JP6832108B2 - Substrate processing method - Google Patents

Description

The present invention relates to a technique for removing organic substances such as polymers adhering to the surface of a substrate with a removing liquid.

For example, in the process of manufacturing a semiconductor device, when a fine circuit pattern is formed on the surface of a semiconductor wafer, a dry etching step such as reactive ion etching is performed. At the time when the etching of the metal film in the dry etching step is completed, a part of the resist film may be altered to generate an organic substance such as a polymer, and the reaction product may be deposited on the surface of the metal film or the like. Since this organic substance is not removed from the wafer in the resist removing liquid treatment step performed after the etching step, it is necessary to remove the organic substance from the surface of the wafer before the resist removing liquid treatment step. Therefore, after the dry etching step, a removing liquid having an action of removing organic substances is supplied to the surface of the wafer, and the removing liquid is used to remove the organic substances from the wafer surface.

It has been proposed to perform pretreatment with a pretreatment agent before performing this removal liquid treatment (for example, Patent Documents 1 and 2). By using ozone water, hydrogen water, ozone gas, and small pieces of dry ice as the pretreatment agent, the organic matter on the substrate is oxidized. Oxidized organic matter can be easily removed by the removing liquid.

JP-A-2002-134401 Japanese Unexamined Patent Publication No. 2004-96055

However, when a liquid such as ozone water is used as the pretreatment agent, the structure such as a metal film may also be oxidized, resulting in loss or deterioration of the structure. On the other hand, when the treatment is performed with a single gas such as ozone gas, there is a problem that it is difficult to shorten the treatment time because the oxidizing power is weak.

Therefore, an object of the present invention is to provide a technique for effectively removing organic substances such as polymers while suppressing deterioration of structures formed on a substrate.

The first aspect is a substrate processing method for treating a substrate in which the Low-K film is exposed and the organic matter remains, and the space above the substrate in which the organic matter remains on the surface is spectroscopically used. An oxidation treatment step of oxidizing the organic matter and the oxidation treatment by bringing ozone gas and radicals generated by irradiating UV until the wave number starts to decrease at around 1026 come into contact with the organic matter remaining on the substrate. After the step, the removal liquid treatment step of removing the organic matter by supplying the removal liquid to the substrate is included.

The second aspect is the first substrate treatment method, wherein the removal liquid is a treatment liquid containing no organic solvent.

The third aspect is a first or a second state like substrate processing method, the oxidation step is performed in a state where the metal film is not lost.

Further, the fourth aspect is the substrate processing method according to any one of the first to third aspects, and the oxidation treatment step is performed in a state where the Low-K film is not deteriorated.

The fifth aspect is the substrate processing method according to the fourth aspect, in which the oxidation treatment step is performed in a state where the Low-K film is not oxidized.

The sixth aspect is the substrate processing method according to any one of the first to fifth aspects, and the oxidation treatment step is a step of treating the substrate after the plasma etching treatment.

The seventh aspect is the substrate processing method according to any one of the first to sixth aspects, after the oxidation treatment step is performed with the substrate arranged in the first chamber. The moving step of moving the substrate to a second chamber different from the first chamber is further included, and the removing liquid treatment step is performed with the substrate arranged in the second chamber.

According to the substrate processing method of the first aspect, the organic matter on the substrate can be oxidized while suppressing the oxidation of the structure formed on the substrate by the ozone gas and radicals generated by UV irradiation. Here, reforming means that the state (a part of the composition) changes while the film remains on the substrate, and oxidation is one aspect of reforming. Since the organic substance modified by partial oxidation can be easily removed from the substrate by using the removing liquid, the amount of the removing liquid used can be reduced or the time required for the removing liquid treatment can be shortened.

Further , the ozone gas and radicals generated by UV irradiation can oxidize the organic matter on the substrate while suppressing the oxidation of the structure formed on the substrate. Since the organic substance modified by partial oxidation can be easily removed from the substrate by using the removing liquid, the amount of the removing liquid used can be reduced or the time required for the removing liquid treatment can be shortened.

According to the substrate treatment method of the second aspect, the organic matter can be effectively removed even with the removing liquid containing no organic solvent by pre-oxidizing the organic matter by the pretreatment.

According to the substrate processing method of the third aspect, the loss of the metal film can be suppressed.

According to the substrate processing method of the fourth aspect, deterioration of the Low-K film can be suppressed.

According to the substrate processing method of the fifth aspect, by suppressing the oxidation of the Low-K film, it is possible to suppress the deterioration of the Low-K film due to oxidation.

According to the substrate processing method of the sixth aspect, the organic matter remaining on the substrate after the plasma etching treatment can be effectively removed.

According to the substrate processing method of the seventh aspect, the dry treatment and the wet treatment can be performed separately.

It is a schematic block diagram of the substrate processing apparatus 100 of 1st Embodiment. It is a schematic side view which shows the modification processing part 10 of 1st Embodiment. It is a schematic side view which shows the removal liquid processing part 20 of 1st Embodiment. It is the schematic sectional drawing which shows the surface of the substrate 90 partially enlarged. It is a figure which shows the structural formula of the CF polymer. It is a figure which shows the change of the contact angle according to the irradiation time of UV. It is a figure which evaluated the change of the coupling state caused by UV irradiation by Fourier transform infrared spectroscopy (FTIR spectroscopy). It is a figure which shows the change of the bonding state of the Low-K film 93 by UV irradiation. It is a figure which shows the change of the film thickness of the Low-K film 93 by UV irradiation. It is a figure which shows the measurement result of the film thickness of copper oxide after UV irradiation. It is a schematic side view which shows the modification processing part 10A of the 2nd Embodiment.

Hereinafter, embodiments of the present invention will be described with reference to the accompanying drawings. It should be noted that the components described in this embodiment are merely examples, and the scope of the present invention is not limited to them. In the drawings, the dimensions and numbers of each part may be exaggerated or simplified as necessary for easy understanding.

<1. First Embodiment>
FIG. 1 is a schematic configuration diagram of the substrate processing apparatus 100 of the first embodiment. FIG. 2 is a schematic side view showing the reforming processing unit 10 of the first embodiment. FIG. 3 is a schematic side view showing the removal liquid treatment unit 20 of the first embodiment.

The substrate processing apparatus 100 is an apparatus for removing organic substances such as polymers adhering to the surface of the substrate 90. Specifically, the substrate 90 is a metal film such as aluminum, copper, titanium, tungsten, etc. formed on the surface of a semiconductor wafer, a silicon oxide film, a silicon nitride film, an organic insulating film, and a low dielectric constant dielectric material film (hereinafter, hereinafter, A low-K film) or the like is dry-etched (for example, plasma-etched) using a resist film as a mask, that is, a substrate 90 in a wiring forming step is assumed. The substrate processing apparatus 100 removes organic substances such as polymers derived from a resist film that adhere to the surface of the substrate 90 after dry etching.

The substrate processing device 100 includes a reforming processing unit 10, a removing liquid processing unit 20, and a transfer device 30. Further, the substrate processing device 100 includes a control unit (not shown) that controls the operations of the reforming processing unit 10, the removing liquid processing unit 20, and the transport device 30.

<Modification processing unit 10>
The reforming processing unit 10 includes a first chamber 11 capable of forming a closed space (see FIG. 1), and the reforming processing unit 10 is provided with a configuration for performing the reforming treatment in the first chamber 11. Specifically, the reforming processing unit 10 includes a stage 12 and a UV irradiator 14 (see FIG. 2).

The stage 12 supports the substrate 90 in a horizontal posture on its upper surface. When mounting the substrate 90 on the stage 12, a plurality of lift pins (not shown) projecting upward from the surface of the stage 12 are used. With the substrate 90 mounted on the plurality of lift pins, the lift pin is lowered and buried below the surface of the stage 12, so that the substrate 90 is mounted on the stage 12. When the substrate 90 is carried out from the stage 12, the substrate 90 is supported by the lift pins by pushing up the substrate 90 by a plurality of lift pins.

A plurality of suction holes for sucking and holding the substrate 90 may be provided on the upper surface of the stage 12. Further, an elongated suction groove may be formed on the stage 12.

The UV irradiator 14 irradiates the surface of the substrate 90 supported by the stage 12 with ultraviolet rays (hereinafter, UV). The UV irradiator 14 is not particularly limited, but may be composed of, for example, an excimer UV lamp (outputs UV having a wavelength of 172 nm) or a low-pressure mercury lamp (outputs UV having wavelengths of 185 nm and 254 nm). The illuminance is also not particularly limited, but it is preferable that the illuminance ^{is set to 20} to 50 mW / cm 2 as an example, and UV can be uniformly irradiated to the entire surface of the substrate 90.

When the UV irradiator 14 irradiates the substrate 90 with UV, ozone gas 18, which is an oxidizing gas, is generated on the substrate 90, and radicals are generated. This promotes oxidation of the polymer, modifies the polymer and increases its solubility. The step of irradiating the substrate 90 with UV in the reforming treatment unit 10 corresponds to the reforming treatment step.

<Removal liquid treatment unit 20>
The removal liquid treatment unit 20 includes a second chamber 21 capable of forming a closed space (see FIG. 1), and the inside of the second chamber 21 is provided with a configuration for performing the removal liquid treatment.

For example, the removal liquid processing unit 20 includes a spin chuck 220, a rotary support shaft 222, and a spin motor 224. The spin chuck 220 is a disk-shaped member that attracts the substrate 90 and holds it in a horizontal posture. The spin chuck 220 is supported by a rotary support shaft 222, and the rotary support shaft 222 is connected to the rotary shaft of the spin motor 224. By driving the spin motor 224, the substrate 90 is supported by the spin chuck 220 and rotates about a vertical axis in a horizontal plane.

The removal liquid treatment unit 20 includes a cup 240 that surrounds the substrate 90. The cup 240 is open upward and is formed in a shape that surrounds the side and the lower side of the substrate 90. The cup 240 is supported so as to move up and down when the substrate 90 is carried in and out. A discharge pipe 242 is connected to the bottom surface of the cup 240. The treatment liquid (removal liquid) dropped from the substrate 90 collides with the inner peripheral wall surface of the cup 240, flows down to the bottom surface along the wall surface, and is discharged to the outside of the cup 240 via the discharge pipe 242.

The removal liquid treatment unit 20 includes a removal liquid supply mechanism 26. The removing liquid supply mechanism 26 is arranged on the outside of the cup 240. The removing liquid supply mechanism 26 includes a discharge nozzle 260, an arm 262, an arm holding portion 264, a rotary support shaft 266, and an arm moving mechanism 268.

The discharge nozzle 260 is arranged above the substrate 90 supported by the spin chuck 220, and the discharge port at the tip thereof is arranged downward so as to face the surface of the substrate 90, and discharges the removing liquid to the surface of the substrate 90. To do. As a result, the removing liquid is supplied to the substrate 90.

The discharge nozzle 260 is supported by the tip of the arm 262. The arm 262 is held by the arm holding portion 264 at its base end, and is arranged along the horizontal direction. The arm holding portion 264 is fixed to the upper end portion of the rotary support shaft 266 arranged along the vertical direction. The rotary support shaft 266 is rotated by the arm moving mechanism 268 around an axis extending in the vertical direction. Further, the rotary support shaft 266 is moved up and down along the vertical direction by the arm moving mechanism 268.

By driving the arm moving mechanism 268, the discharge nozzle 260 reciprocates in a horizontal plane between the central portion and the peripheral portion of the substrate 90. Further, by driving the arm moving mechanism 268, the discharge nozzle 260 is brought close to and separated from the surface of the substrate 90. The arm 262 that supports the discharge nozzle 260 is configured to retract to a position outside the cup 240.

The removal liquid treatment unit 20 includes a removal liquid supply pipe 28. One end of the removal liquid supply pipe 28 is connected to a removal liquid supply device (not shown), and the other end is connected to the discharge nozzle 260. The removal liquid is appropriately supplied from the removal liquid supply device to the discharge nozzle 260 through the removal liquid supply pipe 28, whereby the removal liquid is discharged from the discharge port of the discharge nozzle 260 to the surface of the substrate 90.

The removal liquid treatment unit 20 includes a pair of back surface cleaning nozzles 29. The back surface cleaning nozzle 29 penetrates the bottom of the cup 240, and the discharge port at the upper end thereof faces the back surface of the substrate 90 supported by the spin chuck 220 in close proximity to each other. The back surface cleaning nozzle 29 discharges a cleaning liquid such as pure water or warm pure water from the discharge port to the back surface side of the substrate 90.

The step of supplying the removing liquid to the substrate 90 to remove organic substances such as polymers in the removing liquid treatment unit 20 corresponds to the removing liquid treatment step.

<Transport device 30>
As shown in FIG. 1, the transport device 30 is arranged between the reforming processing unit 10 and the removing liquid processing unit 20, and the substrate 90 modified by the reforming processing unit 10 is treated with the removing liquid. Transport to section 20.

The transport device 30 includes a hand unit 32, an advancing / retreating drive unit 34, and a turntable 36. The hand portion 32 supports the substrate 90 in a horizontal posture. The hand portion 32 is formed in a fork shape, for example, in a plan view, and the fork-shaped portion supports the lower surface of one substrate 90.

The advancing / retreating drive unit 34 is provided on the turntable 36 and is a mechanism for moving the hand unit 32 with respect to the turntable 36. The advancing / retreating drive unit 34 may be composed of, for example, a guide rail in which the base end portion of the hand portion 32 is slidably arranged, and a drive portion that slides the base end portion of the hand portion 32 along the guide rail. .. By extending the guide rail in the horizontal direction, the hand portion 32 moves back and forth in the horizontal direction.

The turntable 36 is a device that integrally rotates the advance / retreat drive unit 34 and the hand unit 32 around the vertical axis. The direction of the tip of the hand portion 32 is appropriately changed by the turntable 36. The advancing / retreating drive unit 34 moves the hand unit 32 to the modification processing unit 10 with the tip of the hand unit 32 facing the modification processing unit 10, so that the substrate 90 is received from the modification processing unit 10. .. Further, with the tip of the hand unit 32 holding the substrate 90 facing the removal liquid processing unit 20, the advancing / retreating driving unit 34 moves the hand unit 32 to the removal liquid processing unit 20 to move the hand unit 32 to the removal liquid processing unit 20. The substrate 90 is handed over to 20.

Instead of providing the advancing / retreating drive unit 34 and the turntable 36, the hand unit 32 may be rotated and translated by using an articulated arm or the like.

The transfer device 30 may receive the substrate 90 before the reforming process from the outside of the substrate processing device 100 and carry the substrate 90 into the reforming processing unit 10. In this case, a carry-in buffer unit may be provided for delivering the substrate 90. Further, the transfer device 30 may receive the substrate 90 for which the removal liquid treatment by the removal liquid treatment unit 20 has been completed and carry it out to the outside of the substrate processing device 100. In this case as well, a carry-out buffer unit may be provided for delivering the substrate 90.

Further, the reforming treatment unit 10 and the removal liquid treatment unit 20 may be stacked and arranged in the vertical direction. Further, the laminated reforming processing unit 10 and the removing liquid processing unit 20 may be arranged in a cluster shape around the transport device 30.

In the substrate processing device 100, after the reforming process, which is a dry process, is performed on the substrate 90 in the reforming processing unit 10, the transfer device 30 transfers the substrate 90 to the second removal liquid processing unit 20. Move to chamber 21. Then, in the second chamber 21, a removal liquid treatment in which the substrate 90 is a wet treatment is performed. By performing the dry treatment and the wet treatment in different chambers in this way, it is possible to protect the configuration provided in the chamber. For example, by arranging the UV irradiator 14 in the first chamber 11 different from the second chamber 21 in which the wet treatment is performed, it is possible to prevent the UV irradiator 14 from being damaged by the removal liquid adhering to it. In addition, since it is possible to prevent the removing liquid from adhering to the UV irradiator 14, maintenance is facilitated.

<About polymer residue>
FIG. 4 is a schematic cross-sectional view showing a partially enlarged surface of the substrate 90.

The substrate 90 is the one after the dry etching step after the wiring forming step, and the metal film 91, the etching stop layer 92, the Low-K film 93, the oxide film 94 and the metal hard mask layer 95 are formed from the lower side. There is. Vias 902 and trenches 904 are formed on the surface of the substrate 90. The via 902 penetrates the metal hard mask layer 95, the oxide film 94, the Low-K film 93, and the etch stop layer 92, and the metal film 91 is exposed to the surface through the via 902. Further, the Low-K film 93 is exposed on the surface through the trench 904.

The polymer 96 remains on the surface of the substrate 90 after the dry etching step. The polymer 96 is, for example, a fluorocarbon-based polymer (hereinafter, referred to as “CF polymer”) or the like.

FIG. 5 is a diagram showing a structural formula of the CF polymer. When the substrate 90 on which the CF polymer remains is irradiated with UV in the modification treatment unit 10, a reaction occurs in which the CF polymer is oxidized. Specifically, as shown in FIG. 5, _{the covalent bond of CF-C 3} F _{7 and} the covalent bond of CF-CF _{2 and} the covalent bond of CF are separated from each other, and an oxygen atom is bonded to a carbon atom. ..

As described above, the oxidized polymer 96 remains on the surface of the substrate 90 that has been modified in the modification processing unit 10. The transfer device 30 transfers the substrate 90 from the reforming processing unit 10 to the removing liquid processing unit 20. Then, the polymer 96 is removed by treating the substrate 90 with the removal liquid in the removal liquid treatment unit 20.

As the removal liquid used in the removal liquid treatment unit 20, a liquid containing an organic alkaline liquid such as dimethylformamide, dimethylsulfoxide and hydroxylamine, a liquid containing an organic amine such as monoethanolamine and alkanolamine, and the like are used. In addition, a liquid containing 1-methyl-2-pyrrolidone, 2- (2-aminoethoxy) ethanol, catechol, aromatic diol and the like, or a mixed solution of the above chemical solutions is used.

The removal liquid used in the removal liquid treatment unit 20 may be a non-organic solvent-based treatment liquid that does not contain an organic solvent. For example, SC1 (ammonia-hydrogen peroxide mixture), hydrogen peroxide solution (H ₂ O ₂ ), hydrofluoric acid (HF), liquid containing inorganic acids such as phosphoric acid, ammonium fluoride-based substances. It may be a liquid containing it.

In the substrate processing apparatus 100, the polymer 96 remaining on the substrate 90 is oxidized by performing a modification treatment by UV irradiation in advance. Therefore, the polymer 96 can be easily removed by the removing liquid. Therefore, the removal liquid treatment unit 20 can reduce the amount of the removal liquid used or shorten the time for the removal liquid treatment.

<Effect of UV irradiation on Low-K film>
Here, the effect of UV irradiation on the Low-K film will be examined. FIG. 6 is a diagram showing changes in the contact angle according to the UV irradiation time. Here, the Low-K film 93 is formed on the surface of the silicon layer 98, and the sample 90A in which the polymer 96 (here, CF polymer) remains on the surface is used. FIG. 6 shows the results of measuring the contact angle in each of the case where the sample 90A was irradiated with UV only and the case where the sample 90A was treated with a removing solution after UV irradiation. UV irradiation is performed in an air atmosphere using a low-pressure mercury lamp (which outputs UV having wavelengths of 185 nm and 254 nm), and the illuminance is 25 mW / cm ² .

In FIG. 6, the horizontal axis represents the UV irradiation time, and the vertical axis represents the contact angle. As shown in FIG. 6, even when only UV irradiation is performed on the sample 90A, the contact angle becomes smaller as the irradiation time increases. For example, the contact angle is 80 degrees when UV is not irradiated, whereas the contact angle is 20 degrees or less only by UV irradiation for 300 seconds. This result suggests that the Low-K film may be deteriorated by long-term UV irradiation.

On the other hand, when the UV irradiation and the removing liquid treatment are combined, the contact angle is significantly reduced even when the UV irradiation time is relatively short (for example, 120 seconds or less). That is, it is considered that the polymer 96 can be removed by performing the removing liquid treatment after UV irradiation for a relatively short time. Further, it is considered that the deterioration of the Low-K film 93 is suppressed by shortening the UV irradiation for a relatively short time.

FIG. 7 is a diagram in which the change in the coupling state caused by UV irradiation is evaluated by Fourier transform infrared spectroscopy (FTIR spectroscopy). UV irradiation is performed in an air atmosphere using a low-pressure mercury lamp (outputs UV having wavelengths of 185 nm and 254 nm), and the illuminance is 25 mW / cm ² .

As shown in FIG. 7, as the UV irradiation time increases, the absorbance of the wave number corresponding to the C = O bond and the CF bond in the polymer 96 decreases. This measurement result shows that the C = O bond and the CF bond in the polymer 96 were reduced by oxidation by UV irradiation, and the CF bond was remarkably reduced by UV irradiation for 120 seconds or longer. is decreasing.

When the UV irradiation time is 300 seconds or more, the absorbance in the vicinity of the wave number "1026" begins to decrease. This wavenumber corresponds to the Si—O bond of the Low—K film 93. That is, since the Si—O bond is reduced, it is considered that the Low-K film may be deteriorated by long-term UV irradiation.

FIG. 8 is a diagram showing changes in the bonding state of the Low-K film 93 due to UV irradiation. The data shown in FIG. 8 is data obtained by using the sample 90B in which only the Low-K film 93 is formed on the silicon layer 98. UV irradiation is performed in an air atmosphere using a low-pressure mercury lamp (outputs UV having wavelengths of 185 nm and 254 nm), and the illuminance is 25 mW / cm ² .

As shown in FIG. 8, by UV irradiation below 120 seconds, reduction of CHx bond or Si-CH ₃ bonds constituting the Low-K film 93 is hardly observed. From this, it is considered that the deterioration of the Low-K film 93 hardly occurs if the UV irradiation is performed for a short time.

FIG. 9 is a diagram showing a change in the film thickness of the Low-K film 93 due to UV irradiation. The data shown in FIG. 9 shows the case where the sample 90B shown in FIG. 8 was not irradiated with UV (◯) and the case where UV irradiation was performed for 5, 30, 60, and 120 seconds (□). , The film thickness of the Low-K film was measured by ellipsometry and obtained. UV irradiation is performed in an air atmosphere using a low-pressure mercury lamp (outputs UV having wavelengths of 185 nm and 254 nm), and the illuminance is 25 mW / cm ² .

As shown in FIG. 9, even if the UV irradiation time is 5 to 120 seconds, no significant change occurs in the film thickness of the Low-K film. In addition, there is no significant difference between the film thickness when UV irradiation is performed and the film thickness when UV irradiation is not performed. From these facts, it is considered that almost no loss occurs in the Low-K film when the UV irradiation is performed for a relatively short time (120 seconds or less).

Based on the above results, by performing the removal liquid treatment after UV irradiation for a relatively short time (120 seconds or less), the Low-K film 93 is not deteriorated and the polymer 96 is effective. It is thought that it can be removed as a target.

<Effect of UV irradiation on metal film>
Next, the effect of UV irradiation on the metal film 91 will be examined. Here, the case where the metal film 91 is a copper film will be examined.

FIG. 10 is a diagram showing the measurement results of the copper oxide film thickness after UV irradiation. 10, 10 seconds UV radiation to a sample copper film is formed as a metal film was irradiated 30 seconds or 60 seconds, copper oxide (cupric oxide (CuO) and cuprous oxide _(Cu 2 O) ) Is measured by the X-ray reflectance method (XRR). UV irradiation is performed in an air atmosphere using a low-pressure mercury lamp (outputs UV having wavelengths of 185 nm and 254 nm), and the illuminance is 25 mW / cm ² .

As shown in FIG. 10, the film thickness of copper oxide formed by UV irradiation is from the reference value of 0.5 nm in both the vicinity of the center and the vicinity of the edge of the substrate regardless of the length of the UV irradiation time. Is also getting smaller. That is, it can be said that oxidation of the copper film (that is, loss of the copper film) hardly occurs by UV irradiation for a relatively short time.

When ozone water is used as the reforming treatment as in the conventional case, the copper film is easily oxidized together with the organic substances such as the polymer, and the copper film is easily lost. On the other hand, in the case of UV irradiation, the copper film is hardly oxidized, so that the loss of the copper film can be suppressed.

<2. Second Embodiment>
Next, the second embodiment will be described. In the following description, elements having the same functions as the elements already described may be given the same code or a code to which alphabetic characters are added, and detailed description may be omitted.

FIG. 11 is a schematic side view showing the reforming processing unit 10A of the second embodiment. The substrate processing apparatus 100 of the second embodiment includes a modification processing unit 10A instead of the modification processing unit 10 that performs UV irradiation. The reforming processing unit 10A includes a base 120 and a hot plate 122. The base 120 is a member on which the hot plate 122 is placed, and supports the hot plate 122 from below. The hot plate 122 supports the substrate 90 in a horizontal position on the upper surface.

The hot plate 122 is provided with a heat source inside, and is configured to be able to heat the substrate 90 supported on the upper surface to a predetermined temperature (for example, 100 degrees or more).

The reforming processing unit 10A includes a nozzle 140, an ozone gas supply pipe 142, and an ozone gas supply unit 144. The discharge port of the nozzle 140 is directed to the substrate 90 held on the hot plate 122. The nozzle 140 is connected to the ozone gas supply unit 144 via the ozone gas supply pipe 142. The ozone gas supply unit 144 supplies ozone gas, which is an oxidizing gas, to the nozzle 140 through the ozone gas supply pipe 142. As a result, the ozone gas 18 is injected from the discharge port of the nozzle 140 toward the surface of the substrate 90. In this way, the reforming processing unit 10A brings the ozone gas 18 into contact with the surface of the substrate 90. When the ozone gas 18 comes into contact with the surface of the substrate 90, organic substances such as polymers adhering to the surface are oxidized.

The nozzle 140 is configured to be rotatable by the nozzle moving mechanism 16. Specifically, the nozzle moving mechanism 16 includes an arm 162, an arm holding portion 164, a rotation support shaft 166, and an arm rotation mechanism 168.

The nozzle 140 is supported by the tip of the arm 162. The arm 162 is held by the arm holding portion 164 at its base end portion and is arranged along the horizontal direction. The arm holding portion 164 is the upper end of the rotary support shaft 166 arranged along the vertical direction. It is fixed to the part. The rotary support shaft 166 is rotated by an arm rotation mechanism 168 around a shaft extending in the vertical direction.

By driving the arm rotation mechanism 168, the nozzle 140 reciprocates between a position near the center of the substrate 90 and a position outside the substrate 90 (a position deviating from above the substrate 90). The movement of the nozzle 140 is executed, for example, when the substrate 90 is carried on the hot plate 122 and when the substrate 90 is carried out from the hot plate 122.

The substrate 90 may be placed and carried out on the hot plate 122 via a plurality of lift pins (not shown). Further, a suction hole, a suction groove, or the like may be formed on the upper surface of the hot plate 122.

In the reforming processing unit 10A, ozone gas 18 is supplied to the substrate 90 from the nozzle 140 while the hot plate 122 heats the substrate 90 while the substrate 90 is supported on the surface of the hot plate 122. By contacting the substrate 90 with the ozone gas 18 while heating the substrate 90, the polymer 96 remaining on the substrate 90 can be efficiently oxidized. Therefore, the polymer 96 can be effectively removed by the removal liquid treatment in the removal liquid treatment unit 20.

<3. Modification example>
Although the embodiments have been described above, the present invention is not limited to the above, and various modifications can be made.

For example, in the reforming processing unit 10A of the second embodiment, the gas discharged from the nozzle 140 is not limited to the ozone gas 18. That is, the gas discharged from the nozzle 140 may be an oxidizing gas that oxidizes the polymer 96. Examples of the oxidizing gas include oxygen gas, carbon dioxide gas, a mixed gas thereof, and the like, in addition to ozone gas 18.

Further, by performing plasma discharge while discharging oxygen gas from the nozzle 140, ozone gas 18 may be generated from the discharged oxygen gas.

In the second embodiment, the substrate 90 is heated by the hot plate 122, but this is not essential. For example, the substrate 90 may be heated by using radiant heat from a heat source such as an infrared heater. Further, the substrate 90 may be heated by raising the temperature of the gas supplied from the nozzle 140 to the substrate 90, such as ozone gas 18.

Further, the reforming processing unit 10A of the second embodiment performs the reforming treatment in a state where the substrate 90 is arranged at a fixed position, but the reforming treatment is performed while transporting the substrate 90 in a predetermined direction. May be good. In this case, the substrate 90 may be conveyed by a transfer mechanism such as roller transfer. Further, it is preferable to dispose a plurality of infrared heaters along the moving direction of the substrate 90 and heat the moving substrate 90 by the radiant heat from the plurality of infrared heaters. Further, it is preferable to move the substrate 90 in an atmosphere containing an oxidizing gas such as ozone gas 18.

In the above embodiment, the case where the processing target of the substrate processing apparatus 100 is a semiconductor wafer has been described. However, the substrates to be processed by the substrate processing apparatus 100 are a glass substrate for a photomask, a glass substrate for a liquid crystal display device, a glass substrate for a plasma display, a glass substrate or a ceramic substrate for a magnetic / optical disk, and a glass substrate for an organic EL. , Other various substrates to be processed for electronic devices such as flexible substrates and printed circuit boards.

Although the present invention has been described in detail, the above description is exemplary in all aspects and the invention is not limited thereto. It is understood that a myriad of variations not illustrated can be envisioned without departing from the scope of the invention. The configurations described in the above embodiments and the modifications can be appropriately combined or omitted as long as they do not conflict with each other.

100 Substrate processing device 10, 10A Modification processing unit 11 1st chamber 122 Hot plate 14 UV irradiator 140 Nozzle 142 Ozone gas supply piping 144 Ozone gas supply unit 18 Ozone gas 20 Removal liquid treatment unit 21 2nd chamber 26 Removal liquid supply mechanism 260 Discharge Nozzle 30 Conveyor 90 Substrate 91 Metal film 92 Etch stop layer 93 Low-K film 94 Oxide film 96 Polymer (organic matter)

Claims (7)

This is a substrate processing method for processing a substrate in which the Low-K film is exposed and organic substances remain.
Ozone gas and radicals generated by irradiating the space above the substrate on which the organic matter remains on the surface with UV until the absorbance at a wave number of around 1026 begins to decrease by spectroscopy are transferred to the organic matter remaining on the substrate. An oxidation treatment step that oxidizes the organic matter by contact with it.
A substrate treatment method comprising a removal liquid treatment step of removing organic substances by supplying a removal liquid to the substrate after the oxidation treatment step. The substrate processing method according to claim 1.
A substrate treatment method in which the removal liquid is a treatment liquid containing no organic solvent. The substrate processing method according to claim 1 or 2.
A substrate processing method in which the oxidation treatment step is performed in a state where the metal film is not lost. The substrate processing method according to any one of claims 1 to 3.
A substrate processing method in which the oxidation treatment step is performed in a state where the Low-K film is not deteriorated. The substrate processing method according to claim 4.
A substrate processing method in which the oxidation treatment step is performed without oxidizing the Low-K film. The substrate processing method according to any one of claims 1 to 5.
The oxidation treatment step is a substrate treatment method, which is a step of treating the substrate after plasma etching treatment. The substrate processing method according to any one of claims 1 to 6.
A moving step of moving the substrate to a second chamber different from the first chamber after the oxidation treatment step is performed with the substrate arranged in the first chamber.
Including
A substrate processing method in which the removing liquid treatment step is performed with the substrate arranged in the second chamber.

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