CN108345185A - The concentration monitoring arrangement and developer solution managing device of developer solution - Google Patents

The concentration monitoring arrangement and developer solution managing device of developer solution Download PDF

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Publication number
CN108345185A
CN108345185A CN201711232885.8A CN201711232885A CN108345185A CN 108345185 A CN108345185 A CN 108345185A CN 201711232885 A CN201711232885 A CN 201711232885A CN 108345185 A CN108345185 A CN 108345185A
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CN
China
Prior art keywords
developer solution
concentration
carbon dioxide
absorbing carbon
dioxide concentration
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CN201711232885.8A
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Chinese (zh)
Inventor
中川俊元
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Hirama Rika Kenkyusho Ltd
Hirama Laboratories Co Ltd
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Hirama Rika Kenkyusho Ltd
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Publication of CN108345185A publication Critical patent/CN108345185A/en
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/70—Microphotolithographic exposure; Apparatus therefor
    • G03F7/70483—Information management; Active and passive control; Testing; Wafer monitoring, e.g. pattern monitoring
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/30—Imagewise removal using liquid means
    • G03F7/3042—Imagewise removal using liquid means from printing plates transported horizontally through the processing stations
    • G03F7/3071—Process control means, e.g. for replenishing
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03D—APPARATUS FOR PROCESSING EXPOSED PHOTOGRAPHIC MATERIALS; ACCESSORIES THEREFOR
    • G03D3/00—Liquid processing apparatus involving immersion; Washing apparatus involving immersion
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/002—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor using materials containing microcapsules; Preparing or processing such materials, e.g. by pressure; Devices or apparatus specially designed therefor
    • G03F7/0022—Devices or apparatus
    • G03F7/0025—Devices or apparatus characterised by means for coating the developer
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/30—Imagewise removal using liquid means
    • G03F7/32—Liquid compositions therefor, e.g. developers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/30—Imagewise removal using liquid means
    • G03F7/32—Liquid compositions therefor, e.g. developers
    • G03F7/322—Aqueous alkaline compositions
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34

Abstract

The present invention provides the concentration monitoring arrangement and developer solution managing device of developer solution.They have densimeter, the density for measuring developer solution.Independently there is good correspondence between the density of developer solution and absorbing carbon dioxide concentration with the concentration of other ingredients such as alkali composition.Measured value of the concentration monitoring arrangement based on density calculates absorbing carbon dioxide concentration according to the correspondence of the density of developer solution and absorbing carbon dioxide concentration.Alert mechanism sends out alarm when the absorbing carbon dioxide concentration value of the developer solution calculated by arithmetical organ deviates preset range of management.Developer solution managing device uses the correspondence of the density and absorbing carbon dioxide concentration of developer solution, the absorbing carbon dioxide concentration value of the density value determined or calculating based on developer solution, by make developer solution absorbing carbon dioxide concentration become defined management value or management value it is below in a manner of to developer solution feed replenisher, thus management developer solution absorbing carbon dioxide concentration.

Description

The concentration monitoring arrangement and developer solution managing device of developer solution
Technical field
The present invention relates in semiconductor or the developing procedure of the circuit board of liquid crystal display panel etc. in order to make photoresist Film develop and use show alkalinity developer solution concentration monitoring arrangement and developer solution managing device.
Background technology
In the photolithographic developing procedure processed for realizing the fine wiring of semiconductor or liquid crystal display panel etc., as general The liquid of photoresist dissolving after being film-made on substrate, uses the developer solution (hereinafter referred to as " alkaline development for showing alkalinity Liquid ").
In the manufacturing process of semiconductor or base plate of liquid crystal panel, in recent years, chip, the enlargement of glass substrate and cloth The miniaturization and highly integrated continuous development of line processing.In such a case, in order to realize large substrate wiring processing Miniaturization and highly integrated, need the concentration for further accurately measuring the main component of alkaline-based developer come to developer solution into Row maintains management.
The measurement of the constituent concentration of existing alkaline-based developer is as described in Patent Document 1, and what is utilized is in alkalinity The concentration (hereinafter referred to as " alkali composition concentration ") of the alkali composition of developer solution can be obtained between conductivity good linear relation this One principle and concentration (hereinafter referred to as " dissolving photoresist agent concentration ") in the photoresist for being dissolved in alkaline-based developer Good linear relation this principle can be obtained between absorbance.
However, alkaline-based developer is easy the carbon dioxide absorbed in air and generates carbonate.At this point, the tool in developer solution There is the alkali composition of developing activity to be consumed and reduce.Thus, in order to accurately carry out maintenance pipe to the developing performance of developer solution Reason needs to consider the influence that the carbon dioxide that developed liquid absorbs brings developing performance to carry out developer solution management.
In order to solve the problems, Patent Document 2 discloses following developer solution modulating device etc., the developer solutions Modulating device is measured the ultrasonic propagation velocity of developer solution, conductivity and absorbance, based on alkali concentration, carbonate concentration And the pre-made relationship (matrix) of ultrasonic propagation velocity in dissolving resin concentration, conductivity and absorbance is aobvious to detect Alkali concentration, carbonate concentration and the dissolving resin concentration of shadow liquid, and the alkali concentration based on the developer solution determined, carbonate concentration With dissolving resin concentration and capable of playing make CD values (critical dimension value) (line width) be fixed value in this way Solvability alkali concentration, the pre-made relationship of carbonate concentration and dissolving resin concentration, to control developer solution stoste Confession give adjust alkali concentration.
In addition, in patent document 3, disclosing following alkaline developer management system etc., which manages system Have：Carbonic acid system salt density measurement device is measured the refractive index, conductivity, absorbance of developer solution, and according to this A little measured values obtain the carbonic acid system salt density in developer solution；And control unit, dress is measured to the carbonic acid system salt density It sets and is controlled with the carbonic acid system salt density in developer solution.
Citation
Patent document
Patent document 1：No. 2561578 bulletins of Japanese Patent No.
Patent document 2：Japanese Unexamined Patent Publication 2008-283162 bulletins
Patent document 3：Japanese Unexamined Patent Publication 2011-128455 bulletins
However, the ultrasonic propagation velocity value or refractive index value of alkaline-based developer are to indicate the alkaline-based developer of multicomponent system Liquid entirety property characteristic value.It is such indicate liquid entirety property characteristic value not usually only in the liquid The concentration of the specific ingredient contained is related.It is such to indicate that the characteristic value of the property of liquid entirety usually contains with the liquid The concentration of various composition be respectively provided with relevance.Therefore, in the characteristic value according to such property for indicating liquid entirety In the case that measured value carrys out the constituent concentration of operation developer solution, if it is only related to certain specific constituent concentration to set certain characteristic value (for example there is linear relations) and ignore the influence that other ingredients bring the characteristic value, then exist can not be calculated with sufficient precision The problem of going out the concentration of the special component.
On the other hand, the function of the concentration of the various composition contained in the characteristic value for setting developer solution is developer solution and root In the case of calculating each constituent concentration according to the measured value of the characteristic value of developer solution, after determining multiple characteristic values, need Using the operation method appropriate for calculating each constituent concentration according to the measured value of these characteristic values.Suitably, however selection is wanted It the characteristic value of measurement and finds and can precisely calculate the appropriate of each constituent concentration according to the measured value of characteristic value Operation method is all very difficult.Therefore, if measured characteristic value and operation method is inappropriate, existing can not be with abundant Precision calculate each constituent concentration the problem of.
In turn, in the liquid of multicomponent system, the concentration of certain usual ingredient can't be only each other with the concentration of other ingredients It is vertical.In the liquid of multicomponent system, there is when the variation of the concentration of certain ingredient other constituent concentrations also phase as variation simultaneously Mutual relation.The calculating for being more difficult to carry out high-precision constituent concentration and high-precision developer solution management are resulted in this way.
In addition, for the concentration (hereinafter referred to as " absorbing carbon dioxide concentration ") for the carbon dioxide that developer solution is absorbed, And it is unaware of and the characteristic value appropriate there are the developer solution of good relevance between the absorbing carbon dioxide concentration, current hardly possible Precisely to measure absorbing carbon dioxide concentration.Moreover, in the management of developer solution, it is important that monitoring developer solution The variation of absorbing carbon dioxide concentration.
Invention content
The subject that the invention solves
The present invention proposes to solve above-mentioned each project.The purpose of the present invention is to provide one kind can be according to multicomponent The density value of the developer solution of system measures the absorbing carbon dioxide concentration of developer solution and can monitor absorbing carbon dioxide concentration Variation concentration monitoring arrangement and can be so that the gas concentration lwevel of developer solution becomes defined management value or does not surpass Cross the developer solution managing device that the mode of defined management value is managed.
Solution for solving the problem
The concentration monitoring arrangement of the developer solution of the present invention has：Densimeter；Arithmetical organ is based on being surveyed by the densimeter That makes shows the density value of the developer solution of alkalinity, according to pair between the density of the developer solution and absorbing carbon dioxide concentration It should be related to calculate the absorbing carbon dioxide concentration of the developer solution；And alert mechanism, it is calculated by the arithmetical organ The developer solution absorbing carbon dioxide concentration value deviate preset range of management when send out alarm.
According to the present invention, since the absorbing carbon dioxide concentration for having pair with developer solution has the close of good correspondence The densimeter that angle value is measured, therefore the absorption dioxy of developer solution can be calculated according to the density value determined by densimeter Change concentration of carbon, and can monitor the concentration of developer solution by the alarm of alert mechanism.
In concentration monitoring arrangement, have the external output signal terminal for sending alarm signal, the alarm to sound the alarm Device, light light or flicker emergency warning lamp, display warning display device and double-throw contact opening and closing Converting terminal in Either one be used as the alert mechanism.
The developer solution managing device of the present invention has：Densimeter；Control mechanism, based on what is determined by the densimeter The density value for showing the developer solution of alkalinity uses the corresponding pass between the density and absorbing carbon dioxide concentration of the developer solution System, by make the absorbing carbon dioxide concentration of the developer solution become defined management value or management value it is below in a manner of to control Valve sends control signal, and the control valve is arranged on the pipeline for the replenisher that conveying is fed to the developer solution；And alarm Mechanism deviates dense with preset absorbing carbon dioxide in the density value of the developer solution determined by the densimeter Alarm is sent out when the corresponding density range of the range of management of degree, the density range is the density and absorption according to the developer solution Correspondence between gas concentration lwevel and determination.
According to the present invention, using the density of developer solution with the correspondence of absorbing carbon dioxide concentration and according to by densimeter The amount of the density value can be known replenisher to be fed of the developer solution determined, thus can so that developer solution absorption titanium dioxide Concentration of carbon feeds replenisher to be managed as defined management value or management value mode below, and can pass through police The alarm of mechanism is reported to monitor the concentration of developer solution.
The developer solution managing device of the present invention has：Densimeter；Operation control mechanism, has operational part and control unit, Density value of the operational part based on the developer solution for showing alkalinity determined by the densimeter, according to the close of the developer solution It spends and calculates the absorbing carbon dioxide concentration of the developer solution, the control the correspondence between absorbing carbon dioxide concentration Absorbing carbon dioxide concentration of the portion based on the developer solution calculated by the operational part, so that the absorption dioxy of the developer solution Changing concentration of carbon becomes defined management value or management value mode below to control valve transmission control signal, and the control valve is set It sets on the pipeline for the replenisher that conveying is fed to the developer solution；And alert mechanism, what is calculated by the operational part The absorbing carbon dioxide concentration value of the developer solution sends out alarm when deviateing preset range of management.
According to the present invention, since the absorbing carbon dioxide concentration for having pair with developer solution has the close of good correspondence The densimeter that angle value is measured, therefore the absorption dioxy of developer solution can be calculated according to the density value determined by densimeter Change concentration of carbon, can by make developer solution absorbing carbon dioxide concentration become defined management value or management value it is below in a manner of Replenisher is fed to be managed, and can monitor the concentration of developer solution by the alarm of alert mechanism.
The developer solution managing device of the present invention has：Densimeter；Arithmetical organ, based on what is determined by the densimeter The density value for showing the developer solution of alkalinity, according to the correspondence between the density of the developer solution and absorbing carbon dioxide concentration To calculate the absorbing carbon dioxide concentration of the developer solution；Control mechanism, it is described aobvious based on being calculated by the arithmetical organ The absorbing carbon dioxide concentration of shadow liquid, so that the absorbing carbon dioxide concentration of the developer solution becomes defined management value or pipe Reason is worth mode below and sends control signal to control valve, and the supplement fed to the developer solution in conveying is arranged in the control valve On the pipeline of liquid；And alert mechanism, in the absorbing carbon dioxide concentration of the developer solution calculated by the arithmetical organ Value sends out alarm when deviateing preset range of management.
According to the present invention, since the absorbing carbon dioxide concentration for having pair with developer solution has the close of good correspondence The densimeter that angle value is measured, therefore the absorption dioxy of developer solution can be calculated according to the density value determined by densimeter Change concentration of carbon, can by make developer solution absorbing carbon dioxide concentration become defined management value or management value it is below in a manner of Replenisher is fed to be managed, and can monitor the concentration of developer solution by the alarm of alert mechanism.
In developer solution managing device, have the external output signal terminal for sending alarm signal, the police to sound the alarm Reporting device, light are lighted or the emergency warning lamp flickered, the Converting terminal for showing the display device of warning and the opening and closing of double-throw contact In either one be used as the alert mechanism.
Invention effect
It was difficult to the absorbing carbon dioxide concentration of the developer solution measured in the past in accordance with the invention it is possible to measure, and can be supervised Depending on the concentration of developer solution.In addition, can be based on the absorbing carbon dioxide concentration value of the density value or calculating determined, so that development The absorbing carbon dioxide concentration of liquid as defined management value or management value mode below to developer solution supply replenisher come into Row management.
Description of the drawings
Fig. 1 is the chart of the relationship of the absorbing carbon dioxide concentration and density that indicate developer solution.
Fig. 2 is the schematic diagram of the concentration monitoring arrangement of the developer solution of first embodiment.
Fig. 3 is the schematic diagram of the representative configurations of oscillatory type densimeter.
Fig. 4 is the schematic diagram of the development treatment process for the developer solution managing device for including second embodiment.
Fig. 5 is the schematic diagram of the development treatment process for the developer solution managing device for including third embodiment.
Fig. 6 is the schematic diagram of the development treatment process for the developer solution managing device for including the 4th embodiment.
Drawing reference numeral explanation：
A ... concentration monitoring arrangement, B ... developing procedures equipment, C ... replenishers reservoir, D ... circulation stirrings mechanism, E ... are aobvious Shadow liquid managing device
1 ... determination part
11 ... densimeters, 12,13 ... measuring means, 14 ... sampling pumps, 15 ... sampling pipings, 16 ... outlet side lines
2 ... operational parts
21 ... computing modules, 22 ... indication mechanisms
23 ... calculation control units (such as computer)
3 ... control units
31 ... control modules
41~43 ... control valves, 44,45,46,47 ... valves,
51 ... sample cells, 52 ... thermometers, 53 ... Peltier's elements, 54 ... thermostat modules, 55 ... thermal insulation barriers, 56 ... shake Son, 61 ... developer solution storagetanks, 62 ... overflow launders, 63 ... liquid level meters, 64 ... developing room shields, 65 ... roller conveyors, 66 ... Substrate, 67 ... developer solution spray nozzles, 71 ... waste drains pumps, 72,74 ... circulating pumps, 73,75 ... filters, 80 ... development liquid pipelines, 81,82 ... replenishers (development stoste and/or new liquid) pipeline, 83 ... pure water pipelines, 84 ... interflow pipelines, 85 ... circulation pipes Road, 86 ... nitrogen pipelines, 91,92 ... replenisher storagetanks
WD ... alert mechanisms.
Specific implementation mode
Hereinafter, suitably referring to attached drawing, the preferred embodiments of the present invention is described in detail.Wherein, as long as no It is particularly limited to, shape, size, size ratio, its relative configuration of device recorded in these embodiments etc. etc. just not only limit Due to the example for illustrating the scope of the present invention.These examples be merely possible to illustrate example and schematically illustrated and .
In addition, in the following description, as the concrete example of developer solution, suitably having used in semiconductor or liquid crystal display panel base Main 2.38wt% tetramethylammonium hydroxide aqueous solutions to be used are (hereinafter, tetramethylammonium hydroxide is claimed in the manufacturing process of plate Make TMAH) it illustrates.But it's not limited to that for the developer solution of the invention that can be applicable in.Developer solution as the present invention Concentration monitoring arrangement or the example of other developer solutions that can be applicable in such as developer solution managing device, hydroxide can also be enumerated The aqueous solution or trimethyl monoethanol base ammonium hydroxide (courage of the inorganic compounds such as potassium, sodium hydroxide, sodium phosphate, sodium metasilicate Alkali) etc. organic compounds aqueous solution.
In addition, in the following description, alkali composition concentration, dissolving photoresist agent concentration, absorbing carbon dioxide concentration etc. Constituent concentration is the concentration based on weight percent concentration (wt%)." dissolving photoresist agent concentration " refer to will dissolve it is photic Resist is converted into the concentration in the case of the amount of photoresist, and " absorbing carbon dioxide concentration " refers to by absorbed dioxy Change carbon is converted into the concentration in the case of the amount of carbon dioxide.
In development process, developer solution dissolves the unnecessary portion of the photoresist film after exposure-processed, by This develops.It is dissolved between the photoresist of developer solution and the alkali composition of developer solution and will produce photoresist salt.Cause This, if not being managed suitably to developer solution, with the progress of development treatment, in developer solution with developing activity Alkali composition is consumed and deteriorates, and developing performance deteriorates.Meanwhile it being dissolved in the photoresist in developer solution and being sent out with alkali composition Life is reacted and is constantly accumulated in the form of photoresist salt.
The photoresist for being dissolved in developer solution shows interfacial activity effect in developer solution.Therefore, it is dissolved in developer solution Photoresist can improve the wellability relative to developer solution of the photoresist film for being used to development treatment so that development The compatibility of liquid and photoresist film improves.Thus, in the developer solution moderately containing photoresist, developer solution is good Ground spreads all in the fine recess portion of photoresist film, so as to implement the concave-convex photoresist for having fine well The development treatment of agent film.
In addition, in development treatment in recent years, with the enlargement of substrate, a large amount of developer solution of Reusability, therefore it is aobvious The chance that shadow liquid is exposed to air increases.However, alkaline-based developer can absorb the carbon dioxide in air if being exposed to air. Carbonate is will produce between absorbed carbon dioxide and the alkali composition of developer solution.Therefore, if inadequately managing developer solution, Carbon dioxide-depleted that the alkali composition with developing activity in developer solution is absorbed and reduce.Meanwhile it being inhaled in developer solution The carbon dioxide of receipts is reacted with alkali composition and is constantly accumulated in the form of carbonate.
Carbonate in developer solution shows alkalinity in developer solution, therefore has development effect.For example, by using 2.38% In the case of TMAH aqueous solutions, if carbon dioxide in developer solution be about 0.4wt% degree hereinafter, if can develop.
In this way, different from " carbon dioxide that the photoresist dissolved in developer solution or developed liquid absorb to development at Unwanted for reason " as existing cognition, in fact, the photoresist dissolved in developer solution or developed liquid absorb Carbon dioxide contribute to the developing performance of developer solution.Therefore, be not into be about to dissolve photoresist or absorb two Carbonoxide excludes such developer solution management completely, but needs to carry out following developer solution management, that is, allows in developer solution It is slightly molten to have photoresist or absorbing carbon dioxide and maintain management at best concentration them.
Based on above-mentioned point, inventor constantly carefully studies, and obtains following opinion.That is, the alkali composition with developer solution is dense Degree, dissolving photoresist agent concentration it is unrelated, developer solution density value compared with it can be obtained between absorbing carbon dioxide concentration value Good correspondence (linear relation).If in addition, using the correspondence (linear relation), surveyed by using densimeter Determine the density of developer solution, it will be able to which measurement was difficult to the absorbing carbon dioxide concentration measured in the past.If moreover, using the correspondence (linear relation) then can pass through the benefit of replenisher based on the absorbing carbon dioxide concentration value of the density value or calculating determined It gives to be managed to the absorbing carbon dioxide concentration of developer solution.
Inventor assumes the case where carrying out the management of 2.38%TMAH aqueous solutions, and alkali composition concentration, dissolving will be made photic anti- Erosion agent concentration, absorbing carbon dioxide concentration occur the TMAH aqueous solutions obtained by various change and are modulated into simulation developer solution sample.Hair A person of good sense's forming substantially using 2.38%TMAH aqueous solutions as developer solution modulates alkali composition concentration (TMAH concentration) of sening as an envoy to, dissolving 11 calibration standard solution obtained by various change occur for photoresist agent concentration, absorbing carbon dioxide concentration.
Inventor is tested as follows：For these simulation developer solution sample, measure alkali composition concentration (TMAH concentration), Absorbing carbon dioxide concentration and density confirm the correlation of constituent concentration and density.
Measurement is carried out by the way that the temperature for correcting standard solution is adjusted to 25.0 DEG C.Temperature adjusts in the following way： The bottle for being put into calibration standard solution is immersed in for a long time in the thermostatic water bath that temperature is managed as near 25 DEG C, from the bottle It is sampled in son, then, 25.0 DEG C is adjusted to again using temperature controller before horse back will be measured.Density measurement, which has used, adopts With the densimeter of self-oscillation method, the self-oscillation method is according to the intrinsic vibration number measured into row energization to U-shaped pipe flow cell To solve density.The unit of the density value determined is g/cm3。
The constituent concentration of each sample and the measurement result of density are shown in table 1 below.
【Table 1】
Absorbing carbon dioxide is easy in view of TMAH aqueous solutions because of strong basicity thus to deteriorate, the constituent concentration of table 1 makes It is separately right that alkali composition concentration (TMAH concentration), the analysis by titration of absorbing carbon dioxide concentration can be accurately analyzed with utilization Each sample is measured the value of gained.Wherein, about dissolving photoresist agent concentration, weight modulation value has been used.
Titration is using hydrochloric acid as the acid-base titration of titer reagent.Mitsubishi Chemical's analytical technology has been used as titration outfit The automatic titration device GT-200 of corporation.
The absorbing carbon dioxide concentration of each sample shown in table 1 and the chart of density is shown in FIG. 1.The chart is will to inhale It receives gas concentration lwevel (wt%) and is taken as horizontal axis and by density (g/cm3) it is taken as the longitudinal axis, it draws and schemes obtained from the value of each sample Table.According to each point drawn out and find out regression straight line using least square method.
According to Fig. 1 it is to be understood that the absorbing carbon dioxide concentration of developer solution and alkali composition concentration or dissolving photoresist It is unrelated why agent concentration is worth, and there are good straight line passes between the absorbing carbon dioxide concentration and the density of developer solution of developer solution System.Inventor has found according to the experimental result：If using corresponding between the absorbing carbon dioxide concentration and density of the developer solution Relationship (linear relation) then can calculate the absorbing carbon dioxide concentration of developer solution by measuring the density of developer solution.
Thus, it is possible to realize the concentration monitoring arrangement of following developer solution：With alkali composition concentration (TMAH concentration) or dissolving The absorption two that photoresist agent concentration is unrelated and utilizes the correspondence (linear relation) and measures developer solution using densimeter Aoxidize concentration of carbon.
In addition, in development treatment process in the alkaline-based developer of Reusability, developer solution managing device pair is usually utilized Alkali composition concentration (TMAH concentration), dissolving photoresist agent concentration are managed.Compared with the experiment of above-mentioned analog sample, make What the linearity between the density and absorbing carbon dioxide concentration of developer solution deteriorated will be because less.Thus, of the invention can survey The concentration monitoring arrangement for determining the absorbing carbon dioxide concentration of developer solution is also adaptable as that absorbing carbon dioxide concentration can be carried out One component of the developer solution managing device of monitoring or management uses.
Moreover, for alkaline-based developer, there is the increased trend of absorbing carbon dioxide, therefore absorb two by supplementing Aoxidizing the small replenisher (such as stoste of developer solution or new liquid etc.) of concentration of carbon, act as a supplement liquid, and thus, it is possible to by developer solution Absorbing carbon dioxide concentration management is at defined management value or manages below at defined management value.
In addition, because there is the corresponding pass being increased monotonically in the absorbing carbon dioxide concentration with density of the developer solution as Fig. 1 It is (linear relation), therefore it is just equivalent so that the absorbing carbon dioxide concentration of developer solution is become defined management value or management value or less In make the density value of developer solution become corresponding as defined in below management value or management value.Thus, if will be with absorbing carbon dioxide The management of concentration is worth the management value that corresponding density value is set as density, by measuring the density of developer solution and so that this was determined Density value becomes its management value or management value mode below is managed, then also can be to make developer solution by developer solution management Absorbing carbon dioxide concentration become defined management value or management value or less.
Here, it is specified that management value refer to, as can make developer solution play well developing performance developer solution two The upper limit of the concentration value of carbonoxide and the concentration value or density value corresponding with the concentration value being previously validated.In theory below It is also the same in bright.
Then, specific embodiment is illustrated with reference to attached drawing.
(first embodiment)
Fig. 2 is the schematic diagram of the concentration monitoring arrangement of the developer solution of present embodiment.
The concentration monitoring arrangement A of the developer solution of present embodiment has determination part 1, operational part 2 and alert mechanism WD.
Determination part 1 has the densimeter of density for measuring developer solution and other characteristic values for measuring developer solution Other measuring means (11~13 in figure), sampling pump 14 and for the temperature of the developer solution of sampling to be adjusted to before the assay The thermostat (not shown) etc. of defined measuring temperature (such as 25 DEG C).
In the case where concentration monitoring arrangement A only measures density, as the measuring means 11~13 of determination part 1, tool Standby densimeter (such as 11), need not measure the measuring means (such as 12,13) of other characteristic values.However, most cases Under, as the concentration monitoring arrangement of alkaline-based developer, absorbing carbon dioxide concentration is not only measured, the dense of alkali composition is also measured Spend, be dissolved in the photoresist agent concentration of developer solution.Therefore, in fig. 2, describe by order to measure alkali composition concentration, dissolving Photoresist agent concentration etc. and other measuring means for needing are also included within interior measuring means 11,12,13.These measuring means One of be densimeter.In the explanation of concentration monitoring arrangement A below, by the measuring means in the measuring means 11~13 of Fig. 2 11 are set as densimeter.
Operational part 2 has the computing module 21 that absorbing carbon dioxide concentration value is calculated according to the density value determined. Pre-entered in computing module 21 between the density of developer solution and absorbing carbon dioxide concentration correspondence (such as Fig. 1 that The linear relation of sample).Computing module 21, which has, solves corresponding absorption titanium dioxide according to the density value of the developer solution determined The function of concentration of carbon value.Additionally, it is preferred that operational part 2 has the indication mechanism for showing the absorbing carbon dioxide concentration calculated 22.In addition, concentration monitoring arrangement A is connect by sampling piping 15 with the slot of storage developer solution.
The assay method that absorbing carbon dioxide is measured to the concentration monitoring arrangement A of present embodiment illustrates.Developer solution It is conveyed into determination part 1 by sampling pump 14.The developer solution for being transported to determination part 1 is adjusted temperature in thermostat first And become defined measuring temperature (such as 25 DEG C).Temperature be adjusted after developer solution to densimeter 11 and other measuring means 12,13 conveying.Densimeter 11 measures the density of developer solution.Other measuring means 12,13 also measure the characteristic value of developer solution respectively. Developer solution after measurement is discharged from outlet side line 16 to outside concentration monitoring arrangement A.
Densimeter 11 and other measuring means 12,13 are connect by signal wire with the computing module 21 of operational part 2.By density The measurement number of the characteristic value of the density value for the developer solution that instrument 11 determines and the developer solution determined by other measuring means 12,13 It is sent to computing module 21 according to via signal wire.
Have received the computing module 21 of the density value of developer solution and the determination data of other characteristic values based on determination data come Calculate the constituent concentration of developer solution.Use correspondence (such as Fig. 1 between the density and absorbing carbon dioxide concentration of developer solution Such linear relation) calculate the absorbing carbon dioxide concentration of developer solution.That is, according to the density of developer solution and absorption titanium dioxide Correspondence between concentration of carbon obtains absorbing carbon dioxide concentration value corresponding with the density value of the developer solution determined, and The value is set as to the measured value of the absorbing carbon dioxide concentration of developer solution.
In this way, the concentration monitoring arrangement A of the developer solution of present embodiment can be based on the measured value of the density of developer solution, root The absorbing carbon dioxide concentration of developer solution is measured according to the correspondence of density and the absorbing carbon dioxide concentration of developer solution.
For the concentration monitoring arrangement A of present embodiment, in addition to determination part 1 and operational part 2 are used as one as shown in Figure 2 The device of body and the case where constitute except, can also by determination part 1, operational part 2 and indication mechanism 22 it is seperated constitute.In fission In the case that ground is constituted, determination part 1 and the signal wire of operational part 2 etc. are connect, so that by the densimeter 11 of determination part 1 And the determination data that other measuring means 12,13 determine is received by the computing module 21 of operational part 2.Wireless side can be passed through Formula transmits and receives determination data between determination part 1 and operational part 2.
The concentration monitoring arrangement A and its determination part 1 of present embodiment can also be connect with the storagetank of storage developer solution, with Make it possible to be sampled developer solution from storagetank.Alternatively, concentration monitoring arrangement A and its determination part 1 can be directly or other It is connected to logically on the recycle circuit for the development treatment process for recycling developer solution.
In addition, in fig. 2, it is illustrated that the mode that each measuring means 11~13 including densimeter is connected in series with, but It's not limited to that for the connection of each measuring means.It can be connected in parallel, can also have liquor charging path independently of one another to carry out It measures.The measurement of densimeter and other measuring means sequence is paid no attention to successively.Can according to the feature of each measuring means and suitably with Best sequence is measured.
In the structure of determination part 1 shown in Fig. 2, sampling pump 14 is not necessary.It is being directly connected in recycle circuit In the case of, sampling pump 14 need not be set in determination part 1.In addition, the case where being sampled to developer solution from storagetank Under, sampling pump 14 can not also be set in determination part 1.On the other hand, although not shown, but it is preferred for developer solution being adjusted to The thermostat of defined measuring temperature is arranged in the immediately front of measuring means.
The computing module 21 of operational part 2 is in addition to having the work(for calculating absorbing carbon dioxide concentration according to the measured value of density Except energy, can also have the work(of other constituent concentrations such as the alkali composition concentration for calculating developer solution, dissolving photoresist agent concentration Energy.In such manner, it is possible to realize the alkali composition concentration that can measure developer solution, dissolving photoresist agent concentration and absorbing carbon dioxide concentration Concentration monitoring arrangement.
The concentration monitoring arrangement A of present embodiment has alert mechanism WD.Alert mechanism WD can be by as calculating machine The absorbing carbon dioxide concentration value for the developer solution that the operational part 2 of one mode of structure calculates is sent out when deviateing preset range of management Go out alarm.
For example, prestoring range of management in operational part 2, it is to judge absorbing carbon dioxide concentration value by operational part 2 It is no outside range of management.The information can be transmitted from operational part 2 to alert mechanism WD, and so that alert mechanism WD is sent out based on information Go out alarm.
In addition, prestoring range of management in alert mechanism WD, the information of constituent concentration is received from operational part 2, by warning Mechanism WD is reported to judge absorbing carbon dioxide concentration value whether within a governance context.Alert mechanism WD can be made to send out based on the judgement Go out alarm.
As long as alert mechanism WD can send out alarm, then the storing mechanism of range of management and decision mechanism are not particularly limited In this.
As alert mechanism WD, it is preferably provided with the external output signal terminal for sending alarm signal, the police to sound the alarm Reporting device, light are lighted or the emergency warning lamp flickered, the Converting terminal for showing the display device of warning and the opening and closing of double-throw contact In either one.
In the case where alert mechanism WD is to send the external output signal terminal of alarm signal, external output signal terminal It is connect with device (not shown).Device can carry out defined dynamic when receiving alarm signal from external output signal terminal Make.For example, if the system for including concentration monitoring arrangement, then system can be made to stop.
Alert mechanism WD be the alarm device to sound the alarm or light light or flicker emergency warning lamp in the case of, The attention of the operator near concentration monitoring arrangement can be aroused.Operator is able to confirm that the state of concentration monitoring arrangement is come Carry out correspondence appropriate.
In the case where alert mechanism WD is the display device for showing warning, it can equally arouse the attention of operator.Separately Outside, in the case where display device is electrically connected with operational part 2 by wired or wireless mode, additionally it is possible to arouse and be supervised far from concentration The attention of the operator of view apparatus.
In the case where alert mechanism WD is the Converting terminal of the opening and closing of double-throw contact, allows hand over and connect with Converting terminal Device switch on and off, and make device carry out as defined in action.
The densimeter 11 of concentration monitoring arrangement A as present embodiment, may be used the float type density using buoyancy Instrument, using the height in liquid different point-to-point transmission pressure difference differential pressure density instrument, utilize the transmissivity of gamma ray The various densimeters such as gamma ray density instrument.It is further preferred that using the pipeline to being filled with liquid intrinsic vibration number into Row detects to obtain the oscillatory type densimeter of density.
Fig. 3 schematically shows the representative configurations of oscillatory type densimeter.
The determination part of oscillatory type densimeter, which has, bends to the sample cell 51 of U-shaped, to the liquid in sample cell 51 The thermostat module 54 for the thermometer 52, encirclement sample cell 51 that the temperature of sample is measured and setting are in thermostat module 54 Periphery thermal insulation barriers 55.Thermostat module 54 is provided with the Peltier's element 53 of the temperature for adjusting sample.In sample list The front end of bending section of member 51 is provided with oscillator 56, by close in a manner of oscillator 56 configured with to oscillator 56 into the driving of row energization The test section of the vibration frequency of portion and detection oscillator 56.
Energized sample cell 51 is vibrated with the intrinsic vibration number of the quality association of the liquid internal with it.Pass through The intrinsic vibration number is detected, thus knows the quality of the liquid in sample cell 51, therefore can be according in sample cell 51 Volume measures the density of liquid.
Oscillatory type densimeter has following feature：Measurement that is highly sensitive and stablizing can be carried out, and can be connected It is continuous to measure.Oscillatory type densimeter passes through thermometer, temperature adjusting mechanism (Peltier's element 53 in Fig. 3) and heat-shield mechanism (Fig. 3 In thermal insulation barriers 55) and can realize the measurement based on good temperature condition and temperature stability.In addition, oscillatory type densimeter Only the density of sample can be measured by conveying the liquid of sample to sample cell.In density measurement, need not be tried The addition etc. of agent, also without waste liquid.
Various measuring means 11~13 in the concentration monitoring arrangement of the developer solution of present embodiment, especially densimeter Set-up mode is not limited to mode shown in Fig. 2.
Densimeter has various measuring principles and mensuration mode, thus with the setting method mutually fitted therewith respectively.It is adopting It uses float type densimeter, differential pressure density instrument as in the case of densimeter, the buoy portion of densimeter, probe portion is impregnated in The mode density of setting instrument of the storagetank of developer solution is preferably.It, can be in developer solution using gamma ray density instrument Direct density of setting instrument on the pipeline of flowing.Using oscillatory type densimeter in the case of, as shown in Fig. 2, by storagetank with it is close If degree instrument is connected by sampling line, it will be able to be sampled to developer solution to carry out METHOD FOR CONTINUOUS DETERMINATION.
Oscillatory type densimeter is suitable for continuous only by the way that developer solution can be measured density to sample cell conveying And online use.In addition, being suitable for steadily being managed the determination conditions such as liquid temperature, can carry out stable and highly sensitive Measurement.It, also can be with 0.001 (g/cm even the oscillatory type densimeter of engineering3) left and right precision be measured, according to The linear relation of Fig. 1, the concentration monitoring arrangement of present embodiment can reach the survey of the carbon dioxide of the left and right about 0.15 (wt%) Determine precision.If the alkali composition concentration of developer solution, dissolving photoresist agent concentration are in the situation being managed, density and absorption two The linearity of oxidation concentration of carbon becomes raising that is more good, but also can expecting the measurement accuracy of densimeter, therefore can also The enough absorbing carbon dioxide concentration for expecting more precisely measured concentration monitoring arrangement.
The concentration monitoring arrangement of the developer solution of present embodiment utilizes the absorbing carbon dioxide concentration that can measure developer solution This characteristic can be efficiently applied to developer solution managing device as managing the component of absorbing carbon dioxide concentration.It is logical It crosses and combines following control mechanism with the concentration monitoring arrangement of present embodiment, and can constitute can be dense to absorbing carbon dioxide Spend the developer solution managing device being managed, the absorption two for the developer solution that the control mechanism is determined based on concentration monitoring arrangement Aoxidize concentration of carbon, by make developer solution absorbing carbon dioxide concentration become defined management value or management value it is below in a manner of to show Shadow liquid feeds replenisher to be controlled.
(second embodiment)
Fig. 4 is the schematic diagram of following developer solution managing device, which is based on being determined by densimeter Developer solution density value, using the correspondence between the density of developer solution and absorbing carbon dioxide concentration come to developer solution mend To replenisher, the gas concentration lwevel of developer solution is thus managed.For convenience of description, by developer solution managing device E with development The mode of processing apparatus B connections illustrates together with developing procedure equipment B, replenisher reservoir C, circulation stirring mechanism D.
First, developing procedure equipment B is simply illustrated.
Developing procedure equipment B mainly by developer solution storagetank 61, overflow launder 62, developing room shield 64, roller conveyor 65, Developer solution spray nozzles 67 etc. are constituted.It is stored with developer solution in developer solution storagetank 61.Developer solution by supplement replenisher come into Row composition management.Developer solution storagetank 61 has liquid level meter 63 and overflow launder 62, the increasing to liquid measure caused by supply replenisher Add and is managed.Developer solution storagetank 61 is connect with developer solution spray nozzle 67 by developing liquid pipeline 80.It is stored in developer solution Developer solution in storagetank 61 is sprayed via filter 73 to developer solution under the action of set on circulating pump 72 of development liquid pipeline 80 Mouth 67 is drenched to convey.Roller conveyor 65 is arranged in the top of developer solution storagetank 61, has photoresist film for conveying to make Substrate 66.Developer solution drips from developer solution spray nozzle 67.The substrate 66 conveyed by roller conveyor 65 passes through the development dripped Developed liquid infiltration among liquid.Later, the developed liquid storagetank 61 of developer solution recycles, and stores again.In this way, developer solution exists It recycles and is used repeatedly in developing procedure.It should be noted that in the developing room of small-sized glass substrate, sometimes through filling The modes such as full nitrogen are handled to implement to prevent to absorb as the carbon dioxide in air
Then, the developer solution managing device E of present embodiment is illustrated.The developer solution managing device of present embodiment E is the developer solution managing device such as under type：The density that developer solution is measured using densimeter, the density using developer solution and suction The correspondence (such as linear relation as Fig. 1) for receiving gas concentration lwevel, so that the absorbing carbon dioxide concentration of developer solution It is worth mode below based on the density value determined as defined management value or management to feed replenisher to developer solution.
Developer solution managing device E has determination part 1, operational part 2, control unit 3 and alert mechanism WD, and is piped by sampling 15 and outlet side line 16 and connect with developer solution storagetank 61.Determination part 1, operational part 2 and control unit 3 are connected by signal wire It connects.
Determination part 1 have sampling pump 14, densimeter 11 and other characteristic values for measuring developer solution measuring means 12, 13.Measuring means 12,13 is, for example, the measuring machine for measuring the alkali composition concentration of developer solution, dissolving photoresist agent concentration Structure.Densimeter 11 and measuring means 12,13 and the back segment of sampling pump 14 are connected in series with.It is preferred that determination part 1 is also equipped with after making sampling Developer solution stabilize to as defined in the thermoregulation mechanism (not shown) of temperature improve measurement accuracy.At this point, preferable temperature tune Section mechanism is arranged in the immediately front of measuring means.Sampling piping 15 connect with the sampling pump 14 of determination part 1, export side line 16 and The piping of measuring means end connects.
Operational part 2 includes the operation mould for calculating the alkali composition concentration of such as developer solution, dissolving photoresist agent concentration Block 21.Computing module 21 is connect by signal wire with the measuring means 12,13 that determination part 1 has.It is filled in developer solution management It sets E only and has the function of and measure the density of developer solution in the case of controlling absorbing carbon dioxide concentration, need not measure Mechanism 12,13 and operational part 2.
Control unit 3 is connect by signal wire with the densimeter 11 of determination part 1.In addition, control unit 3 by signal wire with Control valve 41~43 on the pipeline for conveying from replenisher to developer solution connects.In Fig. 4, control valve 41~43 is as development The internal part of liquid managing device E and be illustrated, but control valve 41~43 be not be present embodiment developer solution managing device E Necessary parts.As long as control unit 3 feeds replenisher can be controlled the action of control valve 41~43 to developer solution Mode and control valve 41~43 get in touch with.Control valve 41~43 can also exist on except developer solution managing device E.
Then, the action of the developer solution managing device of present embodiment is illustrated.
It is adjusted from the developer solution after the sampling of developer solution storagetank 61 by trip temperature of going forward side by side is conveyed into determination part 1.Developer solution Later density value is measured by being conveyed to densimeter 11.The determination data of density is sent to control unit 3.
Control unit 3 be set with density based on developer solution and absorbing carbon dioxide concentration correspondence (such as Fig. 1 that The linear relation of sample) and the management value for being worth corresponding density with the management of absorbing carbon dioxide concentration of decision.Control unit 3 utilizes The measured value of the density of the developer solution received from determination part 1 is controlled as follows.
In the case where being managed in a manner of so that the absorbing carbon dioxide concentration of developer solution is become defined management value, Carry out following management.That is, so that the density value of the developer solution determined becomes the management value pair with absorbing carbon dioxide concentration The mode of the management value for the density answered feeds replenisher to developer solution.In view of if without concentration management, if developer solution tend to Carbon dioxide absorption is made absorbing carbon dioxide concentration increase this case, the replenisher of supply is with the suction of dilute development liquid Receive the replenisher that the mode of gas concentration lwevel acts on.
By make the absorbing carbon dioxide concentration of developer solution become defined management be worth it is below in a manner of the feelings that are managed Under condition, following management is carried out.That is, since the correspondence of the density and absorbing carbon dioxide concentration of developer solution is as shown in Figure 1 It is the relationship being increased monotonically like that, therefore so that the density value of the developer solution determined becomes the pipe with absorbing carbon dioxide concentration The management value mode below that reason is worth corresponding density feeds replenisher to developer solution.The replenisher of supply is with dilute development liquid Absorbing carbon dioxide concentration the replenisher that acts on of mode.
Here, " defined management value " refers to absorption titanium dioxide when can play best developing performance as developer solution Concentration of carbon value and the management value known in advance.Such as it is commented using the line width or residual film thickness that are obtained by development treatment When the liquid properties of valence developer solution, " defined management value " is to refer to that line width or residual film thickness is made to become desired optimum value Developer solution absorbing carbon dioxide concentration value.It is also the same in the following description.
The management of absorbing carbon dioxide concentration as developer solution, for example using 2.38%TMAH aqueous solutions as development In the case of liquid, preferably by the absorbing carbon dioxide concentration management of developer solution be 0.40 (wt%) below.It more preferably manages and is 0.25 (wt%) is below.
It should be noted that in developer solution managing device E, usually to alkali composition concentration, dissolving photoresist agent concentration It is measured and manages, therefore have the measuring means 12,13 being measured to the characteristic value of developer solution required thus.By surveying The characteristic value for determining the developer solution that mechanism 12,13 determines is sent to operational part 2.Operational part 2 is according to the developer solution determined Characteristic value calculates alkali composition concentration, dissolving photoresist agent concentration, and its result is sent to control unit 3.Control unit 3 is based on The alkali composition concentration of developer solution, dissolving photoresist concentration management are best shape by the measurement result or operation result State.
As the replenisher fed to developer solution, such as stoste or new liquid, the pure water etc. that have developer solution.These replenishers are The replenisher of absorbing carbon dioxide concentration for dilute development liquid.These replenishers can also in order to manage the alkali of developer solution at Point concentration, dissolving photoresist agent concentration and be recharged.
Replenisher is stored in the replenisher storagetank 91,92 of replenisher reservoir C.Replenisher storagetank 91,92 with have The nitrogen of valve 46,47 is connected with pipeline 86, is pressurizeed by the nitrogen supplied via the pipeline.In addition, in replenisher storagetank 91, replenisher pipeline 81,82 is connected separately on 92, replenisher is conveyed via the valve 44,45 of normally open.In replenisher It is controlled out by control unit 3 with pipeline 81,82 and pure water with control valve 41~43, control valve 41~43 is provided on pipeline 83 It closes.It is acted, is thus conveyed the supplement hydraulic coupling for being stored in replenisher storagetank 91,92, and convey by control valve Pure water.Later, replenisher collaborates via interflow pipeline 84 and with circulation stirring mechanism D, to the supply of developer solution storagetank 61 and quilt Stirring.
If make because of supply the replenisher being stored in replenisher storagetank 91,92 reduce, interior drops and cause Supply amount becomes unstable, therefore suitably opens valve 46,47 to supply nitrogen, to maintain to ensure to mend according to the reduction of replenisher The internal pressure of filling liquid storagetank 91,92.When replenisher storagetank 91,92 is emptying, valve 44,45 is closed, is changed to and is filled with supplement The new replenisher storagetank of liquid, or the replenisher separately supplied is refilled in empty replenisher storagetank 91,92.
The control of control valve 41~43 for example carries out as follows.The flow flowed through when being opened to adjustment control valve, then fight each other The time for opening control valve is managed, and thus, it is possible to the replenishers for the liquid measure to be fed.Measurement of the control unit 3 based on density Value and management are worth sends control signal so that control valve opens the stipulated time, to make the supplement for the liquid measure to be fed to control valve Liquid stream mistake.
In addition, various controlling parties used in the control for keeping controlled quentity controlled variable consistent with desired value may be used in the mode of control Method.Especially preferred proportion control (P controls) (Proportional Control), integration control (I controls) (Integral Control), differential control (D controls) (Differential Control) and control (the PI controls for being composed them Deng) (Proportional-Integral Control).More preferably applicable PID control (Proportional-Integral- Differential Control)。
As described above, the developer solution managing device of present embodiment can so that developer solution absorbing carbon dioxide concentration at It is worth mode below for defined management value or management and feeds replenisher to developer solution, to the absorbing carbon dioxide to developer solution Concentration is managed.
In addition, alarm can be sent out by alert mechanism WD in absorbing carbon dioxide deviation of concentration range of management.
(third embodiment)
Fig. 5 is the schematic diagram of following developer solution managing device, which is based on being determined by densimeter Developer solution density value, absorption titanium dioxide is calculated according to the correspondence between the density of developer solution and gas concentration lwevel Concentration of carbon, and the absorbing carbon dioxide concentration of the developer solution based on calculating come to developer solution feed replenisher, thus to developer solution Gas concentration lwevel be managed.For convenience of description, sides of the developer solution managing device E to be connect with developing procedure equipment B Formula is illustrated together with developing procedure equipment B, replenisher reservoir C, circulation stirring mechanism D.
The developer solution managing device of present embodiment is the developer solution managing device such as under type：According to the density of developer solution Measured value calculate the operational part of absorbing carbon dioxide concentration and the absorbing carbon dioxide concentration of developer solution controlled Control unit is implemented as the built-in function of the operation control mechanism (such as computer) of one.
The developer solution managing device E of present embodiment has determination part 1, calculation control unit 23 and alert mechanism WD.It measures Portion 1 has densimeter 11 and other measuring means 12,13.Calculation control unit 23 has computing module 21 and control module 31.
In determination part 1, the density value of the developer solution after sampling is measured by densimeter 11.The density value determined passes through Signal wire is sent to calculation control unit 23.In addition, the details of determination part 1 is due to same as second embodiment, thus It omits.
The calculation control unit 23 of the measured value of the density of developer solution is received using computing module 21 and based on developer solution Correspondence (such as linear relation of Fig. 1) between density and absorbing carbon dioxide concentration, is calculated according to the measured value of density Go out the absorbing carbon dioxide concentration of corresponding developer solution.Absorption titanium dioxide of the absorbing carbon dioxide concentration of calculating as developer solution The measured value of concentration of carbon and sent to control module 31.
Calculation control unit 23 can also have dense for calculating the alkali composition concentration of such as developer solution, dissolving photoresist The computing module of degree is used as calculation function.
Control module 31 based on the absorbing carbon dioxide concentration determined so that the absorbing carbon dioxide concentration of developer solution at It is worth mode below for defined management value or management and sends control signal to control valve 41~43.Developer solution tends to dioxy Change carbon absorption and gas concentration lwevel is made to increase, therefore has the function of the supplement of dilution absorbing carbon dioxide concentration by supply Liquid is controlled.The details of control is same as the explanation in second embodiment, therefore omits.
Control unit 3 can also have for controlling the alkali composition concentration of such as developer solution, dissolving photoresist agent concentration Control module is used as control function.
As described above, developer solution managing device E according to the present embodiment, can so that alkaline-based developer absorption dioxy Change concentration of carbon to be managed as defined management value or management value mode below.In addition, can be dense in absorbing carbon dioxide Alarm is sent out by alert mechanism WD when degree deviates range of management.
(the 4th embodiment)
Fig. 6 is the schematic diagram of following developer solution managing device, which is based on being determined by densimeter Developer solution density value, absorption two is calculated according to the correspondence between the density of developer solution and absorbing carbon dioxide concentration Concentration of carbon is aoxidized, the absorbing carbon dioxide concentration of the developer solution based on calculating feeds replenisher to developer solution, thus to developer solution Absorbing carbon dioxide concentration be managed.For convenience of description, developer solution managing device E with developing procedure equipment B to connect Mode be illustrated together with developing procedure equipment B, replenisher reservoir C, circulation stirring mechanism D.
The developer solution managing device of present embodiment is the developer solution managing device such as under type：According to the density of developer solution Measured value controlled with the absorbing carbon dioxide concentration to developer solution to calculate the arithmetical organ of absorbing carbon dioxide concentration Control mechanism constitute seperatedly.
The developer solution managing device E of present embodiment has determination part 1, operational part 2, control unit 3 and alert mechanism WD.It surveys Determine portion 1 and has densimeter 11 and other measuring means 12,13.Operational part 2 has computing module 21, and the computing module 21 is according to close The measured value of degree is simultaneously developed based on the correspondence (such as linear relation of Fig. 1) of density and absorbing carbon dioxide concentration to calculate The absorbing carbon dioxide concentration of liquid.Control unit 3 has control module 31, the absorbing carbon dioxide of the control module 31 based on calculating Concentration, by make developer solution absorbing carbon dioxide concentration become defined management value or management value it is below in a manner of to developer solution benefit It is controlled to replenisher.
In determination part 1, the density value of the developer solution after sampling is measured by densimeter 11.The density value determined passes through letter Number line is sent to operational part 2.In addition to this, the details of determination part 1 is same as second embodiment, therefore omits.
Receive the operational part 2 of the measured value of the density of developer solution using computing module 21 and the density based on developer solution with Correspondence (such as linear relation of Fig. 1) between absorbing carbon dioxide concentration, correspondence is calculated according to the measured value of density Developer solution absorbing carbon dioxide concentration.Absorbing carbon dioxide concentration of the absorbing carbon dioxide concentration of calculating as developer solution Measured value and sent to control unit 3.
Operational part 2 can also have for calculating the alkali composition concentration of such as developer solution, dissolving photoresist agent concentration Computing module is used as calculation function.
Control unit 3 is based on the absorbing carbon dioxide concentration determined, so that the absorbing carbon dioxide concentration of developer solution becomes Defined management value or management are worth mode below and send control signal to control valve 41~43.Developer solution tends to titanium dioxide Carbon absorption and so that gas concentration lwevel is increased, therefore by supply have the function of dilution absorbing carbon dioxide concentration replenisher To be controlled.The details of control is same as the explanation in second embodiment, therefore omits.
Control unit 3 can also have for controlling the alkali composition concentration of such as developer solution, dissolving photoresist agent concentration Control module is used as control function.
As described above, developer solution managing device E according to the present embodiment, can so that alkaline-based developer absorption dioxy Change concentration of carbon to be managed as defined management value or management value mode below.In addition, can be dense in absorbing carbon dioxide Alarm is sent out by alert mechanism WD when degree deviates range of management.
Then, the variation of the developer solution managing device E of present embodiment is illustrated.
In Fig. 4~6, the determination part 1 and operational part 2, control unit 3 of drawing out developer solution managing device are integrally formed Developer solution managing device, but it's not limited to that by the developer solution managing device E of present embodiment.Determination part 1 can also be arranged At the structure seperated with operational part 2 and control unit 3.
Each measuring means 11~13 including densimeter according to the measuring principle respectively used and there are best setting sides Method, it may be thus possible, for example, to by determination part 1 and development 80 on-line joining process of liquid pipeline, or can will measure side of the probe to impregnate Formula is set to developer solution storagetank 61.Each measuring means 11~13 can also be separately arranged.With regard to the aobvious of present embodiment For shadow liquid managing device E, as long as each measuring means 11~13 with operational part 2, control unit 3 can be measured data The scheme that the mode of exchange is mutually got in touch with, it will be able to realize.
Equally, in Fig. 4~6, densimeter is depicted and the development of mode that other measuring means 11~13 are connected in series with Liquid managing device E, but it's not limited to that by the developer solution managing device E of present embodiment.Each measuring means 11~13 can also It is connected in parallel, can also configure independently of one another.According to measuring principle used by each measuring means, reagent is if desired added, Then each measuring means can have the piping for adding reagent, if desired liquid waste, then each measuring means can have use In the pipeline of liquid waste.Even if each measuring means is not connected in series with, the developer solution management dress of present embodiment can be also realized Set E.
The operational part 2 of the developer solution managing device E of present embodiment is in addition to having density and absorption two according to developer solution The measured value of the correspondence (such as linear relation as Fig. 1) and the density based on developer solution between concentration of carbon is aoxidized to calculate Go out other than the calculation function of gas concentration lwevel, can also have other calculation functions.For example, can have for calculating development The alkali composition concentration of liquid, the calculation function for dissolving other constituent concentrations such as photoresist agent concentration.
The control unit 3 of the developer solution managing device E of present embodiment is in addition to having the absorbing carbon dioxide so that developer solution Concentration is worth mode below as defined management value or management and feeds replenisher to developer solution come the control function that is controlled Except, can also have other control functions.For example, can have alkali composition concentration, dissolving photoresist so that developer solution Other constituent concentrations such as agent concentration become defined management value or management value or less or fall into the side in defined range of management The control function that formula is controlled.The control carried out thus is in addition to being the control carried out by feeding replenisher to developer solution In addition, can also suitably add by developer solution discard control, it is additional make to filter out impurity by filter etc. and after regenerating again The various controls such as the control that raw developer solution returns.
In Fig. 4~6, depict in a manner of making internal part of the control valve 41~43 as developer solution managing device E The scheme that developer solution managing device E is connect with replenisher pipeline 81,82 and pure water pipeline 83, wherein control valve 41~ 43 are arranged on the pipeline of replenisher that conveying is fed to developer solution, but the developer solution managing device E of present embodiment and unlimited Due to this.Developer solution managing device can not also by control valve 41~43 as internal part be arranged, can not also with for The pipeline 81~83 that developer solution feeds replenisher connects.
For the developer solution managing device E of present embodiment, as long as control unit 3 with set on for feeding replenisher Control valve 41~43 on pipeline is so that control valve 41~43 receives the control sent by the control unit 3 of developer solution managing device E The scheme that signal and the mode that is controlled mutually are got in touch with.Even if control valve does not become the inside portion of developer solution managing device E Part can also realize the developer solution managing device E of present embodiment.
The control unit 3 of developer solution managing device E can not also be integrally formed with determination part 1, operational part 2, can be with survey Determine portion 1, operational part 2 is constituted seperatedly.Determination part 1, operational part 2 and control unit 3 can exist as device independent of each other. As long as being got in touch in a manner of being exchanged with each other determination data, operation result, control signal etc. by signal wire etc., then all It can realize the developer solution managing device E of present embodiment.
It is preferred that the function that absorbing carbon dioxide concentration is controlled of control unit 3 with to alkali composition concentration, dissolving it is photic The function that other ingredients such as agent concentration against corrosion are controlled is realized by shared control mechanism, but each function can also pass through Seperated control mechanism is realized.Replenisher, the pipeline for conveying replenisher and control valve etc. used in control can be according to wanting The object component of the developer solution of control and prepare respectively, but as long as being commonly to use, then preferably share.
Although the developer solution managing device of the present invention allows above-mentioned various variation, needs to be configured to have density Instrument uses the correspondence (such as linear relation as Fig. 1) between the density and absorbing carbon dioxide concentration of developer solution, base It is calculated in the density value of the developer solution determined by densimeter or according to the density value of the developer solution determined by densimeter Developer solution absorbing carbon dioxide concentration value so that the absorbing carbon dioxide concentration of developer solution become defined management value or pipe Reason value mode below feeds replenisher to be controlled to developer solution.
As described above, developer solution managing device according to the present invention, it can be dense by the absorbing carbon dioxide of alkaline-based developer Degree management is defined management value or management value or less.Thus, developer solution managing device according to the present embodiment can be by alkali Property developer solution be maintained play best developing performance absorbing carbon dioxide concentration state, can realize desired line width Or residual film thickness.
The developer solution managing device of the present invention can also be to the alkali composition concentration of alkaline-based developer, dissolving photoresist In the case that concentration is managed, each constituent concentration of alkaline-based developer is managed as defined state.Therefore, with can not to inhale It receives the existing developer solution management that gas concentration lwevel is managed to compare, developer solution managing device according to the present invention can The developing performance of alkaline-based developer is further precisely maintained to management to fix.Thus, it is possible to expect following effect： Developing powder stabilization when developing to photoresist turns to fixation, and line width or residual film thickness based on development treatment are consolidated Fixedization, product quality are improved, and help to realize further miniaturization and highly integrated.
In turn, developer solution managing device according to the present invention, development liquid energy automatically maintain into best developability always Can, therefore can expect following effect：Finished product rate is improved, and does not need the replacement operation of developer solution, helps to run The reduction of cost and waste liquid cost.

Claims (8)

1. a kind of concentration monitoring arrangement of developer solution, wherein
The concentration monitoring arrangement of the developer solution has：
Densimeter；
Arithmetical organ, based on the density value of the developer solution for showing alkalinity determined by the densimeter, according to the development Correspondence between the density and absorbing carbon dioxide concentration of liquid calculates the absorbing carbon dioxide concentration of the developer solution；With And
Alert mechanism is set in advance in the absorbing carbon dioxide concentration value deviation of the developer solution calculated by the arithmetical organ Alarm is sent out when fixed range of management.
2. the concentration monitoring arrangement of developer solution according to claim 1, wherein
The concentration monitoring arrangement of the developer solution has the external output signal terminal for sending alarm signal, the police to sound the alarm Reporting device, light are lighted or the emergency warning lamp flickered, the Converting terminal for showing the display device of warning and the opening and closing of double-throw contact In either one be used as the alert mechanism.
3. a kind of developer solution managing device, wherein
The developer solution managing device has：
Densimeter；
Control mechanism uses the development based on the density value of the developer solution for showing alkalinity determined by the densimeter Correspondence between the density and absorbing carbon dioxide concentration of liquid, so that the absorbing carbon dioxide concentration of the developer solution becomes Defined management value or management are worth mode below and send control signal to control valve, and the control valve setting is being conveyed to institute On the pipeline for stating the replenisher of developer solution supply；And
Alert mechanism deviates in the density value of the developer solution determined by the densimeter and absorbs two with preset Alarm is sent out when the corresponding density range of range of management for aoxidizing concentration of carbon, the density range is according to the close of the developer solution It spends and the correspondence between absorbing carbon dioxide concentration and determination.
4. developer solution managing device according to claim 3, wherein
The developer solution managing device has the external output signal terminal for sending alarm signal, the alarm to sound the alarm dress Set, light is lighted or flicker emergency warning lamp, display warning display device and double-throw contact opening and closing Converting terminal in Either one is used as the alert mechanism.
5. a kind of developer solution managing device, wherein
The developer solution managing device has：
Densimeter；
Operation control mechanism, has operational part and control unit, and the operational part is shown based on what is determined by the densimeter The density value of the developer solution of alkalinity, is calculated according to the correspondence between the density of the developer solution and absorbing carbon dioxide concentration Go out the gas concentration lwevel of the developer solution, absorption two of the control unit based on the developer solution calculated by the operational part Concentration of carbon is aoxidized, so that the absorbing carbon dioxide concentration of the developer solution becomes defined management value or management is worth side below Formula sends control signal to control valve, and the control valve is arranged on the pipeline for the replenisher that conveying is fed to the developer solution； And
Alert mechanism is preset in the absorbing carbon dioxide concentration value deviation of the developer solution calculated by the operational part Range of management when send out alarm.
6. developer solution managing device according to claim 5, wherein
The developer solution managing device has the external output signal terminal for sending alarm signal, the alarm to sound the alarm dress Set, light is lighted or flicker emergency warning lamp, display warning display device and double-throw contact opening and closing Converting terminal in Either one is used as the alert mechanism.
7. a kind of developer solution managing device, wherein
The developer solution managing device has：
Densimeter；
Arithmetical organ, based on the density value of the developer solution for showing alkalinity determined by the densimeter, according to the development Correspondence between the density and absorbing carbon dioxide concentration of liquid calculates the absorbing carbon dioxide concentration of the developer solution；
Control mechanism, based on the absorbing carbon dioxide concentration of the developer solution calculated by the arithmetical organ, so that described The absorbing carbon dioxide concentration of developer solution becomes defined management value or management is worth mode below and sends control to control valve Signal, the control valve are arranged on the pipeline for the replenisher that conveying is fed to the developer solution；And
Alert mechanism is set in advance in the absorbing carbon dioxide concentration value deviation of the developer solution calculated by the arithmetical organ Alarm is sent out when fixed range of management.
8. developer solution managing device according to claim 7, wherein
The developer solution managing device has the external output signal terminal for sending alarm signal, the alarm to sound the alarm dress Set, light is lighted or flicker emergency warning lamp, display warning display device and double-throw contact opening and closing Converting terminal in Either one is used as the alert mechanism.
CN201711232885.8A 2017-01-23 2017-11-29 The concentration monitoring arrangement and developer solution managing device of developer solution Pending CN108345185A (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004520585A (en) * 2001-01-19 2004-07-08 クラリアント・インターナシヨナル・リミテッド Titration method for aqueous base developer solution
JP2005070351A (en) * 2003-08-22 2005-03-17 Nagase & Co Ltd Method and apparatus for supplying developing solution
CN101563654A (en) * 2006-11-30 2009-10-21 三菱化学工程株式会社 Method for regulating concentration of developing solution, apparatus for preparing the developing solution, and developing solution
CN106094897A (en) * 2016-06-24 2016-11-09 重庆广播电视大学 A kind of computer based gas concentration lwevel monitoring system

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2561578B2 (en) 1991-08-07 1996-12-11 株式会社平間理化研究所 Developer management device
JP3534211B2 (en) * 1995-09-29 2004-06-07 富士写真フイルム株式会社 Automatic developing system for photosensitive lithographic printing plate
JP2006268023A (en) * 2005-02-23 2006-10-05 Fuji Photo Film Co Ltd Method for controlling development in automatic developing device for photosensitive lithographic printing plate and automatic developing device therefor
JP2011128455A (en) 2009-12-18 2011-06-30 Nagase & Co Ltd Device for measuring concentration of carbonic acid-based salt, system for controlling alkali developing solution, and method for measuring concentration of carbonic acid-based salt
JP2012225709A (en) * 2011-04-18 2012-11-15 Toshiba Corp Carbon dioxide concentration measurement instrument, carbon dioxide concentration measurement method, and carbon dioxide collection system
JP6713658B2 (en) * 2015-07-22 2020-06-24 株式会社平間理化研究所 Component concentration measuring device for developer, component concentration measuring method, developer controlling device, and developer controlling method
JP6763608B2 (en) * 2017-01-23 2020-09-30 株式会社平間理化研究所 Carbon dioxide concentration display device for developer and developer management device
JP6712415B2 (en) * 2017-01-23 2020-06-24 株式会社平間理化研究所 Developer management device

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004520585A (en) * 2001-01-19 2004-07-08 クラリアント・インターナシヨナル・リミテッド Titration method for aqueous base developer solution
JP2005070351A (en) * 2003-08-22 2005-03-17 Nagase & Co Ltd Method and apparatus for supplying developing solution
CN101563654A (en) * 2006-11-30 2009-10-21 三菱化学工程株式会社 Method for regulating concentration of developing solution, apparatus for preparing the developing solution, and developing solution
CN106094897A (en) * 2016-06-24 2016-11-09 重庆广播电视大学 A kind of computer based gas concentration lwevel monitoring system

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Application publication date: 20180731