JP4736124B2 - Development device - Google Patents

Description

  The present invention relates to a method for measuring the amount of a surfactant, a method for measuring the amount of an alkali component, and a developing device that are useful for the entire development process related to the field of photolithoelectronics, particularly for the development patterning process in color filter production.

  A color filter used in a liquid crystal display or the like is an optical element having a fine red, green, blue pattern or the like. And the manufacture consists of processes, such as apply | coating a photosensitive resist to transparent substrates, such as glass, exposure, and image development, The same process is repeated about each color. Conventional techniques and problems will be described below from the viewpoint of the color filter developing process.

  The development process is a process in which the photosensitive resist coating resist is exposed to ultraviolet rays using an original mask, and a desired pattern is cured, and then the uncured resist is dissolved and removed. It is a process. The problem is how to transfer a desired pattern accurately.

  Many developers are composed of inorganic and / or organic alkali components. This is because the uncured resist is dissolved and removed by reacting with a functional group having a polymer acid value contained in the resist.

  In addition to the alkali component, a small amount of a surfactant is often added. This has the effect of improving the development speed by improving the permeability to the applied resist film and further improving the pattern shape after development.

  As a method for using the developer, there are a new solution supply method in which the used developer is passed to the waste solution and a developer circulation method in which the used developer is circulated many times.

  The always-new liquid supply method always uses a clean liquid whose concentration is sufficiently controlled in the preparation tank, so there is no deviation of the developer components and the process management is easy. Further, since there is no contamination of the liquid, there is no quality defect caused by developer contamination.

  However, since the new liquid is continuously supplied, there are disadvantages that the amount of liquid used is large and the running cost is high. In recent years, when the size of the substrate is increased, the size of the apparatus is also increased. In recent years, it is required to reduce the running cost.

  On the other hand, in the developer circulation method, since the used solution is circulated many times, the running cost can be kept low.

  However, in order to circulate and use the developer, the dissolved resist component also circulates. As a result, the degree of contamination of the liquid increases, which causes a product defect.

  Further, more importantly, the liquid component deteriorates when used in a circulating manner. This affects the developing speed and makes process management difficult.

  Year after year, the color filter production line is getting larger. In this background, the increase in the size of the display accompanying market demand is involved, which causes a great load on each process of the photolitholine. The development process is no exception.

  In order to keep the running cost low in the development process, it is necessary to adopt a developer circulation system. However, as described above, problems such as liquid contamination and influence on quality due to component fluctuations occur.

  As a means for avoiding liquid contamination while adopting a developer circulation system, a developing device having an ultrafiltration filter has been proposed in the past (Patent Document 1). According to the present invention, the degree of contamination can be kept low while adopting a circulation system.

  However, as long as the circulation system is adopted, deterioration of the developer component cannot be avoided. The fluctuation of the developer component has a greater influence on the quality than the liquid contamination, and therefore, the concentration management and adjustment of the developer is a big problem in the circulation system.

  In order to control and adjust the concentration of the developer, it is naturally necessary to measure the component concentration. However, until now, techniques relating to the measurement of developer components have not been fully studied.

  Measurement of the amount of alkali and the amount of surfactant itself already exists as a known technique. However, it is not easy to measure components in a state where the developer circulation system is employed and the resist is dissolved in the developer.

  The factor that is difficult to measure is that the alkali component in the developer and the surfactant are adsorbed to the dissolved resist, and the adsorbed component substantially loses its original effect.

  Therefore, when the developer component in which the resist is dissolved is measured by a known technique, the component that has lost its effect is quantitatively measured.

When density control is performed in the development process, a technique for measuring only active components that have not lost their effect is required.
International Publication WO2005 / 040930 Pamphlet

  It is an object of the present invention to propose a method for quantitatively measuring only a component that has not lost its effect, that is, a living component, in a developing solution in which a resist is dissolved, on the premise of adopting a developer circulation method. To do.

The invention described in claim 1 includes a developing tank, a developing tank that collects the developing solution from the developing tank via a developing processing solution return path, and a developing solution circulation path that supplies the developing solution from the developing tank to the developing tank. A developing device comprising:
The developer contains a surfactant;
Some of the developer containing the surfactant, the filtered through a developer circulation path out of the ultrafiltration filter, a mechanism for quantitative measurement of the amount of surfactant by complexometric titration by using the resulting filtrate A developing device characterized in that.
The invention described in claim 2 is a developing tank, a developing tank that collects the developing solution from the developing tank through a developing solution return path, and a developing solution circulation path that supplies the developing solution from the developing tank to the developing tank. A developing device comprising:
The developer contains an inorganic and / or organic alkali component,
Part of the developer containing the inorganic and / or organic alkali components is filtered through an ultrafiltration filter outside the developer circulation path, and the amount of alkali components is quantitatively measured by acid-base titration using the obtained filtrate. A developing device including a mechanism for performing the above operation.
The invention according to claim 3 is the developing device according to claim 1 or 2, wherein the molecular weight cutoff of the ultrafiltration filter is in the range of 300,000 or less.
The invention according to claim 4 is the developing device according to claim 3, wherein the molecular weight cut-off of the ultrafiltration filter is in the range of the molecular weight cut-off from 50000 to 150,000.
The invention according to claim 5 further comprises means for adjusting the surfactant amount of the developer to a desired concentration after measuring the surfactant amount. is there.
The invention according to claim 6 is the developing device according to claim 2, further comprising means for adjusting the alkali component amount of the developer to a desired concentration after measuring the alkali component amount.

Since this invention is the above structure, there exist the following effects.
That is, according to the invention according to claim 1, after the developer containing the surfactant is filtered through the ultrafiltration filter, the amount of the surfactant is quantitatively measured using the filtrate, and is adsorbed to the resist. Except for the surfactant, only the amount of the active surfactant can be quantitatively measured. Alkali components and surfactants adsorbed on the resist in the developer are present in the solution as micelles that are much larger than the original single particle size. Therefore, by measuring the surfactant after filtering the micelle body with an ultrafiltration filter, only the single component that is not adsorbed on the resist, that is, the active surfactant that has not lost its function, is quantitatively measured. Can do.

  According to the invention of claim 2, after the developer containing an inorganic and / or organic alkali component is filtered through an ultrafiltration filter, the amount of the alkali component is quantitatively measured using the filtrate. Only the active alkali component can be quantitatively measured except for the alkali component adsorbed on the surface.

  According to the inventions according to claims 3 and 4, the molecular weight cut-off of the ultrafiltration filter according to claims 1 and 2 is 300,000 or less, preferably within the range of the cut-off molecular weight of 50000-150000. The amount of the surfactant and the amount of the alkali component can be measured under appropriate conditions without passing through the developer component that has lost its effect and without trapping the active component.

  Further, according to the invention of claim 5, after measuring the amount of the surfactant by the method of claim 1, the amount of the surfactant is adjusted by adjusting the amount of the surfactant in the developer to a desired concentration. Stable quality control can be performed while suppressing fluctuations and reducing running costs.

  Further, according to the invention according to claim 6, after the alkali component amount is measured by the method according to claim 2, the alkali component amount of the developer is adjusted to a desired concentration, thereby stabilizing the running cost. Quality control.

  Hereinafter, a method for measuring the amount of surfactant and the amount of alkali component in the developer according to the present invention will be described based on the embodiments thereof.

  FIG. 1 is a graph showing variations in the amount of surfactant with respect to the degree of contamination of the developer. Reference numeral 1 is a result of measuring the amount of surfactant by a conventional method. On the other hand, reference numeral 2 is a result of measuring the amount of the surfactant by the method shown in the present invention.

  As shown in FIG. 1, when the amount of the surfactant is measured by the conventional method of reference number 1, the amount of developer contamination, that is, the amount of dissolved resist is measured because the amount consumed is lost. However, the amount of the surfactant does not change at all.

  On the other hand, when the amount of the surfactant is measured with the solution after ultrafiltration shown in the present invention of reference numeral 2, the surfactant that has lost its activity by being adsorbed on the resist is trapped, and only the amount of the active surfactant is trapped. Therefore, the amount of surfactant decreases with the amount of dissolved resist.

  Reference numeral 3 indicates a fluctuating region of the surfactant amount that can be developed. As a result of measuring the active surfactant amount proposed in the present invention, the lower limit is exceeded in a certain resist dissolution amount. The conventional method cannot manage points exceeding the lower limit.

  FIG. 2 is a graph showing variations in the amount of alkali components with respect to the degree of contamination of the developer. Reference numeral 4 indicates the result of measuring the amount of alkali components by a conventional method. On the other hand, reference numeral 5 is the result of measuring the amount of alkali components by the method shown in the present invention.

  As shown in the figure, when the amount of alkali component is measured by the conventional method of reference number 4, the amount of alkali component adsorbed on the resist and lost activity is measured. Although it decreases with an increase in the amount of dissolution, it cannot be said that an accurate amount of alkali components is being measured.

  On the other hand, when the amount of alkali component is measured with the solution after ultrafiltration indicated by the present invention of reference number 5, the alkali component that has lost its activity by adsorbing to the resist is trapped, and only the amount of active alkali component is measured. Therefore, an accurate decline curve can be obtained.

  Reference numeral 6 shows a fluctuating region of the developable alkali component amount. As a result of measuring the active alkali component amount proposed in the present invention, the lower limit is exceeded in a certain resist dissolution amount. In the conventional method, the lowering curve is slow, so that the lower limit is not exceeded, and sufficient process control cannot be performed.

  FIG. 3 shows an example of a developer ultrafiltration method. A developer 8 is introduced into the sealed container 7. Reference numeral 9 denotes an ultrafiltration membrane, which is a flat membrane here. The developer 8 is pressurized by compressed air inserted from the reference numeral 10, passes through the ultrafiltration membrane 9, and a filtrate is obtained from the outlet 11.

  In the embodiment shown in FIG. 3, the filtrate can be collected very easily, which is effective in measuring the amount of active surfactant or alkali component in the developer in which the resist is dissolved at the experimental level.

  FIG. 4 is a schematic diagram of the developing device when the present invention is actually developed in the developing device to manage the developer component. Reference numeral 15 denotes a developing tank. The developing solution is supplied to the developing solution circulation path 17, the developing solution discharge port 12, and the developing tank 13 by the pump 16, and is constantly circulated through the developing solution return path 14.

  Reference numeral 21 denotes an ultrafiltration filter. The developer in the developing tank 15 is sent to the ultrafiltration filter 21 by the pump 20, and the obtained filtrate is sent to the measuring device 23 through the path 22 to quantify its concentration. taking measurement.

  There are various measuring methods such as a liquid chromatograph, a light irradiation method, and a titration method, but there is no particular limitation. Desirably, a titration method is preferably employed. This is because the method for determining the neutralization point by titration can be quantitatively measured with relatively high accuracy in both the alkali amount measurement and the surfactant amount measurement.

  Reference numeral 24 in the figure is a path for dropping an alkali component, or a surfactant, or a mixture thereof, and is used to adjust the amount of the alkali component or the surfactant to a desired concentration based on the result measured by the measuring instrument 23. belongs to. If the filtrate is subjected to component adjustment and returned to the developing tank 15, it can also function as a developer regeneration.

  However, the present invention does not focus on developing solution regeneration by adjusting the concentration of the alkali component or surfactant. The measurement result may be handled as a history of process management items in the production process, or may be performed when measuring a solution in which a resist is dissolved at an experimental level.

  The invention is further illustrated by the following examples. FIG. 4 described above is an actual development of the present invention, which is a developing device equipped with an automatic developer component measuring device and capable of adjusting the developer concentration from the measurement result.

  A constant amount of new developer is always supplied to the developing tank 15 through the path 18, and an amount substantially equal to the supplied amount is periodically drained through the path 19. In this experiment, a solution in which an alkali salt and a surfactant are dissolved is used as a developer, and a new solution is supplied at 2 L / min to obtain a 2 L / min drain.

  As the ultrafiltration filter 21, a cross-flow type made of polyethersulfone having a molecular weight cut off of 150,000 was selected and used. Therefore, although not shown in the figure, the liquid sent to the ultrafiltration filter is sampled as a one-part filtrate, and the rest is returned to the developing tank 15.

  The filtrate was adjusted to be sent from the pump 20 so as to be about 1% of the circulating fluid amount. Although not shown in the figure, the ultrafiltration filter is easily clogged, and therefore, once every 15 minutes, a process of allowing the filtrate to flow back through the ultrafiltration filter, generally called a reverse cleaning, is performed. did.

  The filtrate was periodically sampled and measured, and the amount of alkali and surfactant mixed solution dropped onto the developing tank 15 through the path 24 was adjusted. The concentration can be adjusted based on either the surfactant or the alkali component, but here the concentration was adjusted based on the alkali component.

  For the concentration measurement, a titration method was employed, an alkali amount was acid-base titration, and a surfactant amount was complex titration using a complex as a titrant.

  According to the present invention, the amount of surfactant and the amount of alkali component in the developer in a state where the resist is dissolved can be measured, which is extremely useful for the developer circulation method.

6 is a graph showing fluctuations in the amount of a surfactant with respect to the degree of contamination of a developer. 6 is a graph showing fluctuations in the amount of alkali components with respect to the degree of contamination of a developer. It is a figure for demonstrating one example of the ultrafiltration method. 1 is a schematic view of a developing device of the present invention.

Explanation of symbols

  7 ... Sealed container, 8 ... Developer, 9 ... Ultrafiltration membrane, 12 ... Developer discharge port, 13 ... Developer tank, 14 ... Developer return path, 15 ... Developer tank, 16 …… Developer circulation pump, 17 …… Developer circulation path, 20 …… Ultrafiltration filter feed pump, 21 …… Ultrafiltration filter, 22 …… Measurement filtrate sampling path, 23 Developer component measurement device, 24: Concentration correction droplet lower path.

Claims (6)

A developing device comprising: a developing tank; a developing tank that collects the developing solution from the developing tank through a developing solution return path; and a developing solution circulation path that supplies the developing solution from the developing tank to the developing tank.
The developer contains a surfactant;
Some of the developer containing the surfactant, the filtered through a developer circulation path out of the ultrafiltration filter, a mechanism for quantitative measurement of the amount of surfactant by complexometric titration by using the resulting filtrate A developing device . A developing device comprising: a developing tank; a developing tank that collects the developing solution from the developing tank through a developing solution return path; and a developing solution circulation path that supplies the developing solution from the developing tank to the developing tank.
The developer contains an inorganic and / or organic alkali component,
Some of the developer containing the inorganic and / or organic alkaline component, the filtered through a developer circulation path out of the ultrafiltration filter, quantitative measurement alkali component content by acid-base titration with the resulting filtrate developing apparatus is characterized in that it comprises a mechanism for. The developing device according to claim 1 or 2, wherein the ultrafiltration filter has a molecular weight cutoff of 300,000 or less. The developing device according to claim 3, wherein the ultrafiltration filter has a molecular weight cut-off in the range of 50000 to 150,000. After measuring the interfacial active agent amount, a developing device according to claim 1, further comprising means for adjusting the amount of surfactant in the developing solution to a desired concentration. After measuring the A alkali component amounts, the developing device according to claim 2, further comprising means for adjusting the alkali component of the developing solution to a desired concentration.

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