Apparatus for controlling a developing solution

Abstract: The developing solution is used in developing photosensitive organic resin (photoresist) in a liquid crystal board manufacturing process, printed circuit board manufacturing process or the like. The apparatus comprises means, such as an absorption photometer (16), for detecting the dissolved resin concentration in the developing solution and means, such as an electric conductivity meter (15), for detecting the alkali concentration of the developing solution. Means (3, 18, 21, 22, 24, 25, 26, 28) respond to the two detection means (15, 16) by replenishing the developing solution with undiluted developing solution and/or pure water to produce a desired dissolved resin concentration and a desired alkali concentration. Thus, the developing performance of the developing solution may be kept constant. Down time is save by removing the need to stop the manufacturing process to completely change the developing solution.

Description: The invention relates to apparatus for controlling an alkaline developing solution used in developing photo-sensitive organic resin (photoresist), hereinafter called "resin", in a liquid crystal board manufacturing process, a printed circuit board manufacturing process or the like. In a liquid crystal board manufacturing process or a printed circuit board manufacturing process, an alkaline aqueous solution, such as tetramethyl ammonium hydroxide (TMAH) aqueous solution (for example, 2.380 wt.%) and potassium hydroxide aqueous solution, is used as a developing solution for resin in a spray method or a dip method. In the conventional method, a development processing tank is filled with the specified volume of a fresh developing solution at the specified concentration. The developing solution is consumed and, when it reaches a specified deteriorated concentration, as established by an empirical index such as the number of boards processed, the whole volume is exchanged with a prepared fresh solution as part of the batch operation process. The solution exchanging frequency varies with the type of boards, but it is generally done about once in every six hours. The alkali concentration of the developing solution gradually reduces in the course of use due to reaction with acid in the resin, and absorption and reaction of carbon dioxide and oxygen gas in the air. The amount of resin dissolved in the developing solution gradually increases. For a positive resist, the dissolved resin slightly dissolves the resin in the unexposed area that should not be dissolved, and the residual film thickness of the unexposed part is gradually reduced. Therefore, the alkali concentration and the dissolved resin concentration vary with the passing of time and are not constant, and hence it is difficult to achieve the required dimensional precision when developing the boards. The product quality is unstable, and the yield is reduced. Besides, because time is spent replacing the developing solution, the operation rate is significantly reduced, and the work involved in replacing the developing solution increases the labour cost. Moreover, since the developing solution is adjusted to have a specified concentration and a specified quality, and is shipped in an enclosed container free from contamination by foreign matter, the transportation cost is enormous. Also, compared with undiluted developing solution, the material cost is much higher. US-A-4857750 discloses apparatus which uses an optical sensor to measure the dissolved resin concentration. If the concentration is too high, fresh developing solution is added from a tank. JP-A-60166950 discloses apparatus which uses a sensor to measure the conductivity of the developing solution. If the conductivity is too high, a weak developing solution is added from a source so as to lower the conductivity of the existing developing solution. JP-A-63100460 discloses mixing concentrated developing solution with water and then spraying the resulting diluted developing solution into the main developing tank. According to a first aspect of the present invention, there is provided apparatus for controlling a solution used for developing photosensitive organic resin, comprising: developing solution discharge means for discharging developing solution in response to the dissolved resin concentration detected in the developing solution by dissolved resin concentration detection means; first replenishing means for replenishing the developing solution from a source of undiluted developing solution and a source of pure water in response to the liquid level of the developing solution detected by a liquid level gauge; and second replenishing means for replenishing the developing solution from a source of undiluted developing solution and/or a source of pure water in response to the alkali concentration of the developing solution detected by alkali concentration detection means. According to a second aspect of the present invention, there is provided apparatus for controlling a solution used for developing photosensitive organic resin, comprising: developing solution discharge means for discharging developing solution in response to the dissolved resin concentration detected in the developing solution by dissolved resin concentration detection means; first replenishing means for replenishing the developing solution from a source of diluted developing solution in response to the liquid level of the developing solution detected by a liquid level gauge; and second replenishing means for replenishing the developing solution from a source of undiluted developing solution and/or a source of pure water in response to the alkali concentration of the developing solution detected by alkali concentration detection means. According to a third aspect of the present invention, there is provided apparatus for controlling a solution used for developing photosensitive organic resin, comprising: first replenishing means for replenishing the developing solution from a source of undiluted developing solution and a source of pure water in response to the dissolved resin concentration detected in the developing solution by dissolved resin concentration detection means; and second replenishing means for replenishing the developing solution from a source of undiluted developing solution and/or a source of pure water in response to the alkali concentration of the developing solution detected by alkali concentration detection means. According to a fourth aspect of the present invention, there is provided apparatus for controlling a solution used for developing photosensitive organic resin, comprising: first replenishing means for replenishing the developing solution from a source of diluted developing solution in response to the dissolved resin concentration detected in the developing solution by dissolved resin concentration detection means; and second replenishing means for replenishing the developing solution from a source of undiluted developing solution and/or a source of pure water in response to the alkali concentration of the developing solution detected by alkali concentration detection means. The present invention enables the developing performance of the developing solution to be kept constant, while still enabling the use of the convenient line conveying system of the prior art that is suited to mass production of liquid crystal boards, printed circuit boards or the like. The present invention permits automatic control of the developing solution to achieve a specified alkali concentration and a specified dissolved resin concentration by selectively adding undiluted developing solution and/or pure water to the developing solution. Thus, the replenishment of the developing solution in a development processing tank may be controlled so as to always keep constant the quality of the developing solution, whilst shortening the operation down time and reducing the manufacturing cost. It is possible to adjust and control the resin concentration by measuring the absorbance of the developing solution because experiments have confirmed that the concentration of the resin dissolved in the developing solution is closely related to the absorbance. It is also possible to adjust and control the alkali concentration by measuring the electric conductivity of the developing solution because experiments have confirmed that the alkali concentration in the developing solution is closely related to the electric conductivity. Examples of the undiluted developing solution include, among others, an inorganic alkaline aqueous solution composed of a single inorganic alkali such as potassium hydroxide, sodium hydroxide, sodium phosphate and sodium silicate or a mixture thereof, and an organic alkaline aqueous solution such as tetramethyl ammonium hydroxide (TMAH) and trimethyl monoethanol ammonium hydroxide (choline). The invention will now be described by way of non-limiting embodiments, with reference to the accompanying drawings, in which:- Fig. 1 is a schematic diagram of a first embodiment of apparatus for controlling a developing solution in accordance with the invention; Fig. 2 is a schematic diagram of a second embodiment of apparatus for controlling a developing solution in accordance with the invention; Fig. 3 is a schematic diagram of a third embodiment of apparatus for controlling a developing solution in accordance with the invention; Fig. 4 is a schematic diagram of a fourth embodiment of apparatus for controlling a developing solution in accordance with the invention; Fig. 5 is a graph showing a typical relationship between the alkali concentration and the line width of the resin after development; Fig. 6 is a graph showing a typical relationship between the electric conductivity and the alkali concentration; Fig. 7 is a graph showing a typical relationship between the dissolved resin concentration and the residual film thickness of unexposed resin; Fig. 8 is a graph showing a typical relationship between the absorbance of the developing solution and the dissolved resin concentration; Fig. 9 is a graph showing a typical relationship between the alkali concentration and time, when using apparatus in accordance with the invention; Fig. 10 is a graph showing a typical relationship between the alkali concentration and time, when using the conventional method; Fig. 11 is a graph showing a typical relationship between the dissolved resin concentration and time, when using apparatus in accordance with the invention; and Fig. 12 is a graph showing a typical relationship between the dissolved resin concentration and time, when using the conventional method. Fig. 1 is a schematic diagram of an apparatus showing an embodiment of the invention. In the diagram, reference numbers 1 to 13 correspond to the units for composing the conventional development processing apparatus. That is, the conventional development processing apparatus comprises a development processing tank 1 for storing the developing solution, an overflow tank 2, a liquid level gauge 3, a development compartment hood 4, a developing solution spray 7, a liquid feed pump 8 for feeding the solution to the developing solution spray, a filter 9 for removing fine particles from the developing solution, roller conveyors 5 for moving boards 6, a circulation pump 11 for clarifying and agitating developing solution, a filter 13 for removing fine particles, and pipings for N 2 , pure water, etc. In the first embodiment, the devices attached to the conventional apparatus include an electric conductivity meter 15, absorption photometer 16, liquid discharge pump 18, undiluted developing solution feed tank 19, flow rate regulating valve 21 for feeding undiluted developing solution, flow rate regulating valve 22 for feeding pure water, piping for connecting these devices, electric instrumentation or pneumatic instrumentation. The liquid volume stored in the development processing tank 1 is sufficient to feed the developing solution spray 7, but it must be controlled for the stability of the process. The liquid level gauge 3 detects liquid level drop due to spontaneous decrease as the solution adheres on the board and is brought outside during development process, or detects liquid level drop when the solution deteriorating in development performance is discharged, and controls the liquid volume in the development processing tank 1 in a specific range. Here, the old solution is passed into the drain piping by operating the discharge pump 18. Or the old solution may be directly discharged out of the system without passing through the drain piping. The feed tank 19 of undiluted developing solution (e.g. 15 to 20 wt.% aqueous solution of TMAH, concentrated aqueous solution of KOH) is pressurized to, for example, 1 to 2 kgf/cm 2 by N 2 gas from the piping 20, and the solution is fed under pressure as the undiluted developing solution flow rate regulating valve 21 opens. The pure water is supplied from a branch piping from the existing piping, and is fed as the pure water flow regulating valve 22 opens. The undiluted developing solution and pure water are fed as the individual valves are regulated automatically, and are joined at the duct 23 and led to the duct 12, thereby to enter into the development processing tank 1 and be mixed with the circulating flow. It is also possible to supply the undiluted developing solution and pure water directly into the duct 12 or development processing tank 1 without joining on the way. It is, however, desired to join the undiluted developing solution and pure water at the duct 23 and then lead to the circulating duct 12 because they are mixed sufficiently. A sample solution is fed from the duct 14 into the electric conductivity meter 15 and the absorption photometer 16 (for example, the two instruments are combined in one body) installed online in the duct 10 for the developing solution spray, and the electric conductivity and the absorbance are measured continuously, and the measured solution is returned to the duct 10 through the duct 17. It is also possible to install the electric conductivity meter 15 and the absorption photometer 16 separately. Fig. 2 is a schematic diagram of the second embodiment of the invention. In the second embodiment, fresh (already diluted) developing solution is stored in a feed tank 27 and its flow is controlled by a fresh solution flow rate regulating valve 28 in response to the liquid level of the developing solution detected by the liquid level gauge 3. The rest of the construction is the same as in Fig. 1. Fig. 3 is a schematic diagram of an apparatus showing a different embodiment of the invention. The embodiment is composed so as to detect the dissolved resin concentration in the developing solution for resin by the absorption photometer 16, and to replenish the developing solution with undiluted developing solution and pure water. As shown in Fig. 3, usually the liquid level is near the overflow weir. When undiluted developing solution or pure water is added, the old developing solution overflows the overflow weir, and is discharged automatically. The discharge pump 18 is not necessarily required, and a valve may be disposed in place of the discharge pump 18. The other construction is the same as in Fig. 1. Fig. 4 is a schematic diagram of an apparatus showing a further different embodiment of the invention. The embodiment is designed to use a fresh developing solution already blended from the undiluted developing solution and pure water, instead of separate supplies of the undiluted developing solution and pure water. The fresh developing solution is stored in a feed tank 27 and its flow is controlled by a regulating valve 28 in response to the dissolved resin concentration in the developing solution as detected by the absorption photometer 16. The rest of the construction is the same as in Fig. 3. The control system of the apparatus in the embodiment in Fig. 1 will now be explained. The liquid level gauge 3 and the liquid level in the development processing tank 1, the electric conductivity meter 15 and the alkali concentration of developing solution, and the absorption photometer 16 and the dissolved resin concentration in developing solution are mutually independent functions in nature, but it is characteristic of this embodiment to consider them together. Besides, in the first place, the target value of alkali concentration of the developing solution and the deterioration limit value of the dissolved resin concentration necessary for quality control of product boards must be preset in the controllers on the basis of experience or calculation. The alkali concentration of the developing solution declines due to reaction with board resin, or absorption or reaction of carbon dioxide and oxygen gas in air. As the alkali concentration declines, the line width after development of the board resin increases and differs from the initial design value, which results in poor dimensional precision (see Fig. 5). Therefore, the alkali concentration of the developing solution must be controlled at a specified target value, for example, 2.38 (±0.02) wt. % in the case of TMAH. The present inventors experimentally studied the relation between the alkali concentration of developing solution and the electric conductivity, and learned that the alkali concentration was predominant over the electric conductivity near the concentration of use as shown in Fig. 6 so that it could be measured with an advanced linear function. The electric conductivity meter 15 installed online in the duct 10 has compensating functions to minimize the measuring error and a conductivity controller 25. The conductivity measurement of the sample solution led in from the duct 10 is fed into the conductivity controller 25, and the undiluted developing solution or pure water is automatically controlled by the flow rate regulating valves 21, 22 by the output signal so as to coincide with the target value, and replenished until the alkali concentration is adjusted to the target value. Deterioration of developing performance is also related with the dissolved resin concentration, aside from the alkali concentration. The developing solution used to process the board is taken out from the development processing tank 1 by the liquid feed pump 8, and is circulated through the developing solution spray 7, and therefore the dissolved resin is gradually concentrated in the developing solution. As a result, as shown in Fig. 7, the residual film rate (i.e. thickness) in the unexposed area drops and the developing performance deteriorates significantly. The present inventors studied the relation between the absorbance and the resin contamination state of the developing solution, and obtained the result as shown in Fig. 8 by experiment. As shown in Fig. 8, the dissolved resin concentration and the absorbance are in an advanced linear relation regardless of the alkali concentration, and it is possible to judge the limit of the developing performance by the dissolved resin concentration itself regardless of the number of boards processed. Meanwhile, since the developing solution becomes red due to dissolved resin, the measuring wavelength was 480 nm. Therefore, the absorption photometer 16 installed in the duct 10 in one body with or separately from the electric conductivity meter 15 continuously measures the dissolved resin concentration in the developing solution and, when the value exceeding the deterioration limit is detected, the discharge pump 18 is put in operation by the output signal from the absorbance controller 26, and the deteriorating developing solution is drawn out from the development processing tank 1, and is discharged into the drain pipe, or directly discarded out of the system. As a result, in the development processing tank 1 lowered in level, the liquid level gauge 3 immediately detects the lowered liquid level, and a fresh developing solution is replenished, and the dissolved resin concentration is diluted to the deterioration limit value, so that the developing performance is recovered, and the discharge pump 18 stops. Here is explained the functioning of the control system of the apparatus of the embodiment in Fig. 1. When the development processing tank 1 is empty and building up a solution, the liquid level gauge 3 detects the liquid level, and by the output signal from the liquid level controller 24, the undiluted developing solution and pure water are supplied, at a proper flow rate ratio, by regulating the valve opening degree by means of flow rate regulating valves 21, 22. In succession, the electric conductivity meter 15 continuously measures the electric conductivity of the built-up developing solution, and by the output signal from the conductivity controller 25, the undiluted developing solution or pure water is supplied, at a proper small flow rate, by regulating the valve opening degree by the flow rate regulating valve 21 or 22 so as to be controlled automatically to achieve the alkali concentration of the target value. When the next development processing is started, lowering of alkali concentration, drop of liquid level due to carry-over by boards, and enrichment of dissolved resin occur. When the alkali concentration is lowered, the electric conductivity of the developing solution is continuously measured by the electric conductivity meter 15, and by the output signal of the conductivity controller 25, the undiluted developing solution is supplied at a proper small flow rate by regulating the valve opening degree by the flow rate regulating valve 21 so as to be controlled automatically to maintain the alkali concentration of the target value. When the level of the solution drops because of carry-over by the boards, the liquid level gauge 3 detects the lowered liquid level, and by the output signal of the liquid level controller 24, the undiluted developing solution and pure water are supplied at a proper flow rate ratio by regulating the valve opening degree by means of the flow rate regulating valves 21, 22. When the dissolved resin is concentrated to reach the deterioration limit, the absorption photometer 16 detects the value exceeding the deterioration limit by continuously measuring the dissolved resin concentration of the developing solution, and by the output signal of the absorbance controller 26, the discharge pump 18 is put in action, and the deteriorating developing solution is drawn out from the development processing tank 1, and discarded into the drain pipe, or discarded directly out of the system. As a result, the liquid level drops, and the liquid level gauge 3 detects the lowered liquid level, and by the output signal of the liquid level controller 24, the undiluted developing solution and pure water are supplied at a proper flow rate ratio by regulating the valve opening degree by the flow rate regulating valves 21, 22. Since a fresh developing solution is replenished, the developing performance is recovered as the dissolved resin concentration is diluted to the deterioration limit, and the discharge pump 18 stops. Above the liquid level gauge 3, an overflow weir is disposed at a position not allowing to overflow usually, but a slight overflow does not matter. Next is explained the functioning of the control system of the apparatus of the embodiment shown in Fig. 3. When the development processing tank 1 is empty and building up a solution, by manual operation, the undiluted developing solution and pure water are supplied at a proper flow rate ratio by regulating the valve opening degree by the flow rate regulating valves 21, 22. The electric conductivity meter 15 continuously measures the electric conductivity of the built-up developing solution, and by the output signal of the conductivity controller 25, the undiluted developing solution or pure water is supplied at a proper small flow rate by regulating the valve opening degree by the flow rate regulating valve 21 or 22 so as to be controlled automatically to reach the target of alkali concentration. When next development process begins, lowering of alkali concentration, drop of liquid level due to carry-out by boards, and enrichment of dissolved resin occur. In the case of lowering of alkali concentration, the electric conductivity meter 15 continuously measures the electric conductivity of the developing solution, and by the output signal of the conductivity controller 25, the undiluted developing solution is supplied at a proper small flow rate by regulating the valve opening degree by the flow rate regulating valve 21 so as to be controlled automatically to reach the target of alkali concentration. When the liquid level drops due to carry-out by the boards, the liquid level is slightly lower than the weir position for overflow. When the dissolved resin is enriched to reach the deterioration limit, the absorption photometer 16 continuously measures the dissolved resin concentration in the developing solution, and when any value exceeding the deterioration limit is detected, by the output of the absorbance controller 26, the undiluted developing solution and pure water are supplied at a proper flow rate ratio by regulating the valve opening degree by the flow rate regulating valves 21, 22. Since a fresh developing solution is replenished, the dissolved resin concentration is diluted to the deterioration limit value, so that the developing performance is recovered. The liquid level is near the weir position for overflow, and when the undiluted developing solution or pure water is replenished, the deteriorating developing solution overflows from the overflow weir. The present inventors, by combining the various control functions as described above, found by experiment that the recovery of developing performance, continuous operation, and saving of consumption of developing solution may be realized easily and comprehensively. Moreover, for conceptual understanding, the operational patterns are compared between an embodiment of the invention and the prior art in Figs. 9 to 12. In the prior art, as shown in Fig. 10, the starting alkali concentration was, for example, 2.38 wt.%, and the solution was exchanged when the concentration was lowered to, for example, 2.29 wt.% in the course of time. In this case, as shown in Fig. 10, the alkali concentration transition is in a sawtooth profile, and due to variation of the alkali concentration, the developing performance was not constant. With the embodiment of the invention, on the other hand, as shown in Fig. 9, the alkali concentration remains constant at, for example, 2.38 ± 0.02 wt.% over the course of time, and it is not necessary to exchange the solution, and the development performance is constant. In the prior art, moreover, as shown in Fig. 12, the starting dissolved resin concentration (at this time, the residual film rate in unexposed area is, for example, 99%) increased as the time passed, and the solution was exchanged when the concentration reached a specific value (at this time, the residual film rate in unexposed area is, for example, 90%). In this case, as shown in Fig. 12, the time course change of the dissolved resin concentration is in a sawtooth profile, and variation occurred in the dissolved resin concentration, and hence the developing performance was not stable. With the embodiment of the invention, by contrast, the dissolved resin concentration remains constant after a certain time lapse as shown in Fig. 11, and hence the residual film rate in unexposed area is constant, not lowering, and it is not necessary to exchange the solution, and the developing performance is constant. By applying the invention in the liquid crystal board manufacturing process or the printed board manufacturing process, the alkali concentration and the dissolved resin concentration in the developing solution are always monitored and controlled with the desired target range, and continuous operation is possible for a long period at a stable liquid level. Since the quality of the developing solution may be controlled constant, the developing performance of board is stable, and when applied in the liquid crystal board manufacturing process, comprehensive effects are achieved, including a significant saving of consumption of solution, decrease of down time, and reduction of labor and developing solution cost.

Claims: Apparatus for controlling a solution used for developing photosensitive organic resin, comprising: developing solution discharge means (16, 18, 26) for discharging developing solution in response to the dissolved resin concentration detected in the developing solution by dissolved resin concentration detection means (16); first replenishing means (3, 21, 22, 24) for replenishing the developing solution from a source (19) of undiluted developing solution and a source of pure water in response to the liquid level of the developing solution detected by a liquid level gauge (3); and second replenishing means (15, 21, 22, 25) for replenishing the developing solution from a source (19) of undiluted developing solution and/or a source of pure water in response to the alkali concentration of the developing solution detected by alkali concentration detection means (15). Apparatus for controlling a solution used for developing photosensitive organic resin, comprising: developing solution discharge means (16, 18, 26) for discharging developing solution in response to the dissolved resin concentration detected in the developing solution by dissolved resin concentration detection means (16); first replenishing means (3, 24, 28) for replenishing the developing solution from a source (27) of diluted developing solution in response to the liquid level of the developing solution detected by a liquid level gauge (3); and second replenishing means (15, 21, 22, 25) for replenishing the developing solution from a source (19) of undiluted developing solution and/or a source of pure water in response to the alkali concentration of the developing solution detected by alkali concentration detection means (15). Apparatus for controlling a solution used for developing photosensitive organic resin, comprising: first replenishing means (16, 21, 22, 26) for replenishing the developing solution from a source (19) of undiluted developing solution and a source of pure water in response to the dissolved resin concentration detected in the developing solution by dissolved resin concentration detection means (16); and second replenishing means (15, 21, 22, 25) for replenishing the developing solution from a source (19) of undiluted developing solution and/or a source of pure water in response to the alkali concentration of the developing solution detected by alkali concentration detection means (15). Apparatus for controlling a solution used for developing photosensitive organic resin, comprising: first replenishing means (16, 26, 28) for replenishing the developing solution from a source (27) of diluted developing solution in response to the dissolved resin concentration detected in the developing solution by dissolved resin concentration detection means (16); and second replenishing means (15, 21, 22, 25) for replenishing the developing solution from a source (19) of undiluted developing solution and/or a source of pure water in response to the alkali concentration of the developing solution detected by alkali concentration detection means (15). Apparatus according to any one of claims 1 to 4, wherein the dissolved resin concentration detection means comprises an absorption photometer (16), and the alkali concentration detection means comprises an electric conductivity meter (15).

Inventors: NAKAGAWA TOSHIMOTO, OGAWA SHU, SHIOTSU SHINICHIRO, TSUKADA KOUZO, NAKAGAWA, TOSHIMOTO, OGAWA, SHU, SHIOTSU, SHINICHIRO, TSUKADA, KOUZO
Applicants: HIRAMA RIKA KENKYUJO LTD, NAGASE & CO LTD, HIRAMA RIKA KENKYUJO LTD., NAGASE & COMPANY, LTD.
Application year: 1992
Main classification: G03F7
IPC codes: H01L21, G03F7