided.

(First embodiment)
A first embodiment of the present invention will be described with reference to FIGS.

  As shown in FIG. 1, a substrate processing apparatus 1 according to a first embodiment of the present invention is provided with a processing box 2, a cup 3 provided in the processing box 2, and a substrate W horizontally in the cup 3. A table 4 that is supported in a state, a table rotating mechanism 5 that rotates the table 4 in a horizontal plane, a first processing liquid supply device 6 that supplies a first processing liquid to the surface of the substrate W on the table 4, A second processing liquid supply device 7 that supplies the second processing liquid to the surface of the substrate W on the table 4 and a control unit 8 that controls each unit are provided.

  The processing box 2 is a processing chamber that accommodates the cup 3, the table 4, and the like. At the top of the processing box 2, a fan 2a with a filter for downflow is provided. The fan 2 a is electrically connected to the control unit 8, and its driving is controlled by the control unit 8.

  The cup 3 is formed in a cylindrical shape, and encloses the table 4 from the periphery and accommodates it inside. The upper part of the peripheral wall of the cup 3 is inclined toward the inside in the radial direction, and is opened so that the substrate W on the table 4 is exposed. The cup 3 receives processing liquid that flows down or scatters from the rotating substrate W. A discharge pipe (not shown) for discharging the received processing liquid is provided at the bottom of the cup 3.

  The table 4 is positioned near the upper part in the cup 3 and is provided to be rotatable in a horizontal plane. The table 4 detachably holds a substrate W such as a wafer or a glass substrate by a clamping member (not shown) such as a chuck pin.

  The table rotating mechanism 5 includes a rotating shaft 5a connected to the table 4, and a motor 5b serving as a drive source for rotating the rotating shaft 5a. The motor 5 b is electrically connected to the control unit 8, and its driving is controlled by the control unit 8. The table rotating mechanism 5 rotates the table 4 via the rotating shaft 5a by the motor 5b.

  The first processing liquid supply device 6 includes a first nozzle 6a that supplies the first processing liquid to the surface of the substrate W on the table 4 from above, and a first processing liquid to the first nozzle 6a. And a first supply unit 6b for supplying.

  The first nozzle 6 a is disposed above the table 4 and discharges and supplies the first processing liquid to the surface of the substrate W on the table 4. The first nozzle 6a is connected to the first supply unit 6b by a pipe 6c serving as a first processing liquid supply channel.

The first supply unit 6b includes a tank that stores the first processing liquid, a pump that serves as a drive source, a valve that serves as an adjustment valve that adjusts the supply amount (none of which is shown), and the like. The pump and the valve are electrically connected to the control unit 8, and the driving thereof is controlled by the control unit 8. The first supply unit 6b sends the first supply liquid to the first nozzle 6a by a pump under the control of the control unit 8. In the embodiment of the present invention, for example, ozone (O ₃ ) water is used as the first treatment liquid.

  The second processing liquid supply device 7 includes a second nozzle 7a for supplying the second processing liquid from above to the surface of the substrate W on the table 4, and the second processing liquid to the second nozzle 7a. And a second supply unit 7b for supplying the power.

  The second nozzle 7 a is disposed above the table 4 and discharges and supplies the second processing liquid to the surface of the substrate W on the table 4. The second nozzle 7a is connected to the second supply unit 7b by a pipe 7c serving as a second processing liquid supply channel.

  The second supply unit 7b includes a tank that stores the second processing liquid, a pump that serves as a drive source, a valve that serves as an adjustment valve that regulates the supply amount (none of which are shown), and the like. The pump and the valve are electrically connected to the control unit 8, and the driving thereof is controlled by the control unit 8. The second supply unit 7b sends the second supply liquid to the second nozzle 7a by a pump under the control of the control unit 8. In the embodiment of the present invention, as the second treatment liquid, for example, a solution in which CO (carbon monoxide) is dissolved (CO-dissolved water) or a solution containing CO bubbles (CO bubble water) is used. Used.

  The control unit 8 includes a microcomputer that centrally controls each unit and a storage unit that stores substrate processing information and various programs related to substrate processing. The control unit 8 controls the table rotation mechanism 5, the first processing liquid supply device 6 and the second processing liquid supply device 7 based on the substrate processing information and various programs, and rotates the table 4 by the table rotation mechanism 5. Then, the first processing liquid is supplied from the first nozzle 6a and the second processing liquid is supplied from the second nozzle 7a to the surface of the substrate W on the rotating table 4.

  Here, as shown in FIG. 2, a metal layer M1 made of a transition metal such as Ru is laminated on the entire surface of the substrate W, and a patterned absorber layer is formed on the metal layer M1. M2 is laminated. Further, a resist layer (resist film) M3 is laminated on the absorber layer M2. The absorber layer M2 is a layer that absorbs EUV (Extreme Ultra Violet) light. The resist layer M3 is formed of a photoresist, and is a layer for forming the pattern of the absorber layer M2 on the metal layer M1. The substrate W finally becomes a reflective mask for EUV used in EUV lithography technology.

  The resist layer M3 on the surface of the substrate W is etched and removed by the first treatment liquid. At this time, the surface of the exposed metal layer M1 that is not covered with the resist layer M3 is also the first layer. For example, the processing liquid etches non-uniformly by about 0.1 to 1.0 nm. In order to prevent this, in addition to supplying the first processing liquid to the surface of the substrate W, the second processing liquid is supplied by the second processing liquid supply device 7.

  The second treatment liquid is a treatment liquid containing molecules having adsorption characteristics with respect to a transition metal (for example, Mo, Cr, Ru, etc.) that is a material for forming the metal layer M1. Examples of molecules having this adsorption property include molecules that form coordinate bonds and hydrogen bonds, such as carbon monoxide having unpaired electrons, ethylene having a double bond, and organic compounds having an OH group.

Here, O ₃ water is used as the first processing liquid (processing liquid for removing the resist layer M3), and CO-dissolved water or CO bubble water is used as the second processing liquid (processing liquid for protecting the metal layer M1). Used. Note that competitive adsorption (competitive adsorption) occurs between the first treatment liquid and the second treatment liquid on the surface of the metal layer M1. However, CO molecules (CO) contained in the second treatment liquid are more likely to be adsorbed to the metal layer M1 than the first treatment liquid.

  Therefore, as shown in FIG. 3, CO, which is a molecule of CO contained in the second treatment liquid, is adsorbed (chemically adsorbed) on the surface of the exposed metal layer M1 that is not covered with the resist layer M3. Cover the surface. This CO coating protects the exposed metal layer M1 from the first treatment liquid. Note that the molecules in the second treatment liquid are not so adsorbing to organic compounds such as resist, so that the resist layer M3 is not covered, and the resist layer M3 is covered with the first treatment liquid. It is etched and completely removed.

  Next, substrate processing (substrate processing method) performed by the above-described substrate processing apparatus 1 will be described with reference to FIG. Note that a substrate W is mounted on the table 4, and the preparation is completed.

  As shown in FIG. 4, the control unit 8 controls the table rotating mechanism 5, rotates the table 4, and further controls the second treatment liquid supply device 7, and the second nozzle is supplied from the second supply unit 7b. The second processing liquid is sent to 7a, and the second processing liquid is supplied from the second nozzle 7a to the surface of the substrate W on the rotating table 4 (step S1). The second nozzle 7 a discharges the second processing liquid toward the vicinity of the center of the surface of the substrate W on the rotating table 4. The second processing liquid supplied near the center of the surface of the substrate W spreads over the entire surface of the substrate W due to the centrifugal force generated by the rotation of the substrate W.

  The supply of the second processing liquid is performed before supplying the first processing liquid to the surface of the substrate W. Thereby, before supplying the first treatment liquid, molecules (CO) are adsorbed on the surface of the metal layer M1, and the surface is covered with the molecules (CO) (see FIG. 3). Thereby, even when the first processing liquid is supplied to the surface of the substrate W, the surface of the metal layer M1 can be prevented from being etched by the first processing liquid.

  After the predetermined time of step S1, the control unit 8 controls the first processing liquid supply device 6, sends the first processing liquid from the first supply unit 6b to the first nozzle 6a, and the first nozzle The first processing liquid is supplied to the surface of the substrate W on the rotating table 4 from 6a, and the second processing liquid and the first processing liquid are supplied simultaneously (step S2). Similarly to the second nozzle 7a, the first nozzle 6a also discharges the first treatment liquid toward the vicinity of the center of the surface of the substrate W on the rotating table 4. The first processing liquid supplied to the vicinity of the center of the surface of the substrate W spreads over the entire surface of the substrate W due to the centrifugal force generated by the rotation of the substrate W while being mixed with the second processing liquid.

By supplying the first processing liquid, the resist layer M3 on the surface of the substrate W is etched and removed. At this time, the first treatment liquid (O ₃ water) chemically reacts with the molecules (CO) adsorbed on the surface of the metal layer M1 in the aforementioned step S1, and the adsorbed molecules (CO) become the surface of the metal layer M1. May be removed from. In order to suppress this chemical reaction, the second treatment liquid is also supplied in step S2. Thereby, since the molecules (CO) are replenished, the covering state of the metal layer M1 by the molecules (CO) can be maintained.

  After the predetermined time of step S2, the control unit 8 controls the first processing liquid supply device 6, stops the supply of the first processing liquid from the first supply unit 6b to the first nozzle 6a, and The supply of the second processing liquid by the second nozzle 7a is continued, and only the second processing liquid is supplied to the surface of the substrate W (step S3). The second nozzle 7a discharges the second processing liquid toward the vicinity of the center of the surface of the substrate W on the rotating table 4 as described above. The second processing liquid supplied near the center of the surface of the substrate W spreads over the entire surface of the substrate W due to the centrifugal force generated by the rotation of the substrate W. Thereby, the entire surface of the substrate W is cleaned with the second processing liquid.

  The supply of the second processing liquid is performed to remove the first processing liquid from the surface of the substrate W. If the first processing liquid can be removed in the next rinsing step, the above-described steps are performed. It is also possible to omit S3.

  After the predetermined time of step S3 described above, the control unit 8 controls the second processing liquid supply device 7, stops the supply of the second processing liquid from the second supply unit 7b to the second nozzle 7a, and Ultrapure water is supplied to the surface of the substrate W from the nozzle that does not, and rinse treatment with the ultrapure water is performed (step S4). The ultrapure water supplied to the surface of the substrate W spreads over the entire surface of the substrate W due to the centrifugal force generated by the rotation of the substrate W. As a result, the entire surface of the substrate W is cleaned with ultrapure water.

  After the predetermined time of step S4 described above, the control unit 8 stops the supply of ultrapure water from the nozzle described above, and continues the rotation of the table 4 on which the substrate W is placed for a predetermined time. The surface of is dried (step S5). The ultrapure water remaining on the surface of the substrate W is scattered by the centrifugal force generated by the rotation of the substrate W and collected by the cup 3. After this drying process, the substrate W is removed from the table 4 and taken out from the processing box 2.

  As described above, according to the first embodiment of the present invention, the first processing liquid supply device 6 that supplies the first processing liquid to the surface of the substrate W having the metal layer M1 formed of the transition metal. And a second treatment liquid supply device 7 for supplying a second treatment liquid containing a molecule having an adsorption characteristic for the transition metal on the surface of the substrate W, in addition to the first treatment liquid. The second processing liquid is supplied to the surface of the substrate W. Thereby, molecules (CO) contained in the second treatment liquid are adsorbed to the metal layer M1 on the surface of the substrate W, and the surface of the metal layer M1 is covered and protected by the aforementioned molecules. For this reason, it is possible to prevent the surface of the metal layer M1 from being treated with the first treatment liquid, and to prevent the surface of the metal layer M1 from becoming rough. As a result, it is possible to prevent the functionality of the metal layer M1 on the substrate W from being lowered.

In addition, the second processing liquid is supplied in the above-described step S1, and then the first processing liquid (O ₃ ) is supplied in a state where molecules (CO) are adsorbed on the metal layer M1 on the surface of the substrate W. Since the surface of the metal layer M1 on the substrate W is covered with the molecules (CO) and reliably protected before the supply of the first processing liquid (O ₃ ), the surface is protected with the first processing liquid (O ₃ ). It is possible to reliably suppress the treatment by O ₃ ). As a result, it is possible to reliably prevent the functionality of the metal layer M1 on the substrate W from being lowered.

  In addition, by supplying the first processing liquid and the second processing liquid to the surface of the substrate W at the same time in step S2, the first processing liquid and the second processing liquid can be mixed uniformly. The uniformity of processing on the substrate W can be improved. As described above, in the above-described step S2, the first processing liquid and the second processing liquid are simultaneously supplied to the surface of the substrate W. However, the present invention is not limited to this. For example, the first processing liquid and The second treatment liquid may be alternately supplied to the surface of the substrate W. When the first processing liquid and the second processing liquid are alternately supplied, the above-described chemical reaction between the first processing liquid and the second processing liquid is suppressed as compared with the case where they are supplied simultaneously. Therefore, it is possible to suppress a decrease in the concentration of adsorbed molecules (CO) in the second treatment liquid.

(Second Embodiment)
A second embodiment of the present invention will be described with reference to FIGS.

  The second embodiment of the present invention is basically the same as the first embodiment. In the second embodiment, differences from the first embodiment will be described, the same parts as those described in the first embodiment will be denoted by the same reference numerals, and the description thereof will also be omitted.

  As shown in FIG. 5, in the substrate processing apparatus 1 according to the second embodiment of the present invention, the molecule removal unit 11 that removes molecules (CO) adsorbed on the metal layer M <b> 1 on the surface of the substrate W is provided on the table 4. It is provided above. The molecule removing unit 11 is a removing device that removes molecules (CO) adsorbed on the metal layer M1 by ultraviolet rays, heat treatment, or the like, and is electrically connected to the control unit 8, and its driving is controlled by the control unit 8. Is done. Such a molecule removing unit 11 is provided when it is necessary to remove the molecules (CO) adsorbed on the metal layer M1, that is, when there is a problem if the molecules (CO) remain on the surface of the metal layer M1. It is done.

  Next, substrate processing (substrate processing method) performed by the above-described substrate processing apparatus 1 will be described with reference to FIG. In FIG. 6, step S6 and subsequent steps are described. This step S6 is a step connected to step S5 in FIG. 5 according to the first embodiment, and after step S5 in FIG. 5 is performed, Steps S6 and after in FIG. 6 are performed.

  As shown in FIG. 6, when step S5 is completed, the control unit 8 controls the molecule removal unit 11 to perform a molecule removal process for removing molecules (CO) adsorbed on the surface of the substrate W, that is, the metal layer M1 (see FIG. 6). Step S6). The molecule removing unit 11 irradiates the surface of the substrate W on the table 4 with ultraviolet rays or supplies heat for a predetermined time to remove molecules (CO) adsorbed on the metal layer M1 on the surface of the substrate W. At this time, the control unit 8 may control the table rotating mechanism 5 to rotate the table 4 or not.

  After the predetermined time of step S6 described above, the control unit 8 supplies ultrapure water to the surface of the substrate W from a nozzle (not shown), and performs a rinsing process using the ultrapure water (step S7). The ultrapure water supplied to the surface of the substrate W spreads over the entire surface of the substrate W due to the centrifugal force generated by the rotation of the substrate W. As a result, the entire surface of the substrate W is cleaned with ultrapure water.

  After the predetermined time of step S7 described above, the control unit 8 stops the supply of ultrapure water by the nozzle described above, and continues the rotation of the table 4 on which the substrate W is placed for a predetermined time. The surface of is dried (step S8). The ultrapure water remaining on the surface of the substrate W is scattered by the centrifugal force generated by the rotation of the substrate W and collected by the cup 3. After this drying process, the substrate W is removed from the table 4 and taken out from the processing box 2.

  As described above, according to the second embodiment of the present invention, the same effect as that of the first embodiment can be obtained. Furthermore, by providing a molecule removal unit 11 that removes molecules (CO) adsorbed on the metal layer M1 on the surface of the substrate W, molecules (CO) adsorbed on the metal layer M1 on the surface of the substrate W are provided as necessary. ) Can be removed. That is, when a problem occurs when the molecule (CO) adsorbed on the metal layer M1 remains, the molecule (CO) can be removed, thereby preventing the occurrence of the problem caused by the remaining molecule. be able to.

(Third embodiment)
A third embodiment of the present invention will be described with reference to FIG.

  The third embodiment of the present invention is basically the same as the first embodiment. In the third embodiment, differences from the first embodiment will be described, and the same parts as those described in the first embodiment will be denoted by the same reference numerals, and the description thereof will also be omitted.

  In the substrate processing apparatus 1 according to the third embodiment of the present invention, as shown in FIG. 7, a second nozzle 7a is provided in the first nozzle 6a. The second nozzle 7a functions as an inner cylinder serving as a central flow path through which the second processing liquid passes, and the first nozzle 6a accommodates the aforementioned inner cylinder and has an outer cylinder having a ring-shaped flow path. Function as. The tip of the second nozzle 7a is located in the first nozzle 6a, and in particular, the first nozzle 6a in the vertical direction so that the second processing liquid is well mixed with the first processing liquid. It is located above the center position.

  As described above, according to the third embodiment of the present invention, the same effect as that of the first embodiment can be obtained. Further, the first processing liquid and the second processing liquid are mixed in the first nozzle 6 a and then supplied to the surface of the substrate W on the table 4. As a result, the first processing liquid and the second processing liquid can be mixed uniformly, and the processing uniformity for the substrate W can be improved.

(Fourth embodiment)
A fourth embodiment of the present invention will be described with reference to FIG.

  The fourth embodiment of the present invention is basically the same as the first embodiment. In the fourth embodiment, differences from the first embodiment will be described, and the same parts as those described in the first embodiment will be denoted by the same reference numerals, and the description thereof will also be omitted.

  In the substrate processing apparatus 1 according to the fourth embodiment of the present invention, as shown in FIG. 8, the first nozzle 6 a and the second nozzle 7 a are the first processing liquid with respect to the surface of the substrate W on the table 4. And the second processing liquid are formed at the same supply position. As a result, the first processing liquid and the second processing liquid are supplied to the same position on the surface of the substrate W and mixed at that position.

  As described above, according to the fourth embodiment of the present invention, the same effect as in the first embodiment can be obtained. Further, since the first processing liquid and the second processing liquid are mixed on the surface of the substrate W, the chemical reaction between the first processing liquid and the second processing liquid is compared with the third embodiment described above. Since the start can be delayed, it is possible to suppress a decrease in the concentration of adsorbed molecules (CO) in the second treatment liquid.

(Other embodiments)
In addition, the above-mentioned embodiment which concerns on this invention is an illustration, and the scope of the invention is not limited to them. The above-described embodiment can be variously modified. For example, some components may be deleted from all the components shown in the above-described embodiment, and further, components according to different embodiments may be appropriately combined. Also good.

DESCRIPTION OF SYMBOLS 1 Substrate processing apparatus 6 1st process liquid supply apparatus 7 2nd process liquid supply apparatus 8 Control part 11 Molecule removal part M1 Metal layer W board | substrate

Claims (8)

A first processing liquid supply device for supplying a first processing liquid to a surface of a substrate having a metal layer formed of a transition metal;
A second processing liquid supply device for supplying a second processing liquid containing molecules having adsorption characteristics to the transition metal on the surface of the substrate;
A molecule removing unit for removing the molecules adsorbed on the metal layer;
A substrate processing apparatus comprising:   A controller for controlling the first processing liquid supply device and the second processing liquid supply device so as to simultaneously supply the first processing liquid and the second processing liquid to the surface of the substrate; The substrate processing apparatus according to claim 1.   A controller that controls the first processing liquid supply device and the second processing liquid supply device so as to alternately supply the first processing liquid and the second processing liquid onto the surface of the substrate; The substrate processing apparatus according to claim 1, further comprising a substrate processing apparatus.   The first treatment liquid supply device and the second treatment liquid supply device are configured to supply the second treatment liquid and supply the first treatment liquid in a state where the molecules are adsorbed on the metal layer. The substrate processing apparatus according to claim 1, further comprising a control unit that controls the substrate processing apparatus. Supplying a first treatment liquid and a second treatment liquid containing molecules having an adsorption property to the transition metal to a surface of a substrate having a metal layer formed of a transition metal; and the first treatment liquid; The substrate processing method , wherein after the supply of the second processing liquid is completed, the molecules adsorbed on the metal layer are removed . 6. The substrate processing method according to claim 5 , wherein the first processing liquid and the second processing liquid are simultaneously supplied to the surface of the substrate. 6. The substrate processing method according to claim 5 , wherein the first processing liquid and the second processing liquid are alternately supplied to the surface of the substrate. The substrate processing method according to claim 5, wherein the second processing liquid is supplied and then the first processing liquid is supplied.

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