JP4555729B2 - Resist removing method and resist removing apparatus - Google Patents

Description

The present invention relates to a resist removal method and a resist removal apparatus that can remove even a resist on a substrate surface subjected to a dry etching process and / or a reactive ion implantation process with high efficiency and uniformity.

In the manufacture of substrates for electronic devices such as semiconductor wafers and liquid crystal substrates, it is essential to remove organic substances adhering to the surface of the substrate, such as removing resists and general organic coatings such as oil films and coatings. It is. In particular, the removal of the resist is an extremely important step in the entire production of the electronic device substrate.

For example, when forming a circuit on a compound semiconductor substrate such as a silicon substrate or a gallium arsenide substrate, when forming a plurality of colored pixels having different hues on a liquid crystal substrate, or a circuit pattern to be formed on these When manufacturing a mask substrate having a mask pattern corresponding to the above, a photolithography process is an essential process. When a circuit is formed on a silicon substrate, a resist is applied on a silicon wafer, an image composed of a resist pattern is formed by a normal photo process, and etching is performed using this as a mask, and then unnecessary resist is removed. Then, in order to form a circuit and form the next circuit, a resist is applied again, and a cycle of image formation-etching-resist removal is repeated.

In the resist removal process for removing the resist that is no longer necessary, conventionally, an asher (ashing means), a method of dissolving the resist using a solvent, chemicals, or the like has been used. However, if an asher is used to remove the resist, the semiconductor may be damaged due to the high temperature, and in addition, inorganic impurities cannot be removed. In addition, when the resist is removed using a solvent or a chemical, a large amount of waste liquid is generated, and there is a great disadvantage both in terms of cost and environment in the waste liquid treatment.

On the other hand, ozone water obtained by dissolving ozone gas in water exerts excellent effects on sterilization, deodorization, bleaching, etc. due to the strong oxidizing power of ozone, and ozone gas self-decomposes into harmless oxygen (gas) over time. Therefore, it has been attracting attention as an environmentally friendly sterilization / cleaning / bleaching agent. In recent years, with increasing interest in the environment, a resist removal process using ozone water has attracted attention as an alternative to the resist removal method described above.

However, under normal temperature and normal pressure, ozone can only be dissolved in water at a concentration of about 50 ppm, and this concentration of ozone water requires a long time to remove the resist, making it difficult to apply industrially. . On the other hand, for example, Patent Document 1 discloses a cleaning agent for removing pollutants obtained by dissolving ozone in a solution having a partition coefficient of 0.6 or more with respect to ozone in a gas such as acetic acid. . If such an acetic acid aqueous solution or the like is used, the ozone concentration that can be dissolved can be increased.

However, by preparing and using a high-concentration ozone solution with an acetic acid solution or the like, the resist removal efficiency is improved to some extent, but for example, after a dry etching process or an ion implantation process is performed in a photolithography process. However, the resist on the substrate surface has a problem that the resist removal efficiency as expected cannot be obtained.
JP 2001-340817 A

In view of the present situation, the present invention provides a resist removal method that can remove evenly and efficiently even a resist on a substrate surface that has been subjected to dry etching treatment and / or reactive ion implantation treatment, and An object is to provide a resist removing apparatus.

The present invention is a resist removal method for removing a resist on a surface of a substrate that has been subjected to a dry etching process and / or an ion implantation process, and includes an ozone water treatment for treating a treated surface of the substrate with ozone water, This is a resist removal method in which a set of steps consisting of a solvent treatment for treating a treated surface with an organic solvent is repeated twice or more.
The present invention is described in detail below.

It takes a long time to remove the resist on the substrate surface only with ozone water. In particular, the resist on the substrate surface that has been subjected to dry etching treatment and / or ion implantation treatment can be completely removed only with ozone water. However, when the state of the substrate surface after removing the resist with ozone water was observed in detail, resist residues that could not be completely removed with ozone water were present on the substrate surface. Therefore, as a result of intensive studies, the present inventors have used a treatment with ozone water and a treatment with an organic solvent, and repeatedly performing these treatments, whereby the substrate surface that has been subjected to dry etching treatment and / or ion implantation treatment. It was found that even this resist can be removed quickly and completely, and the present invention has been completed.

The present invention is a resist removal method for removing a resist on a substrate surface that has been subjected to dry etching treatment and / or ion implantation treatment.
The resist to be removed by the resist removal method of the present invention is not particularly limited. For example, a resist that is usually used in a photolithography process in the production of a liquid crystal display element can be mentioned, and among these, a novolak-type resist is suitably removed. it can.
The novolak-type resist contains a novolak resin as a main component and further contains a photosensitizer such as orthodiazoquinone, and the solubility in an alkali solution can be changed by light irradiation. The novolak resist is currently widely used for almost all substrates such as glass substrates, compound substrates, and silicon substrates.

The substrate on which the resist is formed is not particularly limited as long as the resist is formed on the surface and used for the photolithography process. For example, a semiconductor wafer made of silicon or a compound, a photomask substrate, a small liquid crystal A display display, a color filter, etc. are mentioned.

In the resist removal method of the present invention, the substrate on which the resist is formed is subjected to dry etching treatment and / or ion implantation treatment.
The dry etching process is not particularly limited, and examples thereof include a process similar to a conventionally known dry etching process performed using a resist formed on the surface of the substrate as a mask. For example, reactive ion etching, plasma etching, sputter etching, Examples include ion beam etching, reactive ion beam etching, and laser etching. Note that the resist after such a dry etching process is thinner than the thickness before the process.

The ion implantation process is not particularly limited, and examples thereof include a process of implanting ions such as phosphorus and arsenic into the substrate using a conventionally known ion implantation processing apparatus.
The substrate subjected to the ion implantation process may be subjected to the above-described dry etching process, for example, a wet etching process using a chemical solution such as sulfuric acid, nitric acid, phosphoric acid, or hydrofluoric acid. Also good.

The resist on the substrate surface that has been subjected to the dry etching process and / or the ion implantation process has a layer (hereinafter also referred to as a resist-modified layer) in which the resist component is modified on the outermost layer.

The resist-modified layer means a layer containing a hardly soluble resist modified by bonding or adsorbing or cross-linking a hardly decomposable substance such as a halogen substance such as fluorine or chlorine, and the like. The resist having the resist-modified layer formed on the outermost layer is very difficult to remove and cannot be completely removed by the conventional resist removing method.

In the resist removal method of the present invention, as the resist-modified layer formed on the outermost layer of the resist, for example, reactive ion etching using a halogen substance such as fluorine or chlorine in a photolithography process in manufacturing a liquid crystal display element The halogen-containing layer formed by performing the above-described dry etching process, etc .; when using a compound substrate such as a silicon substrate or a gallium arsenide substrate as the substrate and forming a circuit on this compound substrate, the above-described ion implantation process is performed. An ion-implanted layer formed by the method can be used.

The halogen-containing layer is made of a fluorine-containing gas, a chlorine-containing gas, or other halogen-containing gas used when dry etching treatment such as reactive ion etching is performed on a resist pattern formed on a substrate. It is formed by impregnation with a halogen component, and refers to a portion where the halogen substance content is higher than the resist component before etching. In such a halogen substance-containing layer, the closer to the resist surface, the higher the halogen substance content, and the further away from the surface, the lower the halogen substance content.

The ion-implanted layer is formed by impregnating a resist pattern formed on a silicon substrate or the like with ions of impurities such as phosphorus and arsenic used when performing ion implantation. This refers to the portion where the ion content is higher than that of the resist component. Such an ion-implanted layer has a higher ion content as it is closer to the resist surface and lower as it is farther from the surface.

The thickness of the resist-modified layer includes the type of resist to be used and the processing conditions when the resist-modified layer is formed, for example, dry etching when the resist-modified layer is a halogen substance-containing layer. Although it is not particularly limited because it varies depending on the halogen-containing gas used, etching conditions, etc., it is usually less than 100 nm from the resist surface.

In the resist removal method of the present invention, a set of processes (hereinafter referred to as a resist processing process) consisting of an ozone water treatment for treating a treated surface of a substrate with ozone water and a solvent treatment for treating the treated surface of the substrate with an organic solvent. Repeat) two or more times. If it is less than twice, the resist on the substrate surface cannot be removed efficiently and uniformly.
The upper limit of the resist processing step is not particularly limited and is appropriately determined according to the ozone water and the organic solvent to be used, such as the type and thickness of the resist and the resist-modified layer, but is preferably about 20 times. If it exceeds 20, the resist removal efficiency and the removal state on the substrate surface are not improved, and the resist processing process takes a long time, which is disadvantageous in terms of cost.

The ozone water treatment is a treatment for modifying the resist-modified layer formed on the resist on the substrate surface by treating the treatment surface of the substrate surface with ozone water. This ozone water treatment reduces the molecular weight of the resist-modified layer formed on the outermost layer of the resist on the substrate surface to such an extent that it can be dissolved by the organic solvent treated on the treated surface of the substrate by the solvent treatment described below. In addition, the solubility parameter (SP value) of the resist-modified layer can be changed so that it can be easily dissolved in an organic solvent, and the wettability of the resist surface can be improved.
In addition, in this specification, ozone water includes not only ozone gas dissolved in an aqueous solution but also ozone gas dissolved in water in which an organic acid such as acetic acid and citric acid or a derivative thereof is dissolved.

The ozone concentration of the ozone water is preferably 1 ppm or more. If the concentration is less than 1 ppm, it is difficult to sufficiently remove the resist. In particular, the resist-modified layer formed on the outermost layer of the resist does not sufficiently exhibit the removal performance, and the resist organic substance dispersed in ozone water is used. May not be sufficiently decomposed and the ozone solution may not be circulated and used repeatedly. More preferably, it is 30 ppm or more. The upper limit of the ozone concentration is not particularly limited, but the upper limit is substantially about 80 ppm.
In addition, the ozone concentration in the ozone water is difficult to measure accurately because it is consumed successively by the decomposition of organic matter. Further, the ozone concentration is not particularly limited as long as ozone is sequentially dissolved by circulating it in combination with an ozone dissolution module or the like.

The ozone water may be used in combination with a non-hazardous material such as dimethyl oxalate, if necessary, as long as it does not inhibit the object of the present invention and has low reactivity with ozone.

The method for preparing the ozone water is not particularly limited. For example, it is preferable to use an ozone dissolution apparatus such as an ozone dissolution module containing a gas permeable film made of a non-porous film. In the present specification, the non-porous membrane means a membrane that allows gas to permeate but does not allow liquid to permeate. If such an ozone dissolution module is used, ozone molecules permeate between the resin molecular chains constituting the gas permeable membrane and diffuse into the raw material water, but the gas permeable membrane is clogged and resist removal efficiency is reduced. There is no foam mixing. Furthermore, ozone water once used for resist removal can be circulated and used, and an ozone solution having a high ozone concentration can be obtained easily and efficiently.

A specific method for treating the treatment surface of the substrate with the ozone water is not particularly limited. For example, a method of immersing the substrate in a treatment tank storing the ozone water, means for injecting ozone water such as a nozzle The method etc. which inject | pour ozone water into the process surface of a board | substrate using the method are mentioned. Especially, the method of immersing the said board | substrate in the processing tank which stored ozone water is suitable. According to such a method, it is possible to perform batch-type processing that simultaneously performs ozone water processing on a plurality of substrates.

In the present ozone water treatment, the conditions for treating the treated surface of the substrate with ozone water are not particularly limited, and can be appropriately selected depending on the type of resist, the thickness, the concentration of ozone water, and the like. Since the resist removal rate tends to increase as the temperature increases in a range that does not affect the ozone concentration in the ozone water, a processing temperature of about 50 ° C. is suitable. In the present ozone water treatment, the treatment surface of the substrate may be irradiated with ultraviolet rays. Irradiation with ultraviolet rays can further increase the resist removal efficiency.

The solvent treatment is a treatment for dissolving and removing the resist by treating the resist on the substrate surface with an organic solvent.
The organic solvent is not particularly limited, and examples thereof include those similar to the organic solvents conventionally used for resist removal. Specifically, the organic solvent is selected from the group consisting of γ-butyrolactone, ethylene glycol diacetate, and diacetin. It is preferable that the solvent is at least one kind of solvent.
Since at least one solvent selected from the group consisting of γ-butyrolactone, ethylene glycol diacetate and diacetin is excellent in solubility of organic substances, particularly resist, and is liquid at normal temperature and pressure, It is extremely easy to handle as a processing solution. Moreover, since it is excellent in the solubility to water, a washing process etc. can be used together, without passing through a drying process etc. Furthermore, since it is classified as the third petroleum under the Fire Service Act, there is little danger and it is not necessary to perform explosion-proof processing on the device. Of these, γ-butyrolactone and ethylene glycol diacetate are more preferable, and γ-butyrolactone is more preferable because of excellent solubility of the resist.

For example, at least one solvent selected from the group consisting of γ-butyrolactone, ethylene glycol diacetate and diacetin can suitably dissolve and remove the resist-modified layer and the resist on the substrate surface that has undergone the ozone water treatment, for example. By repeating the solvent treatment using the solvent and the ozone water treatment within the above-described range, the resist on the substrate surface is almost uniformly removed.

In the resist removal method of the present invention, the organic solvent used in the solvent treatment is water for 100 parts by weight of at least one solvent selected from the group consisting of γ-butyrolactone, ethylene glycol diacetate, and diacetin. A mixed solvent may be blended so that the lower limit is 5 parts by weight and the upper limit is 100 parts by weight.
As described above, the solvent such as γ-butyrolactone is excellent in resist solubility by itself, but depending on the type of the resist, a mixed solvent in which water is mixed in a predetermined ratio may be used. In some cases, the resist can be removed more efficiently and uniformly than when the resist is removed with 100% of the solvent. The reason for this is not clear, but it is considered that the mixed solvent to be prepared approaches the solubility parameter of the resist by adding water to the solvent in the above range.

In the mixed solvent, if the amount of water is less than 5 parts by weight with respect to 100 parts by weight of the solvent, the resist removal efficiency is hardly improved. When the blending amount of water exceeds 100 parts by weight with respect to 100 parts by weight of the solvent, the amount of the solvent decreases, and conversely, the resist removal efficiency decreases. The preferred lower limit is 10 parts by weight, the preferred upper limit is 60 parts by weight, the more preferred lower limit is 20 parts by weight, and the more preferred upper limit is 40 parts by weight.

The mixed solvent of at least one solvent selected from the group consisting of γ-butyrolactone, ethylene glycol diacetate and diacetin and water, for example, suitably dissolves and removes the resist on the substrate surface that has undergone the ozone water treatment. By repeatedly performing the solvent treatment using the mixed solvent and the ozone water treatment within the above-described range, the resist on the substrate surface is removed almost uniformly.

A specific method for treating the treatment surface of the substrate using the organic solvent or the mixed solvent is not particularly limited. For example, a method of immersing the substrate in a treatment tank storing the organic solvent or the mixed solvent, a nozzle For example, a method of injecting an organic solvent or the like onto the processing surface of the substrate using a means for injecting an organic solvent or the like. Among these, a method of immersing the substrate in a treatment tank storing an organic solvent or a mixed solvent is preferable. According to such a method, it is possible to perform batch processing in which solvent processing of a plurality of substrates is performed simultaneously. In addition, when the substrate is immersed in a treatment tank storing an organic solvent or a mixed solvent, the resist peeling effect on the substrate surface is improved, so that the organic solvent or the mixed solvent is bubbled in the treatment tank. It is preferable that an organic solvent or the like is applied to the processing surface of the substrate forcibly to some extent by aeration, stirring, or the like.

In the resist removal method of the present invention, if the set of steps (resist treatment step) including the ozone water treatment and the solvent treatment is performed alternately with the ozone water treatment and the solvent treatment, the ozone water treatment is performed first. The solvent treatment may be performed first, but the ozone water treatment is preferably performed first. As described above, ozone water has a role of modifying the resist-modified layer formed on the outermost resist layer on the substrate surface, and the organic solvent has a role of dissolving the resist. When the solvent treatment is performed, when the resist treatment process is repeated twice, the resist removal on the substrate surface after the resist treatment process may be insufficient.

Moreover, it does not specifically limit as a process condition at the time of performing the said ozone water process and a solvent process, The frequency | count of repeating the said ozone process process, the kind and state of the resist of the board | substrate surface which is a process target, the ozone water to be used It is appropriately determined according to the ozone concentration, the type of organic solvent, and the like.

In the resist removal method of the present invention, a set of steps consisting of the ozone water treatment and the solvent treatment is repeated twice or more, so that the surface of the resist is removed by dry etching treatment such as reactive ion etching and / or ion implantation treatment. Even in the resist having a resist-modified layer formed thereon, the resist-modified layer is surface-modified with ozone water in the ozone water treatment, and further, the resist-modified layer and the resist are dissolved with an organic solvent in the solvent treatment, The resist can be removed very efficiently. That is, according to the resist removal method of the present invention, even if the resist on the substrate surface has a resist-modified layer formed by dry etching treatment and / or reactive ion implantation treatment, it is removed efficiently and uniformly. be able to.

Such a resist removal method of the present invention includes, for example, at least an ozone dissolution apparatus that generates ozone water by dissolving ozone gas in raw water, and an ozone water treatment tank to which the ozone water generated by the ozone dissolution apparatus is supplied A solvent tank for storing the organic solvent, a solvent treatment tank to which the organic solvent is supplied from the solvent tank, and a substrate transport means for reciprocating the substrate between the ozone water treatment tank and the solvent treatment tank. It can be suitably realized by using a resist removing apparatus.
A resist removal apparatus that can be used in the resist removal method of the present invention is also one aspect of the present invention.

FIG. 1 is a schematic view showing an outline of a resist removing apparatus of the present invention.
As shown in FIG. 1, the resist removing apparatus 1 of the present invention includes an ozone dissolution apparatus 2, an ozone water treatment tank 3, a substrate transport means 4, an ozone water circulation path 5 that connects the ozone dissolution apparatus 2 and the ozone water treatment tank 3. , A solvent tank 6, a solvent treatment tank 7, and a solvent circulation path 8 that connects the solvent tank 6 and the solvent treatment tank 7.
In addition, the arrow of one direction in FIG. 1 shows the direction in which the board | substrate provided for a process is conveyed, and the arrow of both directions shows the direction to which the board | substrate transport means 4 which transports a board | substrate moves. That is, in the resist removal apparatus 1 shown in FIG. 1, the substrate on which the resist is formed is first transported to the ozone water treatment tank 3 and then to the solvent treatment tank 7. Further, the substrate is reciprocated between the ozone water treatment tank 3 and the solvent treatment tank 7 by the substrate transport means 4. In the resist removal apparatus 1 of the present invention, the positions of the ozone water treatment tank 3 and the solvent treatment tank 7 may be reversed.

The ozone water treatment tank 3 is a container for performing ozone water treatment in the resist removal method of the present invention, and the structure thereof is not particularly limited as long as it is a structure capable of performing ozone water treatment on the resist on the substrate surface. For example, the substrate is placed directly or mounted on the substrate transport means 4 and the substrate is rotated, and a nozzle for injecting ozone water onto the surface of the substrate, and the substrate and the nozzle are accommodated. In addition, a stirrer or other stirring means is provided in a container that can store the supplied ozone water and contain the substrate placed on the substrate transporting means 4. The structure etc. are mentioned.
The ozone water treatment tank 3 may be a sealed container or an open container. Further, the container may be a relatively shallow container such as a wet processing apparatus for a plate-like substrate (for example, a glass substrate) or a container in which a conveyance roller is incorporated.

The ozone dissolving device 2 is not particularly limited, and includes the same device as a conventionally known ozone dissolving module. For example, the device includes a module main body, a raw material water inlet, an ozone water outlet, an ozone gas supply port, and an ozone gas outlet. Is mentioned. An ozone gas supply device is connected to the ozone gas supply port so that ozone is supplied to the raw water in the module body, and ozone that has not been used is discharged from the ozone gas discharge port.
The ozone water generated by the ozone dissolving device 2 is discharged from the ozone water discharge port to the ozone water circulation path 5 and sent to the ozone water concentration detector 10, and the dissolved ozone gas concentration of the ozone water is monitored and managed.

The ozone water supplied from the ozone water circulation path 5 to the ozone water treatment tank 3 is used for the surface treatment of the resist on the surface of the substrate carried into the ozone water treatment tank 3. Specifically, the resist removal of the present invention described above is performed. Used for surface modification of ozone water treated resist in the method.

The ozone water circulation path 5 may be further piped so as to go from the ozone water treatment tank 3 to the ozone dissolving device 2. In this case, it is possible to reuse the ozone water used for the surface modification of the resist, and it becomes easy to increase the ozone concentration of the ozone water.

The solvent tank 6 is a container for storing at least one organic solvent selected from the group consisting of γ-butyrolactone, ethylene glycol diacetate, and diacetin, and a mixed solvent of the organic solvent and water. The solvent tank 6 is not particularly limited as long as it has organic solvent resistance.

The solvent treatment tank 7 is a container for performing the solvent treatment in the resist removal method of the present invention. For example, when removing the resist with the organic solvent by the same method as the ozone water treatment or the like, the ozone water treatment tank The thing of the structure similar to 3 is mentioned.

The solvent circulation path 8 is piped so that the organic solvent stored in the solvent tank 6 is sent to the solvent treatment tank 7 by the pump 12, and is further piped toward the solvent tank 6 from the solvent treatment tank 7. It is preferable. That is, it is preferable that the organic solvent be circulated and reused. At this time, the solvent circulation path 8 is provided with a known solvent regeneration module 11 that decomposes the resist in the organic solvent used for resist removal in the solvent treatment tank 7 and performs a regeneration treatment of the organic solvent. preferable.

The substrate transport means 4 is a member on which a substrate can be placed, and plays a role of reciprocating the substrate between the ozone water treatment tank 3 and the solvent treatment tank 7. The substrate transport means 4 not only reciprocates between the ozone water treatment tank 3 and the solvent treatment tank 7, but also from the start to the end of the resist removal method of the present invention performed using the resist removal apparatus of the present invention. You may come to transport.

Such a substrate transport means 4 is not particularly limited as long as the substrate can be placed and the substrate can be transported between the ozone water treatment tank 3 and the solvent treatment tank 7. Further, the substrate transport means 4 may have a structure on which a single substrate can be placed, or may have a structure on which a plurality of substrates can be placed at the same time. Therefore, a structure capable of mounting a plurality of substrates at the same time is preferable.
In this case, the ozone water treatment tank 3 and the solvent treatment tank 7 preferably have a structure capable of containing the substrate transport means 4 on which the plurality of substrates are placed.

In the resist removing apparatus 1 of the present invention as shown in FIG. 1, the substrate on which the resist is formed is carried into the ozone water treatment tank 3 and then between the solvent treatment tank 7 by the substrate transport means 4. It is reciprocated a predetermined number of times, and the ozone water treatment and the solvent treatment described in the resist removal method of the present invention are performed in each treatment tank. The substrate after the ozone water treatment and the solvent treatment are repeated a predetermined number of times is carried into the water washing tank 13 and washed with water, and then dried in the drying tank 14.
In such a resist removal apparatus of the present invention, the resist removal method of the present invention can be suitably realized, and the resist on the substrate surface can be removed efficiently and uniformly.

ADVANTAGE OF THE INVENTION According to this invention, even if it is the resist of the board | substrate surface in which the dry etching process and / or the reactive ion implantation process were performed, the resist removal method and resist removal apparatus which can be removed efficiently and uniformly Can provide.

Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples.

Example 1
A silicon wafer having a diameter of 6 inches was used as a processing sample.
A resist solution (manufactured by Tokyo Ohka Co., Ltd., THMR-IP1800, viscosity: 1.8 Pa · s) was applied on a silicon wafer to a thickness of about 2.15 μm, and heated at 120 ° C. for 60 seconds. Thereafter, exposure and development are performed to form a circuit pattern having a circuit having a width of 1 μm, 10 μm, and 100 μm, and then ion implantation (As) is performed using a high current ion implantation apparatus (NV-10, manufactured by Sumitomo Eton Nova). went.

Thereafter, the resist on the surface of the processed sample prepared using the resist removing apparatus having the configuration shown in FIG. 1 was removed.
That is, first, the ozone water treatment is performed by bringing the treatment sample into an ozone water treatment tank in which ozone water having an ozone concentration of 40 ppm and a temperature of 20 ° C. is stored and immersed in ozone water stirred with a stirrer for 1 minute. It was.
Next, the treated sample is carried into a solvent treatment tank storing γ-butyrolactone (made by Wako Pure Chemicals, Wako Special Grade) having a concentration of 100% and a temperature of 20 ° C., while being gently swung back and forth in γ-butyrolactone. The solvent treatment was performed by immersing for 1 minute, and the first resist treatment step was performed.
Thereafter, the resist processing step under the same conditions was repeated four times, and a total of five resist processing steps were performed.

The processed sample after performing the resist processing step was observed with a microscope, and the removed state of the resist was observed. As a result, as shown in FIG. 2, the resist of the processed sample was almost uniformly removed in widths of 1 μm, 10 μm, and 100 μm, and there was almost no unevenness in removing the resist. FIG. 2 is a micrograph of the processed sample after processing. The opposing arrow in FIG. 2 indicates the removed resist portion, and the numerical value indicates the width (μm) of the removed resist. Yes.

(Comparative Example 1)
The resist of the treated sample was removed in the same manner as in Example 1 except that the resist treatment process was performed only once with the ozone water treatment time of 1 minute and the solvent treatment time of 20 minutes.
The processed sample after performing the resist processing step was observed with a microscope, and the removed state of the resist was observed. As a result, as shown in FIG. 3, the resist of the change processing sample was not removed in some places in the circuit pattern having a width of 1 μm.

(Comparative Example 2)
The resist of the treated sample was removed in the same manner as in Example 1 except that the ozone water treatment was performed only once with the treatment time of the ozone water treatment being 20 minutes.
The treated sample after the ozone water treatment was observed with a microscope, and the resist removal state was observed. As a result, as shown in FIG. 4, the circuit pattern having a width of 1 μm and a part of the processed sample having a width of 10 μm were removed, but the circuit pattern having a width of 100 μm was not removed at all.

ADVANTAGE OF THE INVENTION According to this invention, even if it is the resist of the board | substrate surface in which the dry etching process and / or the reactive ion implantation process were performed, the resist removal method and resist removal apparatus which can be removed efficiently and uniformly Can provide.

It is the schematic which shows the outline of the resist removal apparatus of this invention. 2 is a micrograph of a processed sample according to Example 1 after processing. 2 is a micrograph of a processed sample after processing according to Comparative Example 1; 5 is a micrograph of a processed sample after processing according to Comparative Example 2.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Resist removal apparatus 2 Ozone dissolution apparatus 3 Ozone water treatment tank 4 Substrate transport means 5 Ozone water circulation path 6 Solvent tank 7 Solvent treatment tank 8 Solvent circulation path

Claims (5)

A resist removal method for removing a resist on a substrate surface subjected to dry etching treatment and / or ion implantation treatment,
A resist removing method comprising performing a set of steps consisting of an ozone water treatment for treating a treated surface of the substrate with ozone water and a solvent treatment for treating the treated surface of the substrate with an organic solvent twice or more. . 2. The resist removal method according to claim 1, wherein the organic solvent is at least one solvent selected from the group consisting of γ-butyrolactone, ethylene glycol diacetate and diacetin. The organic solvent is a mixed solvent of 100 parts by weight of at least one solvent selected from the group consisting of γ-butyrolactone, ethylene glycol diacetate and diacetin and 5 to 100 parts by weight of water. Item 3. The resist removal method according to Item 1 or 2. A resist removing apparatus for removing a resist on a substrate surface subjected to dry etching treatment and / or ion implantation treatment,
At least from an ozone dissolving apparatus that generates ozone water by dissolving ozone gas in raw water, an ozone water treatment tank to which ozone water generated by the ozone dissolving apparatus is supplied, a solvent tank that stores an organic solvent, and the solvent tank A resist removal apparatus comprising: a solvent treatment tank to which the organic solvent is supplied; and a substrate transport unit that reciprocates the substrate between the ozone water treatment tank and the solvent treatment tank. 5. The resist removal according to claim 4, wherein the substrate transport means can place a plurality of substrates simultaneously, and the ozone water treatment tank and the solvent treatment tank can contain the substrate transport means. apparatus.

Images