JP2003131398A - Alkaline system working fluid, method and apparatus for preparing working fluid and method and apparatus for feeding working fluid - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an alkaline working fluid which is capable of reducing the rate of consumption during working processing and the amount of waste liquids to be produced and has excellent solubility to organic films, such as photoresists, after exposure and a feeder, etc., for the same. SOLUTION: A developer feeder 100 is constituted by consecutively installing a preprocessing section 20, such as a filter 2, a regulating vessel 5 and a leveling vessel 6 to the rear stage of an accepting vessel 1 connected across piping L1 to a development processor 210. A liquid feed system 8 and a controller 9 are connected to the regulating vessel 5 and the concentrations of the dissolved photoresist components and alkaline components in the used liquid W are regulated to specified values in accordance with the values actually measured by concentration meters 51 and 52. The resultant regenerated liquid is fed through piping L2 to the development processor 210.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an alkaline working liquid, a method and an apparatus for adjusting the same, and a method and a device for supplying an alkaline working liquid, and more specifically, to a photoresist or a functional film coated on a substrate. Alkaline-based working liquid used for development and processing of organic film, method for adjusting the alkaline-based working liquid and apparatus therefor, and method for supplying alkaline-based working liquid for developing photoresist and processing functional film, and therefore Of equipment.

[0002]

2. Description of the Related Art In recent years, various organic films have been used for various purposes in the fields of manufacturing fine elements, micromachining, and the like. A typical example of such an organic film is a thin film of an organic photosensitive resin composition called a photoresist, which is indispensable for photolithography, or a so-called organic functional film.

The photolithography technique is widely used for transferring a fine pattern onto a substrate such as a wafer in the manufacture of semiconductor devices such as memories and logic circuits and liquid crystal devices, and is an extremely important step in the manufacturing process. Is. In general, a thin film of photoresist is applied on a wafer by, for example, spin coating, exposure is performed using a mask, and then development is performed to transfer the mask pattern onto the wafer.

As such photoresists, positive / negative, i-line, KrF excimer laser, ArF
There are many types depending on the use or conditions such as for excimer laser, and also in terms of material, including DQN resist in which diazoquinone (DQ) type photosensitizer is blended with novolac (N; Novolac) resin as a matrix material, A wide variety of products including photo-acid generator-containing resists and chemically amplified resists. Further, for developing such a photoresist (particularly a positive type), an alkaline developing solution such as an aqueous solution of tetramethylammonium hydroxide (TMAH) or an aqueous solution of potassium hydroxide (KOH) is widely used.

Generally, in a lithography process in manufacturing a semiconductor device or a liquid crystal device, development is carried out by spraying an alkaline developing solution on a photoresist after exposure (exposure) by a spray method, a paddle method or a dip method. . In this case, the developing solution is not reused, that is, the new solution is often used in a disposable manner, and there is a remarkable tendency particularly in the manufacture of semiconductor devices.

The reasons are as follows: (1) Currently, the mainstream wafer size used for manufacturing semiconductor devices is 8 inches (200 mm).
mmφ), and the amount used once per wafer is small, (2) the alkali concentration is lowered by being diluted with the rinse water for cleaning, and (3) it is contained in the developer when reused. There is concern that increase / accumulation of particles, metal ions, etc. will affect the post-process. (4) As mentioned above, photoresists and developers have a wide variety of uses and materials, and it is necessary to manage the developers according to each. It is not always done sufficiently.

On the other hand, as the functional film, a protective film for preventing deterioration and damage of liquid crystal display elements, semiconductor circuit elements and the like,
A flattening film for flattening the element surface, an interlayer insulating film for insulating between wirings arranged in layers, a spacer for keeping a constant gap between two substrates enclosing the liquid crystal of a liquid crystal panel, a liquid crystal alignment Liquid crystal alignment film having a function, a light-scattering film for obtaining front brightness for transflective and reflective liquid crystal displays, a low dielectric constant film having a low dielectric property, and the like, and a microlens as an optical element, etc. Is also exemplified as the organic functional film. These functional films have excellent properties such as electrical insulation, flatness, heat resistance, transparency, chemical resistance, mechanical strength, etc., depending on the application.

These functional films are generally based on an alkali-soluble organic resin, and are roughly classified into a positive type and a negative type in the same manner as a photoresist, and a lithography process is frequently used for the forming process. To be done. Even in the lithography process in the production of such a functional film, an alkaline processing liquid is sprayed on the functional film after exposure (photosensitization) by a spray method, a paddle method, or a dip method. In many cases, the new solution is not reused and the new solution is used in a disposable manner.

[0009]

By the way, in recent years, further miniaturization of fine members such as semiconductor devices, liquid crystal devices, and micromachines has been accelerated, and in particular, regarding semiconductor devices, it exceeds the expectations of the conventional design rules. Miniaturization with momentum
Thinning is in progress. For example, a semiconductor memory product corresponding to 0.13 μm is already being manufactured, and the importance of photolithography in the manufacturing process is increasing. Therefore, for patterning the photoresist, it is required to reliably achieve a finer line width than ever before. Under such circumstances, from the viewpoint of preventing the yield reduction, it is necessary to further suppress the mixing of particles and the like into the developing solution, and in this respect, the disposable use of the developing solution may continue in the future.

However, along with the miniaturization and thinning of the wafer, the diameter of the wafer is being increased in order to improve the productivity, and it is expected that 300 mmφ wafers by single wafer processing will become the mainstream in the near future. In this case, the amount of developer and rinse water used increases, so that the material cost rises, and the amount of waste liquid generated and the amount of treatment tend to increase. In addition to this, the present inventor has made a detailed study on a developing process of a photoresist (positive type) using a conventional developer new liquid, and has obtained the following findings.

Usually, the photoresist coated on the wafer is exposed to light after being prebaked for fixing.
Development is performed in order. For positive photoresist,
The functional group of the exposed portion is changed to a chemical form that easily reacts with an alkali such as carboxylic acid, and the dissolution rate of the exposed portion in an alkaline developing solution is remarkably increased as compared with the unexposed portion. Here, a positive type photoresist was applied on the metal thin film formed on the wafer, exposed and developed to perform patterning, and then the metal thin film was etched. In this case, the metal thin film exposed under the exposed portion of the photoresist dissolved by the development is etched.

However, it has been confirmed that etching defects may occur in a part of such a metal thin film depending on the conditions. When such etching failure occurs,
As the conductivity decreases, the reliability of the product decreases,
Alternatively, due to poor conductivity, the product cannot be established and the yield is reduced. In addition, with the miniaturization and thinning of semiconductor devices and liquid crystal devices, the probability of such events increasing,
There is also a risk that productivity will decrease.

The present inventor then conducted research on the cause of such etching defects. As a result, post bake or hard bake after the development process,
Or, in the rinse step, peeling of the surface layer or surface of the photoresist remaining on the wafer occurs, and one of the factors is that the peeled pieces may adhere to the exposed metal thin film and inhibit etching. I found it. If such an event is related to the solubility of the developing solution,
In the conventional developing method using a new solution, it is possible that not only the unexposed portion but also the exposed portion is not sufficiently dissolved. In order to cope with the extremely fine pattern line width, further improvement in the solubility at the time of development and thus the selective solubility is desired.

Further, when forming or molding the functional film, there is a possibility that the same kind of problems as the above-mentioned defective etching at the time of developing the photoresist may occur. That is, when the functional film after exposure is treated with an alkaline processing liquid, processing defects may occur in the same manner as the etching defects that may occur with the photoresist as described above.

Therefore, the present invention has been made in view of the above circumstances, and when used for developing and processing an organic film such as a photoresist or a functional film coated on a substrate, the usage amount and the generation of waste liquid are generated. It is an object of the present invention to provide an alkaline processing liquid that can reduce the amount and is excellent in solubility in an organic film after exposure, and can sufficiently prevent development failure and processing failure such as surface peeling of the organic film. . The present invention also provides a method and apparatus for adjusting the alkaline processing liquid,
Another object of the present invention is to provide a method and an apparatus for supplying the alkaline processing liquid to a process / equipment in which development / processing is performed.

[0016]

In order to solve the above-mentioned problems, the present inventor has conducted earnest research based on the above findings and found that the surface layer of the unexposed portion of the positive photoresist is exposed to an alkaline developer. It was further found that a poorly soluble film that exhibits dissolution resistance is formed, and this film portion can be peeled off thermally or mechanically from the lower layer in the post-baking or rinsing step after development, resulting in peeling of the surface layer. . Further, the permeability of the alkaline developing solution into the photoresist is one factor that influences the solubility of the resist, and in particular, the initial solubility of the poorly soluble film in the photoresist formed on the surface may be greatly affected. I also found out.

Further, such a phenomenon is caused by a protective film for a liquid crystal display device and a semiconductor circuit device, a planarizing film, an interlayer insulating film,
It was confirmed that it was also observed in the molding and processing of spacers between substrates, liquid crystal alignment films, light scattering films, low dielectric constant films, and functional films such as microlenses.

The inventor of the present invention has completed the present invention by further researching based on the above findings.

That is, the alkaline processing liquid according to the present invention is used to develop a photoresist applied on a substrate such as a wafer used for manufacturing a semiconductor device, a liquid crystal device or the like, or to form the above-mentioned various organic functional films. An alkaline processing liquid used for processing, that is, an alkaline processing liquid used for processing an organic film having photosensitivity, which constitutes an organic film of the same or different type as the organic film to be processed. It is characterized in that the component (organic film component) is dissolved at a concentration of 0.001 to 2.0 mass%.

As described above, the alkaline working fluid according to the present invention contains the dissolved first component (dissolved organic film component) as a constituent at the above-mentioned constant concentration. The alkaline processing liquid containing the first component has significantly improved wettability with respect to the organic film after being coated on the wafer and exposed to light, as compared with the conventional method using a new liquid. Specifically, it was confirmed that the surface tension of the alkaline processing liquid on the organic film was significantly reduced. Therefore, the alkaline processing liquid easily permeates the surface of the organic film, which is, so to speak, “friendly”.

In particular, in the example of the above photoresist, the alkali-based processing solution (in this case, the alkali-based developing solution) sufficiently dissolves in the unexposed portion of the hardly soluble film, so that the hardly soluble film is dissolved. Be promoted. In addition, the dissolved first component is preferably the same kind as the organic film to be processed, more preferably the same or substantially the same as the organic film to be processed, in that the wettability between the alkaline processing liquid and the organic film is further increased and the permeation becomes easier. It is preferable that they have the same composition, and further, those that contain the same kind of matrix and / or photosensitizer as the organic film to be processed.

Here, the concentration of the dissolved first component is 0.0
If it is less than 01% by mass, the permeability of the alkaline processing liquid into the organic film cannot be sufficiently enhanced, and it is difficult to recognize the superiority to the conventional new liquid. On the other hand, the concentration of this first component is 2.0
When the content exceeds the mass%, the erosion (edge effect) of the edge portion of the upper surface of the organic film (corresponding to the unexposed portion in the positive type) remaining as a pattern becomes remarkable, and the etching of the underlying layer after that
It is not preferable because it may adversely affect the subsequent processes such as film formation. Further, even if the concentration of the dissolved first component exceeds 2.0% by mass, it is difficult to develop the permeability according to the concentration. In the present invention, the concentration of the component contained in the alkaline working liquid is defined on a mass basis, that is, “mass%”, but it is substantially equivalent to “weight%” which is a weight standard (the same applies below).

In addition, when the organic film is a photoresist, a second component that forms an organic film of the same kind as or a different kind from the photoresist to be developed as processing is used as a first component.
Ingredients 0.001 to 2.0% by mass, preferably 0.01
~ 1.5 mass%, more preferably 0.1-1.0 mass%
It is preferable that it is dissolved at a concentration of. When the second component is the same or different photoresist component as the photoresist to be developed, the second component is substantially a photoresist component, and the second component is an organic film other than the photoresist component, for example, as described later. It may be a functional film component.

In this case, the alkaline processing liquid functions as an alkaline developing liquid containing the second component dissolved as a constituent component at the above-mentioned constant concentration. Such an alkaline processing liquid containing the dissolved second component has a wettability with respect to the photoresist after being coated on the wafer and exposed to light.
It can be significantly increased compared to the conventional method using a new solution. this is,
It is considered that this is because the surface tension of the alkaline processing liquid on the photoresist is significantly lowered and the alkaline processing liquid easily penetrates into the photoresist surface.

The dissolved second component is preferably of the same type as the photoresist to be developed, and more preferably from the viewpoint that the wettability between the alkaline processing liquid and the photoresist is further enhanced to facilitate permeation. It is preferable that they have the same or substantially the same composition, and further, it is desirable that they contain the same matrix and / or photosensitizer as the photoresist to be developed.

Here, the concentration of the dissolved second component is 0.0
If it is less than 01% by mass, the permeability of the alkaline developing solution into the photoresist cannot be sufficiently enhanced, and it is difficult to recognize the superiority to the conventional new solution. On the other hand, when the concentration exceeds 2.0 mass%, the erosion (edge effect) of the edge portion of the upper surface of the photoresist (corresponding to the unexposed portion in the positive type and the exposed portion in the negative type) remaining as the pattern becomes remarkable, It is not preferable because it may adversely affect the subsequent processes such as etching and film formation of the underlying layer. Further, even if the concentration of the dissolved second component exceeds 2.0% by mass, the penetrability according to the concentration is difficult to be expressed.

Alternatively, when the organic film is a functional film, a third component (functional film component) forming an organic film of the same kind or different kind as the functional film to be processed is preferably 0 as the first component. 0.001 to 0.5 mass%, more preferably 0.0
It is also useful if it is dissolved at a concentration of 1 to 0.3% by mass. When the third component is the same or different functional film component as the functional film to be processed, the third component is substantially a functional film component, and the third component is an organic film other than the functional film component,
For example, it may be the above-mentioned photoresist component.

The "functional film" in the present invention will be described below. The functional film contains a photosensitive organic polymer resin as a main component, is processed into a desired pattern shape by an alkaline processing liquid, and is not subjected to a peeling treatment thereafter, and remains as a structural member on the substrate in various required shapes. It is, so to speak, a permanent film. In contrast, photoresist is
Acts as a resist (resistive film) for patterning by etching a metal thin film or a metal oxide thin film on a substrate, and is removed by a resist stripping process after etching,
What does not finally remain on the substrate is a temporary film that is temporarily used.

The positive type of the functional film is, for example, an alkali-soluble organic resin (unsaturated carboxylic acid, unsaturated carboxylic acid anhydride, epoxy group-containing unsaturated compound, olefinic unsaturated compound, etc.). Examples thereof include those made of a polymer, those made of an alkali-soluble cyclic polyolefin-based resin), a solvent, and a solution made of a 1,2-quinonediazide compound as a photosensitizer.

After the raw material solution is applied on the substrate, prebaking is performed to evaporate the solvent and form a positive type photosensitive coating film. Then, after exposure by ultraviolet rays through a mask having a predetermined shape, the exposed portion is dissolved by the alkaline processing liquid of the present invention. The remaining unexposed portion is post-baked together with the substrate to obtain a functional film having a predetermined pattern.

Examples of the negative type functional film include, for example, alkali-soluble organic resins (unsaturated carboxylic acid, unsaturated carboxylic acid anhydride, epoxy group-containing unsaturated compound, olefinic unsaturated compound, etc.). (A copolymer)), a polysynthetic compound having an ethylenically unsaturated bond, a solvent, and a solution containing a radiation-sensitive polymerization initiator as a raw material.

After this raw material solution is applied on the substrate, it is pre-baked to evaporate the solvent and form a negative photosensitive coating film. Then, after being exposed to ultraviolet light through a mask having a predetermined shape, the unexposed portion is dissolved by the alkaline processing liquid of the present invention. The remaining exposed portion is post-baked together with the substrate to obtain a functional film having a predetermined pattern.

In contrast to such a functional film, the alkaline processing liquid functions as an alkaline molding / processing liquid containing the third component (dissolved functional film component) dissolved as a constituent at the above-mentioned constant concentration. To do. The alkaline processing liquid containing the dissolved third component has significantly improved wettability with respect to the functional film after being coated on the wafer and exposed to light, as compared with the conventional method using the new liquid. It is considered that this is because the surface tension of the alkaline processing liquid on the functional film is significantly reduced, and the alkaline processing liquid easily permeates the surface of the functional film.

The dissolved third component is preferably the same kind as the functional film to be processed, in that the wettability between the alkaline processing liquid and the functional film is further enhanced and the permeation is facilitated.
It is more preferable that they have the same or substantially the same composition, and further, it is desirable that they contain the same kind of matrix and / or photosensitizer as the functional film to be processed.

Here, the concentration of the dissolved third component is 0.0
If it is less than 01% by mass, the permeability of the alkaline processing liquid into the functional film cannot be sufficiently enhanced, and it is difficult to recognize the superiority to the conventional new liquid. On the other hand, the concentration of this third component is 0.5
When the content is more than mass%, erosion on the upper surface of the functional film remaining as a pattern (corresponding to the unexposed portion in the positive type and the exposed portion in the negative type) becomes remarkable and a desired pattern cannot be obtained, which is not preferable.

The alkaline component in the alkaline processing liquid is the main factor that influences the solubility of the organic film, and more specifically, the alkaline component is contained at a concentration of 0.05 to 2.5 mass%. It is preferable that it is composed of In addition, in such a suitable range, concentration control can be appropriately performed according to the type of the target organic film and / or alkali.

Further, when the organic film is a photoresist, the concentration of the alkaline component in the alkaline processing liquid is preferably 0.1 to 2.5% by mass, more preferably 0.1 to 2.5% by mass.
A value within the range of 2.4% by mass is preferable.

To give a concrete example, an alkaline component (for example, TMAH) is preferably used as the alkaline developer for photoresists used in the manufacture of semiconductor devices.
It is useful that the amount is 2 to 2.4% by mass, and more preferably 2.3 to 2.4% by mass. In addition, as an alkaline developer for a photoresist (for example, a DQN resist) used for manufacturing a liquid crystal device, an alkaline component is preferably 2.2.
It is useful for it to be -2.4 mass%, more preferably 2.3-2.4 mass%.

If the concentration of the alkali component is less than 0.1% by mass, the dissolution rate of the photoresist tends to decrease to an extent that is practically insufficient. On the other hand, when the concentration of the alkaline component exceeds 2.5% by mass, it becomes difficult to improve the solubility according to the increase in the concentration, and in some cases, the solubility of the photoresist and thus the patterning shape are controlled. It will be difficult.

Alternatively, when the organic film is a functional film, the concentration of the alkaline component in the alkaline processing liquid is preferably 0.05 to 2.4% by mass, more preferably 0.08 to
A value within the range of 2.4% by mass is preferable.

To give a concrete example, as an alkaline working liquid for a negative type (meth) acrylic functional film suitable for a protective film and a spacer, an alkaline component (eg TMAH) is used.
Is preferably 0.05 to 0.6% by mass, more preferably 0.08 to 0.12% by mass. Also,
As an alkaline processing liquid for a positive type (meth) acrylic functional film suitable for a protective film or an interlayer insulating film and a spacer,
Alkaline component (eg TMAH) is preferably 0.05
It is useful that the content is ˜0.6 mass%, more preferably 0.1 to 0.3 mass%.

Further, as an alkaline processing liquid for a negative type (meth) acrylic functional film suitable for a protective film and a liquid crystal alignment film, an alkaline component (eg TMAH) is preferably contained in an amount of 0.05 to 0.6 mass. %, More preferably 0.3 to
It is useful if it is 0.6% by mass. Furthermore, as an alkaline processing liquid for a positive type epoxy functional film suitable for a microlens, an alkaline component (eg TMAH) is used.
Is preferably 0.5 to 2.4 mass%, more preferably 1.0 to 2.4 mass%. In addition, as an alkaline processing liquid for a negative type (meth) acrylic functional film suitable for an interlayer insulating film, an alkaline component (for example, T
It is useful that the MAH) is preferably 1.0 to 2.4% by mass, more preferably 2.3 to 2.4% by mass.

The concentration of this alkaline component is 0.05% by mass.
If it is less than the above, the dissolution rate of the functional film tends to decrease to an extent that is practically insufficient. On the other hand, when the concentration of the alkaline component exceeds 2.4% by mass, it becomes difficult to improve the solubility according to the increase of the concentration, and in some cases, the solubility of the functional film and thus the patterning shape are controlled. It will be difficult.

Further, the method for preparing an alkaline working liquid according to the present invention is a method for effectively adjusting the alkaline working liquid according to the present invention, which is a process for processing an organic film coated on a substrate (in other words, A method for adjusting an alkaline processing liquid used in a treatment step), comprising a first component (dissolved organic) which is included in the alkaline processing liquid and constitutes an organic film of the same kind or different kind as an organic film to be processed. Concentration of membrane component) is 0.0
To a value within the range of 01 to 2.0% by mass, and
The concentration of the alkaline component contained in the alkaline processing liquid is 0.
It is characterized in that the liquidity of the alkaline working liquid is adjusted so as to be a value within the range of 05 to 2.5 mass%.

Specifically, for example, the concentrations of the dissolved first component and alkali component contained in the alkaline working fluid are appropriately measured, and the target set value is set based on the measured values and preset concentration values. If it does not satisfy the above condition, the operation of adding the first component or alkali to dissolve it and, if it exceeds the target set value, diluting can be carried out manually or automatically at any time. Alternatively, the amount of the alkali and the photoresist added and dissolved in the solvent of the alkaline processing liquid may be measured and controlled.

When the organic film is a photoresist, the first component is an organic film which is the same as or different from the photoresist which is contained in the alkaline processing liquid and is to be developed as processing. The concentration of the two components is 0.001
The concentration of the alkaline component contained in the alkaline processing liquid is 0.1 to 2.0% by mass.
It is preferable to adjust the liquidity of the alkaline working liquid so that the value falls within the range of 2.5% by mass.

Specifically, for example, the concentrations of the dissolved second component and alkaline component contained in the alkaline working fluid are appropriately measured, and the target set value is set based on the measured values and preset concentration values. If it does not satisfy the above condition, the second component or the alkali is added to dissolve it, while if it exceeds the target set value, the operation of diluting can be carried out manually or automatically at any time. Alternatively, the amount of addition and dissolution of the alkali and the second component in the solvent of the alkaline processing liquid may be measured and controlled.

Alternatively, when the organic film is a functional film, as a first component, a third component contained in the alkaline processing liquid and forming the same or different organic film as the functional film to be processed is included. So that the concentration is in the range of 0.001 to 0.5% by mass, and the concentration of the alkaline component contained in the alkaline working liquid is in the range of 0.05 to 2.4% by mass. It is preferable to adjust the liquidity of the alkaline processing liquid so that

Specifically, for example, the concentrations of the dissolved third component and alkali component contained in the alkaline working liquid are appropriately measured, and the target set value is set based on the measured values and preset concentration values. If it does not satisfy the above condition, the third component or alkali may be added to dissolve it, while if it exceeds the target set value, dilution may be performed manually or automatically at any time. Alternatively, the amount of addition and dissolution of the alkali and the third component in the solvent of the alkaline processing liquid may be measured and controlled.

The method for supplying the alkaline processing liquid according to the present invention is a method for supplying the alkaline processing liquid prepared according to the present invention to the processing step of the organic film coated on the substrate, wherein (1) ) A receiving step of receiving a used liquid containing a first component (organic film component) constituting the same kind or different kind of organic film as the organic film, and (2) a first component (dissolved organic film component) contained in the used liquid. ) And the concentration measuring step of measuring the concentration of the alkaline component, and (3) the concentration of the first component contained in the used liquid is 0.001 to 2.0 based on the measured concentrations of the first component and the alkaline component. The liquid of the used liquid so that the concentration of the alkaline component contained in the used liquid is in the range of 0.05 to 2.5% by mass, and the value of the used liquid is within the range of mass%. A step of adjusting the properties to obtain a regenerated liquid,
(4) A feeding step of feeding the regenerating liquid to the processing step. The used liquid received in the receiving step may be the one used in the processing step to be fed in the feeding step, or the one used in the processing step of another facility.

The used liquid received in the receiving step is, for example, one that has been used for processing an organic film and in which the first component has been dissolved or dispersed, and is usually diluted with rinsing water so that the alkali component is compared with the initial component. And is diluted. In the concentration measuring step, the concentrations of the dissolved first component and alkaline component contained in the used liquid are measured. Next, in the adjustment step, these measured values are weighed, for example, with a preset density value, and if insufficient, the first value corresponding to the difference is calculated.
While supplementing the components and / or the alkali, if excessive, dilute appropriately. At this time, it is preferable that the concentration measuring step and the adjusting step are continuously performed in parallel to perform the feedback control of the concentration. Then, the regenerated liquid in which the concentrations of the dissolved first component and alkaline component are adjusted to be within the above-mentioned predetermined range is fed to the organic film processing step.

Further, when the organic film is a photoresist, the first component forms an organic film which is the same as or different from the photoresist which is contained in the alkaline processing liquid and is a development target for processing. The concentration of the two components is 0.001
The concentration of the alkaline component contained in the alkaline processing liquid is 0.1 to 2.0% by mass.
It is preferable to adjust the liquidity of the alkaline working liquid so that the value falls within the range of 2.5% by mass. In this case, the regenerant liquid containing the second component and the alkaline component in the above concentration range is fed to the photoresist developing step.

Alternatively, when the organic film is a functional film, as the first component, a third component contained in the alkaline processing liquid and constituting the organic film of the same kind or different kind as the functional film to be processed is used. So that the concentration is in the range of 0.001 to 0.5% by mass, and the concentration of the alkaline component contained in the alkaline working liquid is in the range of 0.05 to 2.4% by mass. It is preferable to adjust the liquidity of the alkaline processing liquid so that In this case, the regenerant liquid containing the third component and the alkaline component in the above concentration range is fed to the functional film processing step.

Further, (5) a filtration step which is carried out between the receiving step and the adjusting step for filtering the used liquid, the first component (or the second component or the third component) remaining in the used liquid.
It is preferable to include a pretreatment process including at least one of a residual component removing step of removing a component) and a metal component removing step of removing a metal component contained in the used liquid.

When the used liquid used for processing the organic film is used, the first component may remain in a dispersed state, a dissolved state, or a residual state in some cases. It may also include metal ions and the like that have been dissolved during the sending to the receiving step. In the manufacture of elements such as semiconductor devices and liquid crystal devices and in micromachining, it is necessary to prevent them from being mixed, and therefore it is desirable to carry out the filtration step and the metal component removal step. In the used liquid, the dissolved first component has an upper limit value of the above predetermined range, that is, a concentration of 2.0.
Since it may be contained in excess of mass%, it is preferable to carry out a residual component removing step to remove a certain amount of the first component prior to the adjusting step.

Furthermore, in the filtration step, the used liquid is separated into a permeated liquid and a non-permeated liquid by cross-flow filtration, and the adjusting step adds the non-permeated liquid to the used liquid. Is also preferable. here,
The "permeated liquid" is a generic term for components (permeated components) that have permeated through the filtering means in filtration, and mainly or substantially consist of liquid components. Further, the "non-permeated liquid" is a generic term for components that do not permeate the filtration means in filtration (non-permeated component). In other words, it indicates a portion of the used liquid other than the "permeated liquid", and mainly Alternatively, it may consist essentially of a liquid component, but depending on the properties of the used liquid, it may contain a solid component as a filtration residue.

The filtration method applied to the filtration step is not particularly limited, but is suitable for the cleanliness, clarification, particle concentration, etc. of the alkaline processing liquid required for manufacturing elements such as semiconductor devices and liquid crystal devices. Cross-flow filtration is desirable in consideration of proper filtration accuracy (particle or molecular weight size). In this case, the used liquid is separated by filtration into a non-permeate liquid containing a substance having a fractional size (filtering size) or more and a permeate liquid containing a substance having a fractional size or less.

The impermeable liquid contains the first component having a size equal to or larger than the fractional size, that is, the organic membrane component, or the second component or the third component, which is added to the used liquid in the impermeable liquid adding step. For example, it can be used to adjust the concentrations of the first to third components dissolved in the used liquid. Therefore, it is not necessary to separately replenish new first to third components in the adjusting step. Further, by appropriately setting the filtration size in the filtration step, the metal ions in the non-permeate can be sufficiently reduced, and therefore it is suitable to be used for concentration adjustment in the adjustment step.

Furthermore, (6) the post-treatment process, which is carried out between the adjusting process and the supplying process and has a particle removing step for removing the particle component from the regenerating liquid, can prevent the mixing of particles into the processing process. It is more preferable because it can.

The processing liquid adjusting apparatus according to the present invention is an apparatus for adjusting the alkaline processing liquid used for processing the organic film applied on the substrate, and is contained in the alkaline processing liquid and contains the organic processing liquid. The concentration of the first component (dissolved organic film component) that constitutes the same or different organic film as the film is 0.001 to
The concentration of the alkaline component contained in the alkaline processing liquid is 0.05 to so that the value falls within the range of 2.0% by mass.
It is equipped with an adjusting unit for adjusting the liquidity of the alkaline working liquid so that the value is within the range of 2.5% by mass.

Further, when the organic film is a photoresist, the adjusting part is an organic material which is the same as or different from the photoresist which is contained in the alkaline processing liquid as the first component and which is a development target for processing. The concentration of the second component constituting the film is set to a value within the range of 0.001 to 2.0% by mass, and the concentration of the alkaline component contained in the alkaline processing liquid is 0.1 to 2. It is preferable that the liquidity of the alkaline working liquid is adjusted so that the value falls within the range of 5% by mass.

Alternatively, when the organic film is a functional film, the adjusting portion constitutes, as the first component, an organic film which is contained in the alkaline processing liquid and is the same or different from the functional film to be processed. The concentration of the third component is in the range of 0.001 to 0.5% by mass, and the concentration of the alkaline component contained in the alkaline working liquid is in the range of 0.05 to 2.4% by mass. It is also preferable that the liquidity of the alkaline processing liquid is adjusted so that the value falls within the range.

The alkaline developing solution supply apparatus according to the present invention is an apparatus for supplying an alkaline processing solution to a processed portion of an organic film coated on a substrate, and is of the same type as (a) organic film. Or a receiving part to which a used liquid containing a first component (dissolved organic film component) constituting an organic film of a different type is supplied,
(B) a concentration measuring unit for measuring the concentrations of the first component and the alkaline component contained in the used liquid; and (c) the first concentration contained in the used liquid, based on the measured values of the concentrations of the first component and the alkaline component. A value within the range of 0.05 to 2.5 mass% so that the concentration of the component is within the range of 0.001 to 2.0 mass% and the concentration of the alkaline component contained in the used liquid is within the range of 0.05 to 2.5 mass%. In order to obtain the regenerated liquid, the adjusting unit for adjusting the liquid property of the used liquid to obtain the regenerated liquid, and (d) the feeding unit for feeding the regenerated liquid to the processing unit.

Further, when the organic film is a photoresist, the receiving portion is supplied with the used liquid containing the second component which constitutes the organic film of the same kind or different kind as the photoresist. The concentration measuring unit measures the concentrations of the second component and the alkaline component contained in the used liquid, and the adjusting unit includes the used liquid in the used liquid based on the measured values of the concentrations of the second component and the alkaline component. So that the concentration of the second component is 0.001 to 2.0% by mass,
Moreover, the concentration of the alkaline component contained in the used liquid is 0.1
It is preferable to adjust the liquidity of the used liquid so that the value is within a range of from 2.5% by mass to 2.5% by mass.

Alternatively, when the organic film is a functional film, the receiving portion is supplied with the used liquid containing the third component which constitutes the organic film of the same kind or different kind as the used film. The concentration measuring section measures the concentrations of the third component and the alkaline component contained in the used liquid, and the adjusting section
Based on the measured values of the concentrations of the third component and the alkaline component, the concentration of the third component contained in the used liquid is 0.001 to 0.5.
Liquidity of the used liquid so that the value is within the range of mass% and the concentration of the alkaline component contained in the used liquid is within the range of 0.05 to 2.4% by mass. It is also suitable to adjust.

Specifically, (e) a filtering section provided between the receiving section and the adjusting section for filtering the used liquid, the first component (or the second component or the second component remaining in the used liquid). It is more preferable to include a pretreatment unit having at least one of a residual component removal unit for removing the three components) and a metal component removal unit for removing the metal components contained in the used liquid.

Further, the filtering section separates the used liquid into a permeated liquid and a non-permeated liquid by cross-flow filtration, and (f) is connected to the filtering section and the adjusting section, and
It is more preferable to include a non-permeate transfer section for transferring the non-permeate from the filtration section to the adjustment section. Further, (g) a particle component contained in the regenerant liquid provided between the adjustment section and the feeding section It is more preferable to include a post-treatment section having a particle removal section to be removed.

In addition, (h) is connected to the adjusting section,
The regenerated liquid is naturally transferred from the adjustment unit due to the head pressure difference,
It is useful to provide a leveling unit for leveling the concentrations of the first component (or the second component or the third component) and the alkaline component contained in the regenerating liquid. As a result, it becomes easier to continuously supply the regenerating liquid as the alkaline processing liquid to the processing part of the organic film, and moreover, as compared with the case where the regenerating liquid is fed by the batch method, The concentrations of the one component (or the second component or the third component) and the alkaline component can be maintained more stably.

[0069]

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be described in detail below. The alkaline processing liquid according to the present invention is used for processing an organic film applied on a substrate in a photolithography process applied to element manufacturing of semiconductor devices, liquid crystal devices, etc. and micro processing, especially for developing a photoresist or for forming a functional film. The first component (organic film component), which is used for processing and constitutes the same or different organic film as the organic film to be processed, has a concentration within the range of 0.001 to 2.0% by mass. It is made by melting.

<First Embodiment> This embodiment is one mode in which the organic film is a photoresist. In this embodiment, the alkaline processing liquid functions as an alkaline developing liquid for the photoresist. The dissolved photoresist component (dissolved second component) as the dissolved organic film component contained in the alkaline developer (alkali processing liquid) is not particularly limited, and may be the same type as the photoresist to be developed. Although it may be one of different types, it is desirable that it has excellent affinity with the photoresist to be developed, and from this viewpoint, it is preferably the same type as the photoresist to be developed, for example, the same matrix. Desirably, a resin-containing material, more preferably the same type of sensitizer component, and even more preferably the same or substantially the same composition.

Specific examples of such a photoresist include:
For example, a matrix material such as a novolac resin or an acrylic (based) resin containing a diazoquinone, particularly a diazonaphthoquinone-based photosensitizer may be used. They are,
In recent years, it has been widely used in photolithography in manufacturing semiconductor devices and liquid crystal devices.

The alkaline component contained in the alkaline developing solution of the present embodiment is not particularly limited, but examples thereof include alkali metal hydroxides and substituted or unsubstituted ammonium hydroxides. But TM
AH and KOH are preferred. Further, it is preferable that the content of the alkali component is 0.1 to 2.5% by mass, more preferably 0.1 to 2.4% by mass.

Furthermore, within such a preferable range, concentration control can be appropriately performed depending on the type of the photoresist and / or the alkali to be targeted. For example,
As an alkaline developing solution for a photoresist used for manufacturing a semiconductor device, an alkaline component (for example, TMAH) is used.
Is preferably 2.2 to 2.4% by mass (more specifically 2.375 to 2.385% by mass), and more preferably 2.
3 to 2.4 mass% (more specifically, 2.377 to 2.3)
83% by mass) is useful.

Further, as an alkaline developing solution for a photoresist (for example, a DQN resist) used for manufacturing a liquid crystal device, an alkaline component is preferably 2.2 to 2.4 mass% (more specifically, 2.370). It is useful that the amount is from about 2.390% by mass), more preferably from 2.3 to 2.4% by mass (more specifically from 2.375 to 2.385% by mass).

Next, with reference to the drawings, a working fluid adjusting method and apparatus and a working fluid supply method and apparatus according to the present invention will be described. In addition, the same reference numerals are given to the same elements,
A duplicate description will be omitted. Further, the positional relationship such as up, down, left and right is based on the positional relationship shown in the drawings unless otherwise specified. The dimensional ratios in the drawings are not limited to the illustrated ratios.

FIG. 1 is a schematic diagram showing the configuration of a preferred embodiment of the working fluid supply apparatus according to the present invention. The developing solution supply apparatus 100 (working solution supply apparatus; also serving as the working solution adjusting apparatus) is a development processing apparatus 210 of the semiconductor manufacturing facility 200.
It is connected to the (processing section) via a pipe L1 and a pipe L2 (feeding section), and circulates and supplies the alkaline developing solution of the present invention to the development processing apparatus 210. The developing solution supply apparatus 100 includes a pretreatment unit 20, an adjusting tank 5, and a leveling tank 6 at a stage subsequent to the receiving tank 1 (receiving unit) connected to the pipe L1.
The (leveling section) is connected in series, and a pipe L2 (feeding section) provided with a particle remover 7 (particle removing section) is connected to the final leveling tank 6.

The receiving tank 1 is equipped with a stirrer M, and the used solution W used for developing the photoresist in the developing processing apparatus 210 is introduced through the pipe L1. The pretreatment section 20 arranged in the subsequent stage is provided with the pipe L3 in the receiving tank 1 respectively.
Through L5, the filter 2, the residual photoresist remover 3 and the metal ion remover 4 are arranged in this order.

The filter 2 (filter section) is provided with a membrane separation module 21 composed of a single or a plurality of filtration membranes or a multi-stage unit thereof, and the used liquid W sent from the receiving tank 1 is used. Is filtered. Membrane separation module 21
The type of membrane used in the above is not particularly limited, and examples thereof include a microfiltration (MF) membrane, an ultrafiltration (UF) membrane, a nanofiltration (NF) membrane, and a reverse osmosis (RO) membrane.

These are properly used depending on the required filtration accuracy, but from the viewpoint of being used in the semiconductor manufacturing facility 200, MF membranes, UF membranes, NF membranes that can realize high-performance filtration by crossflow (crossflow filtration). Membranes and RO membranes are preferable, and it is preferable to use UF membranes or NF membranes in consideration of filtration performance, filtration rate and simplicity. Moreover, the property of the membrane is not particularly limited, and may be, for example, a flat membrane, a hollow fiber, or the like.

As with the filter 2, the residual photoresist remover 3 (residual component remover) is provided with a membrane separation module 31 composed of a single or a plurality of filtration membranes or a multi-stage unit thereof. Further, with respect to a permeation component (a permeation liquid when cross flow filtration using UF or NF is adopted, which is sent from the membrane separation module 21 through a pipe, it will be referred to as a “permeation liquid” hereinafter). Membrane filtration is performed. The type of membrane used for the membrane separation module 31 is not particularly limited, but one having higher filtration accuracy than the membrane constituting the membrane separation module 21 of the filter 2 (for example, the pore diameter is larger than that of the membrane constituting the membrane separation module 21). Then the smaller one) is used.

For example, when the membrane separation module 21 uses the MF membrane, the membrane separation module 31 uses the UF membrane,
It is desirable to use an NF film or an RO film. Similarly,
If the former uses a UF membrane, the latter uses an NF membrane or RO.
It is preferable to use a membrane, or if the former is an NF membrane, the latter is an RO membrane. Note that the same type of membrane may be used for both, and the membrane filtration accuracy of the membrane separation module 31 may be increased as described above.

Further, the receiving tank 1, the filter 2, and the residual photoresist remover 3 are connected to the drain system 10 by a pipe L6. As a result, the excess liquid from the receiving tank 1 and the non-permeated liquid from the filter 2 and the residual photoresist remover 3 are discharged to the drain system 10 as waste liquid. Further, a part of the non-permeated liquid from the filter 2 is transferred to the adjustment tank 5 through the pipe L7 (non-permeated liquid transfer section) having the flow rate adjusting valve V4.

The adjusting tank 5 is connected to the metal ion remover 4 via a pipe L8, and has an agitator M inside. A circulation pipe L9 provided with densitometers 51 and 52 is installed outside the tank. Piping L to this adjusting tank 5
The leveling tank 6 connected via 10 is naturally fed with a regenerant liquid Ws, which will be described later, adjusted in the adjusting tank 5, and a circulation pipe L11 provided with concentration meters 61 and 62 is installed outside the tank. Has been done.

The densitometer 51 is for detecting the concentration of the dissolved photoresist component contained in the used liquid W in the adjusting tank 5, and includes an absorptiometer, a refractometer, a viscometer, an ultrasonic densitometer, and a liquid. Various measuring instruments such as a densitometer and an automatic titrator are used. Here, for example, Japanese Patent No. 2561578 by the present applicant shows a high correlation between the concentration of the dissolved resin in the alkaline developing solution and the absorbance, and the concentration of the dissolved photoresist component is measured by an absorptiometer. It is understood that it is measured with high accuracy.

On the other hand, the densitometer 52 detects the concentration of the alkaline component contained in the used liquid W in the adjusting tank 5, and includes a conductivity meter, an ultrasonic densitometer, a liquid densitometer, an automatic titrator, Various measuring devices such as a phase difference densitometer using an electromagnetic induction coil are adopted. For example, the above-mentioned Japanese Patent No. 256157.
Japanese Patent Laid-Open No. 8 shows a high correlation between the alkali concentration in the alkaline developer and the conductivity, and it is understood that the concentration of the dissolved photoresist component can be measured with high accuracy by the conductivity meter. In this way, the concentration measuring section is constituted by the densitometers 51 and 52. Also, the densitometers 61 and 62 are
Each is for detecting the dissolved photoresist component concentration and the alkaline component concentration of the regenerant liquid Ws in the leveling tank 6, and the same measuring equipment as the densitometers 51 and 52 can be used.

The developing solution supply apparatus 100 further includes a solution supply system 8 and a controller 9. The liquid supply system 8 includes pipes L21 to L1 having flow rate adjusting valves V1 to V3, respectively.
A pure water supply system 81 connected to the adjusting tank 5 via L23,
It is composed of a developing solution stock solution supply system 82 and a developing solution new solution supply system 83. The pure water supply system 81 has a device (not shown) for storing or generating so-called pure water or ultrapure water in which the ion concentration, particle concentration, etc. are appropriately controlled. On the other hand, the developing solution undiluted solution supply system 82 holds, for example, a TMAH solution adjusted to have an alkaline component concentration of about 20% by mass, and the developing solution undiluted solution supply system 83 previously holds the undiluted solution of the developing solution. A new developer solution obtained by diluting to T, for example, T adjusted to an alkali component concentration of 2.38% by mass.
The MAH solution is retained.

Further, the control unit 9 is one in which interfaces 91 and 93 are connected to a computing unit 92 such as a CPU or MPU. The interface 91 is an input interface and is connected to the densitometers 51, 52, 61, 62. The concentration detection signals of the dissolved photoresist component and the alkaline component obtained by these densitometers are input to the arithmetic unit 92 via the interface 91. On the other hand, the interface 93 is an output interface and is connected to the flow rate adjusting valves V1 to V4, and the control signal of the valve opening / closing amount, opening / closing time or time from the arithmetic unit 92 is output to each valve. The controller 9, the adjusting tank 5, and the liquid supply system 8 constitute an adjusting unit.

Furthermore, the leveling tank 6 and the development processing apparatus 2
The specific removing means used as the particle remover 7 provided in the pipe L2 connecting with 10 is not particularly limited, but since the particles are fine particle components, using a filtering means such as membrane filtration ensures reliable and simple processing. Therefore, it is preferable.

The developing solution supply apparatus 10 configured as described above
An example of the method for adjusting the working fluid and the method for supplying the working fluid according to the present invention using 0 will be described. FIG. 2 is a flow chart showing an outline of the procedure of a preferred embodiment of the working fluid supply method according to the present invention. In addition, in each of the following processing steps, the temperature is appropriately adjusted as necessary.

First, the processing is started, and the semiconductor manufacturing facility 20
The used liquid W used for the development is received in the receiving tank 1 from the developing device 210 of No. 0 through the pipe L1 (step S1; receiving step). Next, the used liquid W that has been sufficiently stirred and mixed by the stirrer M in the receiving tank 1 is introduced into the filter 2 through the pipe L3, and the membrane separation module 21 is circulated to perform membrane filtration (step S2; filtration step). Then, the permeated liquid is sent to the residual photoresist remover 3 through the pipe L4, and a part of the non-permeated liquid is fed into the pipe L as described later.
It is supplied to the adjusting tank 5 through 7. The rest of the non-permeated liquid is sent to the drain system 10 through the pipe L6.

In the residual photoresist removing device 3, the residual photoresist dissolved in the used liquid W is removed by membrane filtration (step S3; residual component removing step).
The permeated liquid from which the photoresist has been removed is introduced into the metal component remover 4 through the pipe L5 to remove metal ions from the used liquid (step S4; metal ion removal step).
In this way, the pretreatment process is composed of steps S2 to S4.

Next, the used liquid W from which metal ions have been removed
Is supplied to the adjusting tank 5. In the adjusting tank 5, this used liquid W
While being stirred by the stirrer M, a part thereof is circulated through the circulation pipe L9. In the meantime, the dissolved photoresist component concentration and the alkaline component concentration of the used liquid W are measured by the densitometers 51 and 52 (step S51; concentration measuring step). The case where the densitometers 51 and 52 are an absorptiometer and a conductivity meter, respectively, will be described in more detail.
When the used liquid flowing through the circulation pipe L9 passes through the densitometers 51 and 52, the absorbance detection signal according to the absorbance and the conductivity detection signal according to the conductivity are continuously or intermittently supplied to the control device 9 Is output to.

Correlation data of the concentration of the dissolved photoresist component and the concentration of the alkaline component with respect to these detection signal intensities are input or stored in the arithmetic unit 92 in advance. Then, the dissolved photoresist component concentration and the alkali component concentration (hereinafter, referred to as “concentration actual measurement value”) in the adjustment tank 5 are obtained from the actually measured detection signal intensity. Further, the calculation unit 92 has
Target set values of the dissolved photoresist component concentration and the alkaline component concentration are input or stored in advance. The calculation unit 92 further obtains the difference between the density value thus set (hereinafter, “density setting value”) and the actual density value.

Here, in this embodiment, the concentration set value of the dissolved photoresist component is 0.001 to 2.0% by mass,
The value is preferably 0.01 to 1.5% by mass, more preferably 0.1 to 1.0% by mass. Moreover, the concentration set value of the alkaline component is preferably set to a value within the range of 0.1 to 2.5 mass%.

When the measured concentration value of the dissolved photoresist component is lower than the concentration set value, the control device 9 outputs a valve opening signal for a predetermined time to the flow rate adjusting valve V4 to supply the photoresist into the adjusting tank 5 ( Non-permeate addition step). When the measured concentration value of the dissolved photoresist component exceeds the concentration set value, for example, a valve open signal for a certain period of time is output to the flow rate adjusting valve V3, and the new liquid is supplied into the adjusting tank 5.

Similarly, when the actual measured value of the concentration of the alkaline component is lower than the set concentration value, the controller 9 outputs a valve opening signal for a fixed time to the flow rate adjusting valve V2 to supply the stock solution of the developing solution into the adjusting tank 5. To do. When the actually measured concentration of the alkaline component exceeds the concentration set value, a valve opening signal for a certain period of time is output to the flow rate adjusting valve V1, and pure water is supplied into the adjusting tank 5.

Then, the dissolved photoresist component concentration and the alkali component concentration are continuously or intermittently measured while the used liquid W to which pure water or the like has been added is sufficiently stirred and mixed by the stirrer M. Then, when the difference between the measured density value and the density set value becomes a predetermined value, or when the density range is set to the density set value, the measured density value becomes a value within the density range ( In step S52), the liquid properties of the dissolved photoresist component and the alkaline component in the used liquid W are continuously adjusted (step S54). In this way, the adjustment process is composed of steps S52 to S54.

Next, the used liquid W whose concentration has been adjusted is transferred to the leveling tank 6 as the regenerated liquid Ws. The regeneration liquid Ws is
Natural liquid is sent through the pipe L10. That is, unless the pipe L10 is shut off from the adjusting tank 5 to the leveling tank 6,
The liquid is constantly sent according to the difference in head pressure between the two. Therefore, the leveling tank 6 can be made to function as a buffer tank for the regenerating liquid Ws whose dissolved photoresist component concentration and alkali component concentration are standardized.

Further, the densitometers 61 and 62 may be used to measure the dissolved photoresist component concentration and the alkaline component concentration of the regenerant liquid Ws in the leveling tank 6. In principle, the liquid properties in the adjusting tank 5 and the leveling tank 6 are the same, but if there is some variation due to the installation conditions of both, or the timing of liquid transfer, etc. Control device 9
It is also possible to perform control so that the actual measured values of these concentrations are fed back to the liquid property adjustment in the adjusting tank 5. The concentration measurement by these densitometers 61 and 62 does not always have to be continuously performed, and if such concentration adjustment is unnecessary, the densitometer 6
It is not necessary to install 1,62.

Then, the regenerant liquid Ws is passed through the pipe L2.
Is sent to the particle remover 7 to remove the fine particle component (step S7; particle removing step, post-processing step). Then, the regenerated liquid W from which the particles have been removed
The required amount of s is supplied to the development processing apparatus 210 through the pipe L2 (supplying step), and the supply processing of the alkaline developer is completed.

According to the developing solution supplying apparatus 100 having such a structure and the processing solution supplying method using the same, the regenerating solution of the alkaline developing solution to be supplied to the developing processing apparatus 210 dissolves 0.001 of the dissolved photoresist component. Since it is contained at a concentration of ˜2.0% by mass, the penetrability and wettability to the photoresist which has been coated and exposed on the substrate such as a wafer is enhanced. When the concentration of the dissolved photoresist component is less than 0.001% by mass, the penetrability into the photoresist is insufficient, while when this concentration exceeds 2.0% by mass, the photoresist remaining as a pattern (positive type In this case, the erosion (edge effect) of the edge portion on the upper surface may be remarkable, which corresponds to the unexposed portion.

Therefore, by adjusting the concentration of the dissolved photoresist component to a value within the range of 0.001 to 2.0 mass%, sufficient penetrability can be obtained, that is, "familiarity" with the photoresist during development. And the degree of controllability of the pattern shape can be prevented. Therefore, it is possible to achieve the penetration and dissolution of the unexposed portion into the surface layer of the photoresist, the formation of the hardly soluble layer and the peeling thereof, and it is possible to prevent the adverse effect on the processing in the post-process after the development. As a result, for example, it is possible to sufficiently prevent the etching failure of the lower layer, which is presumed to be caused by the peeling of the poorly soluble layer, and suppress the reduction in the yield of the semiconductor device or the liquid crystal device.

Further, even if the concentration of the dissolved photoresist component exceeds 2.0% by mass, the penetrability corresponding to the concentration tends to be hardly exhibited. Therefore, if this concentration is set to 2.0% by mass or less, it is possible to suppress the excessive use of the dissolved photoresist component, and it is possible to reduce labor and cost.

Further, since the concentration of the alkaline component contained in the regenerant is preferably 0.1 to 2.5% by mass, a practically sufficient photoresist dissolution rate can be obtained. When the concentration of the alkaline component exceeds 2.5% by mass, it becomes difficult to improve the solubility according to the increase of the concentration, and in some cases, it becomes difficult to control the solubility of the photoresist and thus the patterning shape. When the above-mentioned TMAH is used as the alkali, a stock solution of the TMAH solution having a concentration of about 20% by mass is generally used. Therefore, if the concentration is too high, it may be difficult to adjust the liquid properties.

Here, as shown in FIG. 1, when used for developing a photoresist in the manufacture of a semiconductor device, the concentration of the alkaline component (eg TMAH) in the regenerant is preferably 2.2 to 2.4% by mass. Preferably 2.3-2.4
It is useful that the content is% by mass. By doing so, there is an advantage that patterning in which the unexposed portion is formed with a line width and a film thickness of a predetermined dimension can be performed extremely reproducibly and reliably.

When used for developing a photoresist (for example, a DQN resist) in the manufacture of liquid crystal devices, the concentration of the alkaline component in the regenerating liquid is preferably 2.2 to 2.4.
It is preferable that the content is mass%, more preferably 2.3 to 2.4 mass%. Also in this case, the patterning in which the unexposed portion is formed with the line width and the film thickness of a predetermined dimension can be performed extremely reproducibly and reliably.

Further, in the developing solution supplying apparatus 100, since the regenerating solution obtained from the used solution which has been once used for the development can be supplied to the developing processing apparatus 210 as the alkaline developing solution of the present invention, the conventional new solution is disposable. The amount of waste liquid generated can be significantly reduced as compared with the case of using the method. Furthermore, in order to adjust the concentration of the dissolved photoresist component, the filter 2 in the pretreatment process is used.
Since the non-permeated liquid from Example 1 is used, the dissolved photoresist component can be effectively used and the waste liquid can be further reduced.

Furthermore, since the dissolved photoresist component concentration and the alkali component concentration of the used liquid W in the adjusting tank 5 are measured and the liquid properties are adjusted based on the measured concentration values, the accuracy and precision are excellent. Concentration control can be realized. At this time, if the concentration adjustment is performed continuously or intermittently, the concentration of the dissolved photoresist component and the concentration of the alkaline component can be more reliably and stably maintained within a certain concentration value or concentration range. Further, by using the leveling tank 6, and by using the actual concentration measured value in the leveling tank 6 for the concentration adjustment in the adjusting tank 5, the stable supply of the regenerant solution to the development processing apparatus 210 can be made more reliable. be able to.

<Second Embodiment> The present embodiment is one mode in which the organic film is a functional film. In this aspect,
The alkaline processing liquid functions as a molding processing liquid for various functional films. Dissolving functional film component as an organic film component contained in this molding processing liquid (alkali processing liquid) (dissolved third
The component) is not particularly limited, and may be the same kind or different kinds as the functional film to be processed, but one having excellent affinity with the functional film to be processed is preferable. From this viewpoint, it is preferable that the functional film to be processed is of the same kind, for example, the same matrix resin is contained, more preferably the photosensitizer component is also the same kind, and more preferably the same or substantially the same composition. .

As described above, the functional film is composed of a photosensitive organic polymer resin as a main component, is processed into a desired pattern shape by an alkali processing liquid, and is not subjected to a peeling treatment thereafter, and is a structural member on a substrate. It is a so-called permanent film that fulfills various functions required to remain in, and is generally based on an alkali-soluble organic resin, and is roughly classified into a positive type and a negative type similar to photoresists. A lithography process is often used for the molding process.

The positive functional film is made of, for example, a copolymer of an alkali-soluble organic resin (unsaturated carboxylic acid, unsaturated carboxylic acid anhydride, epoxy group-containing unsaturated compound, olefinic unsaturated compound, etc.). And a solution of a 1,2-quinonediazide compound as a photosensitizer and a solvent. On the other hand, the negative functional film includes, for example, a copolymer of an alkali-soluble organic resin (unsaturated carboxylic acid, unsaturated carboxylic acid anhydride, epoxy group-containing unsaturated compound, olefinic unsaturated compound, etc. ), A polysynthetic compound having an ethylenically unsaturated bond, a solvent and a radiation-sensitive polymerization initiator as a raw material.

When the functional film is classified from the viewpoint of use, for example, a protective film for preventing deterioration or damage of a liquid crystal display device, a semiconductor circuit device, a flattening film for flattening the device surface, and a layered structure. Interlayer insulating film for insulating between the wirings arranged in a space, a spacer for keeping a constant space between two substrates for enclosing the liquid crystal of the liquid crystal panel, a liquid crystal aligning film having a liquid crystal aligning ability, a semi-transmissive type and a reflective type Examples thereof include a light-scattering film for obtaining front luminance for liquid crystal displays, a low dielectric constant film having a low dielectric property, and the like, and microlenses as optical elements can be exemplified as the organic functional film. These functional films have electrical insulating properties, flatness,
It has excellent properties such as heat resistance, transparency, chemical resistance, and mechanical strength.

Here, the alkaline component contained in the alkaline working liquid of the present embodiment is not particularly limited,
Examples thereof include alkali metal hydroxides and substituted or unsubstituted ammonium hydroxides. Among them, T
MAH and KOH are preferred. Furthermore, it is suitable that the content concentration of the alkali component is preferably 0.05 to 2.4 mass%, more preferably 0.08 to 2.4 mass%. Further, the concentration set value of the dissolved functional film component (dissolved third component) contained in the alkaline processing liquid is preferably 0.001 to 0.5% by mass, more preferably 0.01 to 0.3% by mass. Set to a value within the range.

Furthermore, in such a preferable range, the concentration of the alkaline component can be appropriately controlled according to the type of functional film and / or alkali to be targeted. As an example, a negative type (meth) suitable for a protective film and a spacer
As the alkaline working liquid for the acrylic functional film, an alkaline component (eg, TMAH) is preferably 0.05 to
It is useful to be 0.6% by mass, more preferably 0.08 to 0.12% by mass. In addition, as an alkaline processing liquid for a positive (meth) acrylic functional film suitable for a protective film or an interlayer insulating film and a spacer, an alkaline component (for example, T
MAH) is preferably 0.05 to 0.6% by mass, more preferably 0.1 to 0.3% by mass.

Further, as the alkaline working liquid for the negative type (meth) acrylic functional film suitable for the protective film and the liquid crystal alignment film, an alkaline component (eg TMAH) is preferably contained in an amount of 0.05 to 0.6 mass. %, More preferably 0.3 to
It is useful if it is 0.6% by mass. Furthermore, as an alkaline processing liquid for a positive type epoxy functional film suitable for a microlens, an alkaline component (eg TMAH) is used.
Is preferably 0.5 to 2.4 mass%, more preferably 1.0 to 2.4 mass%. In addition, as an alkaline processing liquid for a negative type (meth) acrylic functional film suitable for an interlayer insulating film, an alkaline component (for example, T
It is useful that the MAH) is preferably 1.0 to 2.4% by mass, more preferably 2.3 to 2.4% by mass.

Further, the working fluid adjusting method and apparatus and the working fluid supplying method and apparatus of the present invention suitable for this embodiment are
"Photoresist" and "development" are read as "functional film" and "formation / processing" of various functional films, respectively, and the above-mentioned alkaline processing liquids corresponding to various functional films are used instead of the alkaline developing liquid. Other than that, the developer supply device 1
A machining fluid adjusting device and a machining fluid supplying device configured in the same manner as 00, and a machining fluid adjusting method and a machining fluid supplying method using them can be exemplified.

According to this embodiment, since the regenerating liquid of the alkaline processing liquid contains the dissolved functional film component in a concentration of 0.001 to 0.5% by mass, it is applied to the substrate such as a wafer and exposed. The penetrability and wettability into the broken functional film are enhanced. If the concentration of the dissolved functional film component is less than 0.001% by mass, the permeability to the functional film is insufficient, while if the concentration exceeds 0.5% by mass, the upper surface of the functional film remaining as a pattern is eroded. Becomes remarkable and a desired pattern cannot be obtained.

Therefore, the concentration of the dissolution functional film component is set to 0.001.
By adjusting the value within the range of up to 0.5 mass%, sufficient permeability can be obtained, that is, the degree of “familiarity” with the functional film at the time of molding / processing can be improved and the shape controllability can be improved. It can suppress the decline. Therefore, the remaining unexposed portion or exposed portion can be penetrated / dissolved in the surface layer of the functional film, and the formation of the hardly-solubilized layer and the peeling thereof can be suppressed. As a result, for example, it is possible to sufficiently prevent the etching failure of the lower layer, which is supposed to be caused by the peeling of the hardly soluble layer, and prevent the yield of the structure including the functional film from decreasing.

Further, even if the concentration of the dissolution functional membrane component exceeds 0.5% by mass, the permeability depending on the concentration tends to be difficult to be expressed. Therefore, if this concentration is 0.5 mass% or less,
Excessive use of the dissolution function film component can be suppressed, and labor and cost can be reduced.

Furthermore, since the concentration of the alkaline component contained in the regenerant is preferably 0.05 to 2.4 mass%, a practically sufficient dissolution rate of the functional film can be obtained. If the concentration of the alkaline component exceeds 2.4% by mass, it becomes difficult to improve the solubility according to the increase of the concentration, and in some cases, it becomes difficult to control the solubility of the functional film and thus the patterning shape. There is. When the above-mentioned TMAH is used as the alkali, a stock solution of the TMAH solution having a concentration of about 20% by mass is generally used. Therefore, if the concentration is too high, it may be difficult to adjust the liquid properties.

Further, since the regenerated liquid obtained from the used liquid which has been once used for processing can be supplied to the processing apparatus as the alkaline processing liquid of the present invention, compared with the case where the conventional new liquid is used in a disposable system. As a result, the amount of waste liquid generated can be significantly reduced. Further, since the non-permeated liquid from the filter 2 in the pretreatment step is used for adjusting the concentration of the dissolved functional film component, the dissolved functional film component can be effectively used and the waste liquid can be further reduced.

Furthermore, since the concentration of the dissolved functional film component and the concentration of the alkaline component of the used liquid W in the adjustment tank 5 are measured and the liquid property is adjusted based on the measured concentration values, the accuracy and precision are excellent. Concentration control can be realized. At this time, if the concentration adjustment is performed continuously or intermittently, the concentration of the dissolved functional film component and the concentration of the alkaline component can be more reliably and stably maintained at a constant concentration value or concentration range. Further, by using the leveling tank 6, and by providing the actual concentration measured value in the leveling tank 6 for concentration adjustment in the adjusting tank 5, it is possible to more reliably ensure stable supply of the regenerant liquid to the processing apparatus. You can

The present invention is not limited to the above-described embodiment. For example, the photoresist is dissolved by dissolving the photoresist in the undiluted solution or the new solution without reusing the used solution W and dissolving it. The concentration-adjusted product may be used as an alkaline developing solution (alkali processing solution according to the present invention). Further, as the residual photoresist remover 3, instead of the one including the membrane separation module 31, for example, an electrodialysis unit, an electrolysis unit, an ion exchange unit, and an evaporation concentration unit may be used to reduce the scale of equipment and to reduce alkali components. From the viewpoint of suppressing decomposition, the advantage of using membrane filtration is great.

Furthermore, it is desirable that the densitometers 51 and 52 have a temperature compensating function, or, instead, the control device 9 has a temperature compensating function of the measured concentration value, for example, a detection signal based on the measured temperature value. It may have a function of correcting the intensity. Furthermore, the working liquid adjusting apparatus of the present invention may be incorporated in the development processing apparatus 210 to carry out the working liquid adjusting method of the present invention in the development processing step. In this case, as an example, there is a case of applying to the developer management device described in the above-mentioned Japanese Patent No. 2561578. In addition, an input / output interface having an input / output function may be used instead of the interfaces 91 and 93, and manual control may be performed instead of the automatic control using the control device 9.

Further, it is desirable to install the pretreatment section 20, the posttreatment section, or the leveling tank 6, but when the used liquid W is not used as described above, or when the used liquid W is used, It may not be provided depending on the clarity. Further, as the pretreatment or the posttreatment, the dissolved gas contained in the used liquid W or the regenerated liquid Ws may be removed. Furthermore, in calculating the dissolved photoresist component concentration and the alkaline component concentration, in order to measure the liquid amount in the adjusting tank 5 or the leveling tank 6, each tank 5, 6 is equipped with a liquid level meter, a volume meter, or a weight meter. May be provided.

Furthermore, the used liquid W can be regenerated not only once but also a plurality of times. However, in consideration of deterioration of the developing solution due to thermal history, natural oxidation, etc., the used solution W can be regenerated a certain number of times or a certain time. It may be replaced with a new solution at the time of performing. For example, it is possible to employ a method in which the number of substrates processed in the development processing apparatus 210 is counted and the substrate is replaced when a predetermined number of processes is reached.
In the present invention, even when the new liquid is used,
The concentration of the dissolved photoresist component is set within the above-mentioned fixed concentration range.

Furthermore, the used liquid used for the processing such as development may be supplied to the receiving tank 1 in a facility different from the semiconductor manufacturing facility 200. In this case, the alkaline processing liquid used in other equipment can be supplied to the development processing apparatus 210 of the semiconductor manufacturing equipment 200 and reused. Further, the alkaline processing liquid used therein can be used in the semiconductor manufacturing facility 200 or other facilities. The above alternative example can be similarly applied to the case where the functional film is processed as the organic film.

[0128]

EXAMPLES Hereinafter, specific examples according to the present invention will be described, but the present invention is not limited thereto.

Example 1 A new novolak / diazonaphthoquinone type positive resist (manufactured by Nagase Chemtex Co., Ltd.) was added to a new alkaline developer containing TMAH as an alkali (manufactured by Nagase Chemtex Co., Ltd .; NPD-18). NPR3510PG) was dissolved to obtain an alkaline working liquid of the present invention having a dissolved photoresist component concentration of 0.12% by mass and an alkaline component concentration of 2.376% by mass.

<Comparative Example 1> The new liquid (concentration of alkali component: 2.380% by mass) used in Example 1 was used as an alkaline working liquid.

<Photoresist Dissolution Characteristic Test> On the wafer on which the ITO thin film was formed, the same photoresist solution as that dissolved in the alkaline processing liquid in Example 1 was spin-coated to a film thickness of 1.5 μm. Then, a sample for development was prebaked at 100 ° C. for 2 minutes. This sample had an exposure wavelength of 436 nm and an exposure intensity of 20 mJ / c.
Exposure was carried out under the conditions of m ² and exposed / unexposed areas. The alkaline working liquids of Example 1 and Comparative Example 1 were supplied onto the post-exposure sample, and development was performed at a temperature of 23 ° C. Development is performed by DRM (Development Rate Monitor; PERKI).
It was carried out by using NELMER, model: MODEL E900) while monitoring the photoresist film thickness against the development time.

FIG. 3 is a graph showing changes in the photoresist film thickness of the unexposed portion with respect to the development time in the photoresist dissolution test. Curves C1 and C2 show the results when the alkaline working fluids of Example 1 and Comparative Example 1 were used, respectively. From this, in this test, the solubility of the alkaline working liquid of Example 1 to the photoresist in the unexposed portion (film reduction amount) was higher than that of Comparative Example 1 until the developing time was about 70 seconds. Was confirmed. Further, after that, it was observed that the solubilities of the alkaline working liquids of Example 1 and Comparative Example 1 were reversed. That is, it was found that Example 1 was excellent in solubility in the unexposed portion of the photoresist surface layer at the initial stage of development.

When the DRM analysis wavelength in the unexposed area during development was confirmed, the intensity change of the first wave was relatively remarkable when the alkaline processing liquid of Example 1 was used. Further, the average value of the residual film rate (ratio of the residual film thickness to the initial film thickness) for the two samples in the developing time of 60 seconds was 95.3% in the case of Example 1, whereas that of Comparative Example 1 was In the case, it was 96.2%. Also from these results, the alkaline working liquid of Example 1 is better than Comparative Example 1
It was found that the change in the film thickness of the photoresist surface layer in the unexposed area was faster than that of No.

Although the detailed mechanism of action is still unclear, the alkaline working liquid of Example 1 has a higher surfactant effect on the photoresist than the conventional product of Comparative Example 1. It is presumed that one of the reasons is that the “familiarity” with the photoresist surface layer is improved, which promotes dissolution of the surface layer. However, the operation is not limited to this.

Example 2 The same new alkaline developer (Nagase Chemtex Co., Ltd .; NPD-18) used in Example 1 was added to a novolak / diazonaphthoquinone positive resist (Nagase). Chemtex Co., Ltd .; NPR3510PG), and the dissolved photoresist component concentration is 0.005, 0.01, 0.05, 0.1,
It was dissolved so as to be 0.5, 1.0, 1.5 and 2.0% by mass to obtain various alkaline developers according to the present invention.

<Surface Tension Measurement Test 1> Alkali-based working liquid adjusted to various dissolved photoresist component concentrations in Example 2 and alkaline-based working liquid of Comparative Example 1 (dissolved photoresist component concentration 0%) The surface tension was measured 5 times using an automatic surface tension measuring device (manufactured by Kyowa Interface Science Co., Ltd .; CBVP-A3). The measurement results and average values are shown in Table 1. 4 and 5 are graphs showing changes in the surface tension (average value) with respect to the concentration of the dissolved photoresist component, in which the horizontal axis is displayed on a linear scale and a logarithmic scale, respectively.

[0137]

[Table 1]

From these results, it was confirmed that the surface tension was remarkably reduced when the dissolved photoresist component was added to the new solution at a concentration of 0.001% by mass or more. The improvement of wettability due to such a decrease in surface tension,
It is considered to be one of the factors that improve the “familiarity” with the photoresist surface layer in the unexposed area. Under this test condition where the concentration of the alkali component is about 2.38% by mass, the decrease in the surface tension becomes slower when the concentration of the dissolved photoresist component exceeds 0.1% by mass, and when the concentration exceeds several% by mass. It is predicted that the tendency will be saturated.

<Example 3> As an undiluted solution of an alkaline working solution, the same new alkaline developer solution as used in Example 1 (NPD-18 manufactured by Nagase Chemtex Co., Ltd.) was used. Novolac / diazonaphthoquinone type positive resist (Nagase Chemtex Co., Ltd .; NPR3)
510 PG) was dissolved to obtain an alkaline working liquid of the present invention having a dissolved photoresist component concentration of 0.005, 0.1 and 0.3% by mass and an alkaline component concentration of 0.4% by mass.

Comparative Example 2 An alkaline working liquid having an alkali component concentration of 0.4% by mass was obtained in the same manner as in Example 3 except that the positive resist was not dissolved.

<Surface Tension Measurement Test 2> Regarding the alkaline-type working liquid adjusted to various dissolved photoresist component concentrations in Example 3 and the alkaline-based working liquid of Comparative Example 2 (dissolved photoresist component concentration 0%) The surface tension was measured 5 times using an automatic surface tension measuring device (manufactured by Kyowa Interface Science Co., Ltd .; CBVP-A3). Table 2 shows the measurement results (only the average value). FIG. 6 is a graph showing changes in surface tension (average value) with respect to the concentration of dissolved photoresist components.

[0142]

[Table 2]

Under this test condition where the concentration of the alkali component is 0.4% by mass, the decrease in the surface tension becomes blunt from the concentration of the dissolved photoresist component of around 0.3% by mass, and the decreasing tendency tends to be saturated gradually. Expected to be.

[0144]

As described above, according to the alkaline processing liquid of the present invention, when it is used for processing such as development and molding of the organic film coated on the substrate, the amount used and the amount of waste liquid generated are reduced. It can be reduced and the solubility in the organic film after exposure is excellent, and the surface layer peeling of the organic film after processing can be sufficiently prevented. Further, according to the processing liquid adjusting method and apparatus and the processing liquid supply method and apparatus of the present invention, the alkaline processing liquid of the present invention thus excellent can be effectively adjusted, and the processing liquid of the present invention can be applied to the organic film. It becomes possible to effectively supply the alkaline processing liquid.

[Brief description of drawings]

FIG. 1 is a schematic diagram showing a configuration of a preferred embodiment of a developer supply device according to the present invention.

FIG. 2 is a flowchart showing an outline of a procedure of a preferred embodiment of a developing solution supply method according to the present invention.

FIG. 3 is a graph showing a change in photoresist film thickness of an unexposed portion with respect to a developing time in a photoresist dissolution test.

FIG. 4 is a graph showing changes in surface tension (average value) with respect to dissolved photoresist concentration.

FIG. 5 is a graph showing changes in surface tension (average value) with respect to dissolved photoresist concentration.

FIG. 6 is a graph showing changes in surface tension (average value) with respect to dissolved photoresist concentration.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 ... Receiving tank (reception part), 2 ... Filter (filtration part), 3 ... Residual photoresist removal device (remaining component removal part), 4 ... Metal ion removal device (metal component removal part), 5 ... Adjustment tank ( Adjusting part), 6 ... Leveling tank (leveling part), 7 ... Particle remover (particle removing part, post-treatment part), 8 ... Liquid supply system (adjusting part), 9 ... Control device (adjusting part), 20 ... pretreatment section, 51, 52 ... densitometer (concentration measurement section), 100 ... developing solution supply device (processing solution supply apparatus), 210 ... development processing apparatus (processing section), L2 ... pipe (feeding section), L7 ... Piping (non-permeated liquid transfer section), V1 to V4 ... Flow rate adjusting valve, W ... Used liquid, Ws ... Regeneration liquid.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Toshimoto Nakagawa             31 Tajiri-cho, Nakahara-ku, Kawasaki-shi, Kanagawa Stock             Company Hirama Rika Institute (72) Inventor Yuko Katagiri             31 Tajiri-cho, Nakahara-ku, Kawasaki-shi, Kanagawa Stock             Hirama Rika Research Laboratories (72) Inventor Osamu Ogawa             Nagase, 5-1, Kobunecho, Nihonbashi, Chuo-ku, Tokyo             Sangyo Co., Ltd. (72) Inventor Satoru Morita             Nagase, 5-1, Kobunecho, Nihonbashi, Chuo-ku, Tokyo             Sangyo Co., Ltd. (72) Inventor Makoto Kikukawa             1-19-20 Shin-Yokohama, Kohoku Ward, Yokohama City, Kanagawa Prefecture             Nhamada Building 1st floor             Kunology Co., Ltd. (72) Inventor Takahiro Takayama             236 Nakai, Tatsuno-cho, Tatsuno-shi, Hyogo Nagasechem             Inside Tex Co., Ltd. F-term (reference) 2H096 AA25 GA08 GA09 GA10                 5F046 LA12

Claims (25)

[Claims] 1. An alkaline processing liquid used for processing a photosensitive organic film coated on a substrate, which comprises an organic film of the same or different type as the organic film to be processed. An alkaline working fluid, characterized in that one component is dissolved at a concentration of 0.001 to 2.0 mass%. 2. When the organic film is a photoresist, as the first component, the second component constituting the organic film of the same kind or different kind as the photoresist to be developed as the processing is 0. The alkaline working liquid according to claim 1, wherein the alkaline working liquid is dissolved at a concentration of 0.001 to 2.0% by mass. 3. When the organic film is a functional film, the first component is 0.001 as a third component which constitutes an organic film of the same kind or different kind as the functional film to be processed.
The alkaline working liquid according to claim 1, wherein the alkaline working liquid is dissolved at a concentration of 0.5% by mass. 4. The alkali component is 0.05 to 2.5% by mass.
The alkaline working fluid according to claim 1, wherein the alkaline working fluid is contained at a concentration of. 5. The alkaline working liquid according to claim 2, wherein the alkaline component is contained at a concentration of 0.1 to 2.5 mass%. 6. The alkali component is 0.05 to 2.4% by mass.
The alkaline working fluid according to claim 3, wherein the alkaline working fluid is contained at a concentration of. 7. A processing liquid adjusting method for adjusting an alkaline processing liquid used in a processing step of processing an organic film coated on a substrate, wherein the organic processing liquid is contained in the alkaline processing liquid and is a processing target. The concentration of the first component constituting the same kind or different kind of organic film as the film is set to a value within the range of 0.001 to 2.0% by mass, and of the alkaline component contained in the alkaline processing liquid. A method for adjusting a working fluid, which comprises adjusting the liquidity of the alkaline working fluid so that the concentration is within a range of 0.05 to 2.5 mass%. 8. When the organic film is a photoresist, as the first component, an organic material that is the same as or different from the photoresist that is contained in the alkaline processing liquid and is a development target for the processing. The concentration of the second component constituting the film is set to a value within the range of 0.001 to 2.0% by mass, and the concentration of the alkaline component contained in the alkaline processing liquid is 0.1 to 2. 8. The working fluid adjusting method according to claim 7, wherein the liquidity of the alkaline working fluid is adjusted so that the value falls within the range of 5% by mass. 9. When the organic film is a functional film, an organic film which is contained in the alkaline processing liquid as the first component and is the same or different from the functional film to be processed is formed. The concentration of the third component is set to a value within the range of 0.001 to 0.5% by mass, and the concentration of the alkaline component contained in the alkaline working liquid is 0.05 to 2.4% by mass. The method for adjusting a working fluid according to claim 7, wherein the liquidity of the alkaline working fluid is adjusted so that the value falls within the range. 10. A processing liquid supply method for supplying an alkaline processing liquid to a processing step of an organic film coated on a substrate, wherein a first component constituting an organic film of the same kind or different kind as the organic film is provided. A receiving step of receiving the used liquid containing, a concentration measuring step of measuring the concentration of the first component and the alkaline component contained in the used liquid, based on the measured concentration of the first component and the alkaline component, The concentration of the first component contained in the used liquid is 0.0
To a value within the range of 01 to 2.0% by mass, and
The concentration of the alkaline component contained in the used liquid is 0.05 to
An adjusting step of adjusting the liquidity of the used liquid to obtain a regenerated liquid so that the value is within a range of 2.5% by mass; and a feeding process of feeding the regenerated liquid to the processing step. A method for supplying a working fluid, comprising: 11. When the organic film is a photoresist, in the receiving step, as the used liquid, an organic film that is the same as or different from the photoresist is formed.
Accepting those containing components, in the concentration measuring step, the concentrations of the second component and the alkaline component contained in the used liquid are measured, and in the adjusting step, the concentrations of the second component and the alkaline component are measured. Based on the measured value, the concentration of the second component contained in the used liquid is set to a value within the range of 0.001 to 2.0% by mass, and the alkaline component contained in the used liquid is A liquid regenerant is obtained by adjusting the liquidity of the used liquid so that the concentration becomes a value within the range of 0.1 to 2.5% by mass.
The working fluid supply method according to claim 10, wherein 12. When the organic film is a functional film, in the receiving step, as the used liquid, a liquid containing a third component constituting an organic film of the same kind or different kind as the functional film is received. In the concentration measuring step, the concentrations of the third component and the alkaline component contained in the used liquid are measured, and in the adjusting step, based on the actual measurement values of the third component and the alkaline component, The concentration of the third component contained in the used liquid is in the range of 0.001 to 0.5% by mass, and the concentration of the alkaline component contained in the used liquid is 0.05 to 11. The method for supplying a working liquid according to claim 10, wherein the regenerant liquid is obtained by adjusting the liquidity of the used liquid so that the value is within the range of 2.4% by mass. 13. A filtration step performed between the receiving step and the adjusting step for filtering the used liquid, a residual component removing step for removing a first component remaining in the used liquid, and 11. The working liquid supply method according to claim 10, further comprising a pretreatment process including at least one step of removing metal components contained in the used liquid. 14. In the filtration step, the used liquid is separated into a permeated liquid and a non-permeated liquid by cross-flow filtration, and the adjusting step adds a non-permeated liquid to the used liquid. 14. The working liquid supply method according to claim 13, further comprising a permeated liquid adding step. 15. The post-treatment process, which is carried out between the adjusting process and the feeding process and has a particle removing step for removing particle components from the regenerating liquid, according to claim 10. Working fluid supply method. 16. A processing liquid adjusting device for adjusting an alkaline processing liquid used for processing an organic film applied on a substrate, which is contained in the alkaline processing liquid and is of the same kind as the organic film. Alternatively, the concentration of the first component constituting the heterogeneous organic film is 0.00
The concentration of the alkaline component contained in the alkaline working liquid is set to be a value within the range of 1 to 2.0% by mass.
A working fluid adjusting device, comprising: an adjusting unit for adjusting the liquidity of the alkaline working fluid so that the value is within a range of 05 to 2.5 mass%. 17. When the organic film is a photoresist, the adjusting unit is the same as the photoresist that is contained in the alkaline processing liquid as the first component and is a development target for the processing. Or the concentration of the second component constituting the heterogeneous organic film is in the range of 0.001 to 2.0% by mass, and the concentration of the alkaline component contained in the alkaline working liquid is 0. The working fluid adjusting device according to claim 16, wherein the liquidity of the alkaline working fluid is adjusted so as to be a value within the range of 1 to 2.5% by mass. 18. When the organic film is a functional film, the adjusting unit is the same as or different from the functional film that is contained in the alkaline processing liquid as the first component and is a processing target. The concentration of the third component constituting the organic film is 0.00
The concentration of the alkaline component contained in the alkaline working liquid is 0. 1 so that the value falls within the range of 1 to 0.5% by mass.
The working fluid adjusting device according to claim 16, wherein the liquidity of the alkaline working fluid is adjusted so as to be a value within the range of 05 to 2.4 mass%. 19. A working liquid supply device for supplying an alkaline working liquid to a processed portion of an organic film coated on a substrate, the first liquid forming an organic film of the same kind or different kind as the organic film. A receiving part to which a used liquid containing a component (dissolved organic film component) is supplied, a concentration measuring part for measuring the concentrations of the first component and the alkaline component contained in the used liquid, the first component and the Based on the measured concentration of the alkaline component, the concentration of the first component contained in the used liquid was 0.0
To a value within the range of 01 to 2.0% by mass, and
The concentration of the alkaline component contained in the used liquid is 0.05 to
An adjusting unit that adjusts the liquidity of the used liquid to obtain a regenerated liquid so that the value is within a range of 2.5 mass%; and a feeding unit that feeds the regenerated liquid to the processing unit. A machining fluid supply device comprising: 20. When the organic film is a photoresist, the receiving portion is supplied with the used liquid containing a second component that forms an organic film of the same kind as or different from the photoresist. The concentration measuring unit measures the concentration of the second component and the alkaline component contained in the used liquid, and the adjusting unit measures the concentration of the second component and the alkaline component. Based on the value, the concentration of the second component contained in the used liquid becomes a value within the range of 0.001 to 2.0% by mass, and the concentration of the alkaline component contained in the used liquid. Of 0.1 to 2.5% by mass,
20. The working fluid supply device according to claim 19, wherein the fluidity of the used fluid is adjusted. 21. When the organic film is a functional film, the receiving part is supplied with the used liquid containing a third component that constitutes an organic film of the same kind as or different from the functional film. The concentration measuring unit measures the concentration of the third component and the alkaline component contained in the used liquid, and the adjusting unit measures the concentration of the third component and the alkaline component. Based on the value, the concentration of the third component contained in the used liquid becomes a value within the range of 0.001 to 0.5% by mass, and the concentration of the alkaline component contained in the used liquid. 20. The working liquid supply apparatus according to claim 19, wherein the liquid property of the used liquid is adjusted so that the value becomes within a range of 0.05 to 2.4% by mass. 22. A filtering unit provided between the receiving unit and the adjusting unit for filtering the used liquid, and a residual component removing unit for removing the first component remaining in the used liquid. 20. The processing liquid supply apparatus according to claim 19, further comprising: a pretreatment unit having at least one of a metal component removal unit that removes a metal component contained in the used liquid. 23. The filtration unit filters the used liquid into a permeated liquid and a non-permeated liquid by cross-flow filtration, and is connected to the filtration unit and the adjustment unit, and 20. The working liquid supply apparatus according to claim 19, further comprising a non-permeated liquid transfer unit that transfers the non-permeated liquid from the filtration unit to the adjustment unit. 24. A post-treatment unit is provided between the adjusting unit and the feeding unit, the post-treatment unit having a particle removing unit for removing a particle component contained in the regenerant liquid. 19. The working fluid supply device according to item 19. 25. The regenerant is connected to the adjuster, and the regenerant is naturally transferred from the adjuster by a head pressure difference, and the concentrations of the first component and the alkaline component contained in the regenerant are leveled. 20. The machining fluid supply device according to claim 19, further comprising a leveling unit.