CN108345186A - Developer solution managing device - Google Patents

Developer solution managing device Download PDF

Info

Publication number
CN108345186A
CN108345186A CN201711234783.XA CN201711234783A CN108345186A CN 108345186 A CN108345186 A CN 108345186A CN 201711234783 A CN201711234783 A CN 201711234783A CN 108345186 A CN108345186 A CN 108345186A
Authority
CN
China
Prior art keywords
developer solution
concentration
carbon dioxide
managing device
value
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201711234783.XA
Other languages
Chinese (zh)
Inventor
中川俊元
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hirama Rika Kenkyusho Ltd
Hirama Laboratories Co Ltd
Original Assignee
Hirama Rika Kenkyusho Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Hirama Rika Kenkyusho Ltd filed Critical Hirama Rika Kenkyusho Ltd
Publication of CN108345186A publication Critical patent/CN108345186A/en
Pending legal-status Critical Current

Links

Classifications

    • 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
    • G03F7/0032—Devices or apparatus characterised by heat providing or glossing means
    • 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
    • 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
    • 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
    • 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

Landscapes

  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Automation & Control Theory (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Manufacturing & Machinery (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)
  • Exposure Of Semiconductors, Excluding Electron Or Ion Beam Exposure (AREA)

Abstract

The present invention provides developer solution managing device, can realize can maintain desired developing performance and can maintain the desired line width of the wiring pattern on substrate and the development treatment of residual film thickness, and monitor conductivity, dissolving photoresist agent concentration and the absorbing carbon dioxide concentration of developer solution.Have control mechanism and alert mechanism, control mechanism has：Data store, it is stored with conductivity data, the conductivity data has the conductivity values of the developer solution of developing performance as defined in confirmed to realize in advance according to the concentration range of determination with the dissolving photoresist agent concentration and a concentration of index of absorbing carbon dioxide；And control unit, using the conductivity values of identified concentration range as control targe value, signal is sent to control valve in a manner of so that the conductivity is become control targe value, either one of alert mechanism in the conductivity, dissolving photoresist agent concentration and absorbing carbon dioxide concentration sends out alarm when deviateing the range of management of setting.

Description

Developer solution managing device
Technical field
The present invention relates to the management method of developer solution and developer solution managing device, be especially for in semiconductor or In developing procedure of the circuit board of liquid crystal display panel etc. in order to make photoresist film develop and Reusability show alkalinity The developer solution managing device that developer solution is managed.
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.
What the measurement of the constituent concentration of existing alkaline-based developer utilized be the alkali composition of alkaline-based developer concentration it is (following Referred to as " alkali composition concentration ") good linear relation this principle (for example, patent document 1) can be obtained between conductivity.
However, in recent years, causing the chance that alkaline-based developer is contacted with air to increase due to development treatment, alkaline development Liquid can absorb the carbon dioxide in air, and therefore, the uptake of the carbon dioxide of alkaline-based developer increases.If the titanium dioxide absorbed Concentration of carbon is got higher, then in the developer solution management carried out based on existing method, generation is unable to maintain that defined line width processing etc. is asked Topic.
The reason of causing the problem is as follows：The alkali composition with developing activity in alkaline-based developer is due to carbon dioxide Absorb and be generated the reaction consumption of carbonate.In addition, the reason of causing the problem also has：There is development in alkaline-based developer Active alkali composition is generated the reaction consumption of photoresist salt due to the dissolving of photoresist.
For this problem, the development liquid pipe that the various alkali compositions reduced to being consumed are fed has been attempted Reason.Above-mentioned trial carries out as follows：Carbonate concentration is measured, to be consumed to the reaction for being generated carbonate using replenisher Alkali composition is fed and is made the concentration immobilization of the alkali composition with developing activity.For the dissolving because of photoresist by The alkali composition consumed is also the same.Above-mentioned trial can lose developing activity from the alkali composition for becoming carbonate or photoresist salt And it is feasible (for example, patent document 2) to cause to inactivate for such viewpoint.
Citation
Patent document
Patent document 1：No. 2561578 bulletins of Japanese Patent No.
Patent document 2：Japanese Unexamined Patent Publication 2008-283162 bulletins
However, the trial using above-mentioned various developer solution management is still difficult to realize satisfied developer solution management.
Invention content
The subject that the invention solves
The present inventor carefully studies for developer solution management and is found：Carbonate or resist salt in developer solution one Part occurs free and may also contribute to development effect, moreover, by be considered as inactivation mentioned component tribute that development is acted on Offering the developer solution management taken into account can be managed by the conductivity values to developer solution to realize, in addition, such The management value of conductivity is various according to absorbing carbon dioxide concentration and dissolving photoresist agent concentration.
Think the foundation of above-mentioned discovery：Become the alkali composition of carbonate or photoresist salt and non-deactivated, but one Distribution is raw free and development is contributed to act on, moreover, the alkali composition with developing activity, it is free from carbonate and resist salt and Can conductivity be acted by contributing to the ingredient that development acts on.That is, inventor has found that the ingredient with development effect is overall On be managed using the conductivity values of developer solution if can manage into it is best, thereby completing the present invention.
The present invention is proposed in order to solve above-mentioned problem, and it is an object of the present invention to provide can be to as defined in photoresist realization The developer solution managing device of developing performance.
Solution for solving the problem
In order to reach the purpose, developer solution managing device of the invention has control mechanism and alert mechanism, the control Mechanism processed has：Data store is stored with conductivity data, and the conductivity data is according to Reusability and showing alkalinity Developer solution dissolving photoresist agent concentration and a concentration of index of absorbing carbon dioxide and determination concentration range, have advance It confirmed the conductivity values of the developer solution of developing performance as defined in realizing；And control unit, it will be according to the developer solution Dissolving photoresist agent concentration measured value and absorbing carbon dioxide concentration measured value and the concentration range of determination storage In the data store the conductivity values as control targe value so that the conductivity of the developer solution becomes the control The mode of desired value processed 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, the alert mechanism is in the conductivity of the developer solution, dissolving photoresist agent concentration and absorbing carbon dioxide Alarm is sent out when the range of management of either one deviation setting in concentration.
In order to reach the purpose, developer solution managing device of the invention has control mechanism, and the control mechanism has： Data store is stored with conductivity data, and the conductivity data is according to Reusability and showing the developer solution of alkalinity The concentration range of photoresist agent concentration and a concentration of index of absorbing carbon dioxide and determination is dissolved, has and confirmed to realize in advance The conductivity values of the developer solution of defined developing performance；And control unit, it will be photic according to the dissolving of the developer solution The measured value of agent concentration against corrosion and the measured value of absorbing carbon dioxide concentration and the concentration range of determination are stored in the data The conductivity values of storage part are as control targe value, so that the conductivity of the developer solution becomes the control targe value Mode sends control signal to control valve, and the pipeline of the replenisher fed to the developer solution in conveying is arranged in the control valve On, in the developer solution managing device, according to the conductivity of the developer solution, dissolving photoresist agent concentration and absorb dioxy Change concentration of carbon and be provided with alert mechanism, the alert mechanism is in the conductivity of the developer solution, dissolving photoresist agent concentration and suction It receives when gas concentration lwevel deviates the range of management of setting and sends out alarm.
Developer solution managing device according to the present invention, no matter developer solution dissolving photoresist agent concentration and absorb titanium dioxide What concentration of carbon becomes, and can be maintained active ingredient is acted on to development in developer solution into fixation, therefore energy It enough maintains desired developing performance and maintains the desired line width and residual film thickness of the wiring pattern on substrate, and can Monitor the concentration of developer solution.
The preferred mode of developer solution managing device according to the present invention, the developer solution managing device have transmission alarm The external output signal terminal of signal, the alarm device to sound the alarm, light light or flicker emergency warning lamp, display warning Either one in the Converting terminal of the opening and closing of display device and double-throw contact is used as the alert mechanism.
The preferred mode of developer solution managing device according to the present invention, the developer solution managing device are also equipped with multiple surveys Determine device, the multiple measurement device is associated described aobvious to having comprising the dissolving photoresist agent concentration with the developer solution The characteristic value of shadow liquid and including there is the characteristic value of the associated developer solution with the absorbing carbon dioxide concentration of the developer solution Multiple characteristic values of the developer solution be measured, the control mechanism is also equipped with operational part, and the operational part is according to by institute It states the multiple characteristic values for the developer solution that multiple measurement devices determine and calculates the development using multiple-regression analysis The measured value of the dissolving photoresist agent concentration of liquid and the measured value of absorbing carbon dioxide concentration.
The preferred mode of developer solution managing device according to the present invention, the developer solution managing device are also equipped with：It is multiple Measurement device, to having the characteristic value of the associated developer solution comprising the dissolving photoresist agent concentration with the developer solution And there is the developer solution including the characteristic value of the associated developer solution with the absorbing carbon dioxide concentration of the developer solution Multiple characteristic values be measured；And arithmetical organ, according to the developer solution determined by the multiple measurement device Multiple characteristic values and calculated using multiple-regression analysis the developer solution dissolving photoresist agent concentration measured value and The measured value of absorbing carbon dioxide concentration.
The preferred mode of developer solution managing device according to the present invention, the developer solution managing device have densimeter, The control mechanism is also equipped with operational part, between absorbing carbon dioxide concentration and density of the operational part based on the developer solution Correspondence, the absorption two of the developer solution is calculated according to the density value of the developer solution determined by the densimeter Carbonoxide concentration value.
The preferred mode of developer solution managing device according to the present invention, the developer solution managing device are also equipped with：Density Instrument；And arithmetical organ, the correspondence between absorbing carbon dioxide concentration and density based on the developer solution, according to by The density value for the developer solution that the densimeter determines calculates the absorbing carbon dioxide concentration value of the developer solution.
Developer solution managing device according to the present invention, the developer solution managing device have control mechanism and alert mechanism, The control mechanism has：Data store is stored with alkali composition concentration data, and the alkali composition concentration data is according to repeatedly Using and show alkalinity developer solution with dissolving photoresist agent concentration have associated absorbance and absorbing carbon dioxide it is dense Degree concentration range of determination for index, has the alkali composition of the developer solution of developing performance as defined in confirmed to realize in advance Concentration value；And control unit, it will be determined according to the measured value of the absorbance of the developer solution and absorbing carbon dioxide concentration Concentration range the alkali composition concentration value for being stored in the data store as control targe value so that the development The mode that the alkali composition concentration of liquid becomes the control targe value sends control signal to control valve, and the control valve is arranged defeated It is sent on the pipeline of the replenisher of the developer solution supply, the alert mechanism is in the alkali composition concentration of the developer solution, extinction Alarm is sent out when the range of management of either one deviation setting in degree and absorbing carbon dioxide concentration.
Developer solution managing device according to the present invention, the developer solution managing device have control mechanism, the control machine Structure has：Data store is stored with alkali composition concentration data, and the alkali composition concentration data is according to Reusability and showing The developer solution of alkalinity with dissolving photoresist agent concentration there is associated absorbance and a concentration of index of absorbing carbon dioxide and Determining concentration range has the alkali composition concentration value of the developer solution of developing performance as defined in confirmed to realize in advance；With And control unit, by the concentration range of determination according to the measured value of the absorbance of the developer solution and absorbing carbon dioxide concentration The alkali composition concentration value for being stored in the data store as control targe value so that the alkali composition of the developer solution The mode that concentration becomes the control targe value sends control signal to control valve, and the control valve setting is being conveyed to described aobvious On the pipeline of the replenisher of shadow liquid supply, in the developer solution managing device, according to the alkali composition concentration of the developer solution, inhale Luminosity and absorbing carbon dioxide concentration are provided with alert mechanism, and the alert mechanism is in the alkali composition concentration of the developer solution, extinction Alarm is sent out when degree and the range of management of absorbing carbon dioxide deviation of concentration setting.
The preferred mode of developer solution managing device according to the present invention, the developer solution managing device have transmission alarm The external output signal terminal of signal, the alarm device to sound the alarm, light light or flicker emergency warning lamp, display warning Either one in the Converting terminal of the opening and closing of display device and double-throw contact is used as the alert mechanism.
Invention effect
According to the present invention, no matter developer solution dissolving photoresist agent concentration and absorbing carbon dioxide concentration what becomes Sample, can will be in developer solution active ingredient is acted on to development maintain into fixation, therefore can realize and can maintain institute Desired developing performance and the desired line width of wiring pattern on substrate and the development treatment of residual film thickness can be maintained, and It can monitor the concentration of developer solution.
Description of the drawings
Fig. 1 is the schematic diagram of the developing procedure of the developer solution managing device for illustrating first embodiment.
Fig. 2 is the schematic diagram of the developing procedure of the developer solution managing device for illustrating second embodiment.
Fig. 3 is the schematic diagram of the developing procedure of the developer solution managing device for illustrating third embodiment.
Fig. 4 is the schematic diagram of the developing procedure of the developer solution managing device for illustrating the 4th embodiment.
Fig. 5 is the chart of the relationship of the absorbing carbon dioxide concentration and density that indicate developer solution.
Fig. 6 is the schematic diagram of the developing procedure of the developer solution managing device for illustrating the 5th embodiment.
Drawing reference numeral explanation
A ... developing procedures equipment, B ... replenishers reservoir, C ... circulation stirrings mechanism, D ... developer solution managing devices
1 ... determination part
It is 11 ... conductivity meters, 12 ... first concentration mensuration mechanisms, the first characteristic values of 12A ... measuring means, 13 ... second dense Spend measuring means, the second characteristic values of 13A ... measuring means, 13B ... densimeters
14 ... sampling pumps, 15 ... sampling pipings, 16 ... outlet side lines
21 ... control mechanisms (such as computer)
23 ... data stores,
31 ... control units, 32,33 ... operational parts, 36,37 ... arithmetical organs
41~43 ... control valves, 44,45,46,47 ... valves
61 ... developer solution storagetanks, 62 ... overflow launders, 63 ... liquid level meters, 64 ... developing room shields, 65 ... roller conveyors, 66 ... substrates, 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 lines, 86 ... nitrogen pipelines
91,92 ... replenishers (development stoste and/or new liquid) storagetank
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 Management method, the example of other developer solutions that can be applicable in of managing device, potassium hydroxide, sodium hydroxide, phosphorus can also be enumerated The organic compounds such as the aqueous solution or trimethyl monoethanol base ammonium hydroxide (choline) of the inorganic compounds such as sour sodium, sodium metasilicate Aqueous solution.
In the following description, the ingredients such as alkali composition concentration, dissolving photoresist agent concentration, absorbing carbon dioxide concentration are dense Degree is the concentration based on weight percent concentration (wt%)." dissolving photoresist agent concentration " refers to the photoresist that will be dissolved It is converted into the concentration in the case of the amount of photoresist, " absorbing carbon dioxide concentration " refers to changing absorbed carbon dioxide It is counted as 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, The absorbed carbon dioxide-depleted of the alkali composition with developing activity in developer solution and reduce.Meanwhile being absorbed in developer solution Carbon dioxide is reacted with alkali composition and is constantly accumulated in the form of carbonate.
However, the carbonate in developer solution shows alkalinity in developer solution, therefore there is development effect.
In this way, different from " carbon dioxide that the photoresist dissolved in developer solution or developed liquid absorb can make development Existing cognition as the developing activity inactivation of processing ", in fact, the photoresist dissolved in developer solution or developed liquid are inhaled The carbon dioxide of receipts contributes to the developing performance of developer solution.Therefore, it is not into being about to dissolve photoresist or absorption Carbon dioxide excludes such developer solution management completely, but needs to carry out following developer solution management, that is, allows in developer solution In it is molten have dissolving photoresist or absorbing carbon dioxide and by they maintain management at best concentration.
In addition, a part for the photoresist salt or carbonate that generate in developer solution dissociates, and generate photic Various dissociated ion such as resist ion or carbonate ions, carbonic acid hydrogen ion.Also, these dissociated ions are with various Activity ratio has an impact the conductivity of developer solution.
Based on above-mentioned point, the present inventor carefully studies developer solution management and finds：Carbonate or resist salt exist A part occurs free and may also contribute to development effect in developer solution, moreover, will be considered as the mentioned component of inactivation to aobvious The developer solution management that the contribution of shadow effect takes into account can be managed to realize, separately by the conductivity values to developer solution Outside, the management value of such conductivity is various according to absorbing carbon dioxide concentration and dissolving photoresist agent concentration.
Therefore, the case where inventor assumes to carry out the management as the TMAH aqueous solutions of developer solution, makes dissolving photoresist Agent concentration, absorbing carbon dioxide concentration various change, so as to find out to the desired developing performance of photoresist and developer solution The relationship of conductivity values.
Absorbing carbon dioxide concentration of sening as an envoy to is modulated to change between 0.0~1.3 (wt%) and keep dissolving photoresist dense Degree is in 0.0~0.40 (wt%) (being equivalent to the absorbance 0.0~1.3 (abs) under wavelength 560nm) (hereinafter, sometimes similarly one And be denoted as concentration and absorbance) between variation gained TMAH aqueous solutions developer solution sample.Inventor is directed to these samples Following experiment is carried out：The conductivity, absorbing carbon dioxide concentration and dissolving photoresist agent concentration of developer solution are measured, and really Recognize the correlation between developing performance and conductivity, absorbing carbon dioxide concentration and dissolving photoresist concentration components.It makes Absorbing carbon dioxide concentration is transversely or longitudinally arranged as a project and photoresist agent concentration will be dissolved as it Its project and matrix (combination table) made of transversely or longitudinally arranging.According to absorbing carbon dioxide concentration and dissolving photoresist Each combination of agent concentration to solve the conductivity met to the developer solution of the desired developing performance of photoresist, and is included in Matrix is completed on each column.
Here, it is specified that developing performance refer to the line width for realizing the wiring pattern on the substrate to be realized in developing procedure Or the developing performance of developer solution when residual film thickness.
Exemplify the survey of the absorbing carbon dioxide concentration, dissolving photoresist agent concentration and conductivity of representative each sample Determine result.(it is equivalent to 0.0 in absorbing carbon dioxide a concentration of 0.0 (wt%), dissolving photoresist a concentration of 0.0 (wt%) (abs)) in the case of (so-called new liquid), the conductivity that can play the developer solution of defined developing performance is 54.58 (mS/ cm)。
It (is equivalent in absorbing carbon dioxide a concentration of 0.0 (wt%), dissolving photoresist a concentration of 0.25 (wt%) In the case of 0.8abs), the conductivity that can play the developer solution of defined developing performance is 54.55 (mS/cm), in dissolving light In the case of causing resist a concentration of 0.40 (wt%) (being equivalent to 1.3abs), the conductivity of developer solution is 54.53 (mS/cm).
In addition, in dissolving photoresist a concentration of 0.0 (wt%) (being equivalent to 0.0 (abs)), absorbing carbon dioxide concentration In the case of 0.6 (wt%), the conductivity of developer solution is 54.60 (mS/cm), in absorbing carbon dioxide a concentration of 1.3 (wt%) in the case of, the conductivity of developer solution is 54.75 (mS/cm).
In addition, in absorbing carbon dioxide a concentration of 0.6 (wt%), dissolving photoresist a concentration of 0.22 (wt%) (phase When in 0.7abs) in the case of, the conductivity of developer solution is 54.60 (mS/cm), in dissolving photoresist a concentration of 0.40 (wt%) in the case of (relative to 1.3abs), the conductivity of developer solution is 54.58 (mS/cm).
In addition, in absorbing carbon dioxide a concentration of 1.3 (wt%), dissolving photoresist a concentration of 0.22 (wt%) (phase When in 0.7abs) in the case of, the conductivity of developer solution is 54.75 (mS/cm), in dissolving photoresist a concentration of 0.40 (wt%) in the case of (being equivalent to 1.3abs), the conductivity of developer solution is 54.75 (mS/cm).
It should be noted that in above-mentioned experiment, in certain concentration range, if absorbing carbon dioxide concentration becomes larger, The management value of conductivity is intended to become larger, if dissolving photoresist agent concentration becomes larger, the management value of conductivity is intended to become smaller.
In above-mentioned experiment, the conductivity of the developer solution of each sample has used the value determined using conductivity meter.It inhales It receives gas concentration lwevel and has used the value determined using analysis by titration.Dissolving photoresist agent concentration has used weight modulation Value.Titration is using hydrochloric acid as the acid-base titration of titer reagent.As titration outfit, analytical technology company of Mitsubishi Chemical has been used The automatic titration device GT-200 of system.
It should be noted that above-mentioned conductivity, absorbing carbon dioxide concentration and dissolving photoresist agent concentration are for looking for Go out conductivity, absorbing carbon dioxide concentration and dissolving photoresist agent concentration and developing performance between it is relational, do not limit In each numerical value.
As discussed above, it should be understood that being that can play the conductivity of developing performance according to absorbing carbon dioxide concentration and molten Solve photoresist agent concentration and it is various.In this way, in the management of developer solution, photic comprising absorbing carbon dioxide and dissolving In the developer solution of resist, by regarding conductivity as management value and measuring absorbing carbon dioxide concentration and dissolving photoresist Concentration keeps the management value of conductivity different based on each measurement result, and thus, it is possible to play defined developing performance.
That is, storage is determined according to a concentration of index of dissolving photoresist agent concentration and absorbing carbon dioxide with developer solution Concentration range and the conductivity values of developer solution with developing performance as defined in confirmed to realize in advance conductivity data (square Battle array), by using conductivity data (matrix), and it can realize the management for the developer solution that can play defined developing performance.
In addition, inventor to developer solution management carefully study and find：Carbonate or resist salt are in developer solution A middle part occurs free and may also contribute to development effect, moreover, will be considered as that the mentioned component inactivated acts on development The developer solution management that takes into account of contribution can be managed by the alkali composition concentration value to developer solution to realize, separately Outside, the management value of such alkali composition concentration value has phase according to absorbing carbon dioxide concentration and with dissolving photoresist agent concentration The absorbance of pass relationship and it is various.
Therefore, the case where inventor assumes to carry out the management as the TMAH aqueous solutions of developer solution makes to be based on showing alkalinity Developer solution conductivity and measure alkali composition concentration, with the dissolving photoresist agent concentration of developer solution there is correlativity Absorbance, the absorbing carbon dioxide concentration various change of developer solution, and find out to the desired developing performance of photoresist and show The relationship of the alkali composition concentration of shadow liquid.
Absorbing carbon dioxide concentration of sening as an envoy to is modulated to change between 0.0~1.3 (wt%) and make and dissolving photoresist Absorbance of the concentration with correlativity changes the sample of the developer solution of the TMAH aqueous solutions of gained between 0.0~1.3 (abs) This.Inventor has carried out following experiment for these samples：Measure the alkali composition concentration of developer solution, absorbing carbon dioxide concentration and Absorbance, and confirm developing performance and alkali composition concentration, the correlation of absorbing carbon dioxide concentration and absorbance.Producing will inhale Gas concentration lwevel is received transversely or longitudinally to arrange as a project and absorbance is lateral or vertical as other projects Matrix (combination table) made of being arranged to ground.According to each combination of absorbing carbon dioxide concentration and absorbance, meet to solve To the alkali composition concentration of the developer solution of the desired developing performance of photoresist, and it is included in each column, completes matrix.
Here, it is specified that developing performance refer to the line width for realizing the wiring pattern on the substrate to be realized in developing procedure Or the developing performance of developer solution when residual film thickness.
Exemplify the absorbing carbon dioxide concentration of representative each sample, the measurement result of absorbance and alkali composition concentration. In the case where absorbing carbon dioxide a concentration of 0.0 (wt%), absorbance are 0.0 (abs) (so-called new liquid), rule can be played The alkali composition a concentration of 2.380 (wt%) of the developer solution of fixed developing performance.
In the case where absorbing carbon dioxide a concentration of 0.0 (wt%), absorbance are 0.8abs, can play defined aobvious The alkali composition a concentration of 2.379 (wt%) of the developer solution of shadow performance, in the case where absorbance is 1.3abs, the alkali of developer solution at Divide a concentration of 2.378 (wt%).
In addition, in the case where absorbance is 0.0 (abs), absorbing carbon dioxide a concentration of 0.6 (wt%), developer solution Alkali composition a concentration of 2.381 (wt%), in the case of absorbing carbon dioxide a concentration of 1.3 (wt%), the alkali composition of developer solution A concentration of 2.388 (wt%).
In addition, in the case where absorbing carbon dioxide a concentration of 0.6 (wt%), absorbance are 0.7abs, the alkali of developer solution Constituent concentration is 2.381 (wt%), in the case where absorbance is 1.3abs, the alkali composition a concentration of 2.380 of developer solution (wt%).
In addition, in the case where absorbing carbon dioxide a concentration of 1.3 (wt%), absorbance are 0.7abs, the alkali of developer solution Constituent concentration is 2.388 (wt%), in the case where absorbance is 1.3abs, the alkali composition a concentration of 2.388 of developer solution (wt%).
It should be noted that in above-mentioned experiment, in certain concentration range, if absorbing carbon dioxide concentration becomes larger, The management value of alkali composition concentration is intended to become larger, if absorbance becomes larger, the management value of alkali composition concentration is intended to become smaller.
In above-mentioned experiment, the alkali composition concentration of the developer solution of each sample can be by measuring conductivity with conductivity meter To solve.Specifically, in advance by the alkali composition concentration of the new liquid of TMAH aqueous solutions (the TMAH aqueous solutions before development) and conduction The correlativity (such as linear relation) of rate value is made for calibration curve.It can be solved based on the calibration curve and according to conductivity values Alkali composition concentration.
Absorbing carbon dioxide concentration has used the value determined using analysis by titration.Titration is tried hydrochloric acid as titration The acid-base titration of agent.As titration outfit, the automatic titration device GT-200 of Mitsubishi Chemical's analytical technology corporation has been used.It inhales The measurement of luminosity has used extinction photometer.
It should be noted that above-mentioned alkali composition concentration, absorbing carbon dioxide concentration and absorbance are for finding out alkali composition It is relational between concentration, absorbing carbon dioxide concentration and absorbance and developing performance, it is not limited to each numerical value.
As discussed above, it should be understood that being：The alkali composition concentration of developing performance can be played according to absorbing carbon dioxide concentration And absorbance and it is various.In this way, in the management of developer solution, comprising absorbing carbon dioxide and dissolving photoresist In developer solution, by the way that alkali composition concentration to be used as to the management value of developer solution and measures absorbing carbon dioxide concentration and absorbance, base Keep the management value of alkali composition concentration different in each measurement result, thus, it is possible to play defined developing performance.
That is, storage according to the absorbance of developer solution and a concentration of index of absorbing carbon dioxide and the concentration range of determination and The alkali composition concentration data (matrix) of alkali composition concentration value with the developer solution that confirmed to realize defined developing performance in advance, By using alkali composition concentration data (matrix), and defined developing performance can be played.
Then, specific embodiment is illustrated with reference to attached drawing.
(first embodiment)
Fig. 1 is the schematic diagram of the developing procedure of the developer solution managing device D for illustrating present embodiment.The present invention's is aobvious Shadow liquid managing device D and developing procedure device A, replenisher reservoir B, circulation stirring mechanism C etc. are illustrated together.
First, developing procedure device A is simply illustrated.
Developing procedure device A 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 is recycled and is stored 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, also sometimes through It is handled as the carbon dioxide in air full of modes such as nitrogen to implement to prevent to absorb.It should be noted that deteriorate Developer solution is discarded (discharge) by so that waste drains pump 71 is acted.
Circulation stirring mechanism C is illustrated.Circulation stirring mechanism C is mainly used for making to be stored in developer solution storagetank 61 Developer solution recycle and the developer solution is stirred.
The bottom of developer solution storagetank 61 is with the side of developer solution storagetank 61 by being equipped with circulating pump 74 and mistake in midway The circulation line 85 of filter 75 and connect.When making circulating pump 74 act, the developer solution being stored in developer solution storagetank 61 passes through It is recycled by circulation line 85.Developer solution is store via circulation line 85 from the side of developer solution storagetank 61 back to developer solution Slot 61 is deposited, to be stirred to the developer solution of storage.
In addition, in the case where replenisher is flowed into via interflow pipeline 84 to circulation line 85, the replenisher one of the inflow Side mixes with the developer solution recycled in circulation line 85 and is supplied on one side into developer solution storagetank 61.
Then, the developer solution managing device D of present embodiment is illustrated.The developer solution managing device of present embodiment D is the developer solution managing device such as under type：Using according to show alkalinity developer solution dissolving photoresist agent concentration and A concentration of index of absorbing carbon dioxide and the concentration range of determination and with the aobvious of developing performance as defined in confirmed to realize in advance The conductivity data of the conductivity values of shadow liquid, will be according to the measured value and absorption dioxy of the dissolving photoresist agent concentration of developer solution Change concentration of carbon measured value and the concentration range of determination conductivity as control targe value so that the conductivity of developer solution becomes The mode of control targe value feeds replenisher to developer solution.
Developer solution managing device D has determination part 1 and control mechanism 21.Developer solution managing device D is by sampling piping 15 And outlet side line 16 is connect with developer solution storagetank 61.
Determination part 1 has sampling pump 14, conductivity meter 11, the first concentration mensuration machine for measuring dissolving photoresist agent concentration Structure 12 and the second concentration mensuration mechanism 13 for measuring absorbing carbon dioxide concentration.Conductivity meter 11, the first concentration mensuration Mechanism 12 and the second concentration mensuration mechanism 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 and the sampling pump 14 of the determination part 1 of developer solution managing device D connect It connects, outlet side line 16 is connect with the piping of measuring means end.
In addition, in fig. 1 it is illustrated that going out conductivity meter 11, the first concentration mensuration mechanism 12 and the second concentration mensuration mechanism 13 The mode being connected in series with, but the connection of conductivity meter 11, the first concentration mensuration mechanism 12 and the second concentration mensuration mechanism 13 is not It is defined in this.It can also be connected in parallel, can also have liquor charging path to be independently of one another measured.Conductivity meter 11, The sequence of one concentration mensuration mechanism 12 and the second concentration mensuration mechanism 13 is also not particularly limited successively.As long as according to each measuring means Feature and be suitably measured with best sequence.
Control mechanism 21 has data store 23 and control unit 31.In data store 23, it is stored with conductivity number According to the conductivity data is a concentration of according to the dissolving photoresist agent concentration and absorbing carbon dioxide of the developer solution to show alkalinity The concentration range of index and determination has developing performance, developer solution to be used conduction as defined in confirmed to realize in advance Rate value.
Control mechanism 21 is dense by conductivity meter 11, the first concentration mensuration mechanism 12 and second of signal wire and determination part 1 Measuring means 13 is spent to connect.Conductivity values, dissolving photoresist concentration value and the absorbing carbon dioxide determined by determination part 1 Concentration value is sent to control mechanism 21.
The control unit 31 of control mechanism 21 passes through signal wire and the control on the pipeline for conveying replenisher to developer solution Valve 41~43 connects.In Fig. 1, control valve 41~43 is illustrated as the internal part of developer solution managing device D, but is controlled Valve 41~43 is not the necessary parts for the developer solution managing device D for being present embodiment.As long as control unit 31 can be to control The action of valve 41~43 processed to feed the mode of replenisher to developer solution and control valve 41~43 is got in touch with.Control valve 41~43 It can also exist on except developer solution managing device D.
The developer solution managing device D of embodiment has alert mechanism D.Alert mechanism WD can be in the conduction of developer solution It is sent out when the range of management of either one deviation setting in rate, dissolving photoresist agent concentration and absorbing carbon dioxide concentration Alarm.
For example, can judge conductivity, dissolving photoresist agent concentration and the absorption of developer solution using control mechanism 21 Whether either one in gas concentration lwevel constituent concentration be outside the range of management of setting.It can be from control mechanism 21 to police It reports mechanism WD to send the information, and so that alert mechanism WD is sent out alarm based on the information.
As long as alert mechanism WD can send out alarm, decision mechanism is not particularly limited.
The transmission external output signal terminal of alarm signal, the alarm device to sound the alarm, light is preferably provided with to light Or either one in the Converting terminal of the opening and closing of the emergency warning lamp of flicker, the display device of display warning and double-throw contact is made For alert mechanism WD.
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).When device receives alarm signal from external output signal terminal, defined action can be carried out. 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.
In addition, also alarm can be arranged according to conductivity, dissolving photoresist agent concentration and absorbing carbon dioxide concentration Mechanism WD, alert mechanism WD are set in the conductivity of developer solution, dissolving photoresist agent concentration and absorbing carbon dioxide deviation of concentration Alarm is sent out when fixed range of management.By according to conductivity, dissolving photoresist agent concentration and absorbing carbon dioxide concentration come Alert mechanism WD is set, and thus, it is possible to the conductivity of developer solution, dissolving light are known according to the alarm sent from alert mechanism WD Which side deviation range of management in agent concentration and absorbing carbon dioxide concentration against corrosion caused.
Then, the action of the developer solution managing device D of present embodiment is illustrated.
The developer solution sampled from developer solution storagetank 61 is conveyed into determination part 1 and is adjusted by temperature.Later, developer solution It is conveyed to conductivity meter 11, the first concentration mensuration mechanism 12 and the second concentration mensuration mechanism 13, to measure conductivity, dissolving light Cause agent concentration and absorbing carbon dioxide concentration against corrosion.Each determination data is sent to control mechanism 21.
In control unit 31, it is set with the management value of conductivity corresponding with the conductivity values of conductivity data, the conduction Rate data concentration area of determination according to dissolving photoresist agent concentration and a concentration of index of absorbing carbon dioxide with developer solution Domain has the conductivity values of the developer solution of developing performance as defined in confirmed to realize in advance.Control unit 31 connects according to from determination part 1 The determination data of receipts, is controlled as follows.
Control unit 31 is solved based on the dissolving photoresist agent concentration and absorbing carbon dioxide concentration received from determination part 1 The suction for being stored in dissolving photoresist agent concentration in the conductivity data of data store 23, that basis determines and determining Receive the conductivity values of gas concentration lwevel and the concentration range of determination.The conductivity values found out are set as to the conductivity of developer solution Control targe value.
Control unit 31 carries out the conductivity determined received from determination part 1 and the conductivity for being set as control targe value Compare, is managed as follows according to comparison result.That is, in the conductivity for being set as control targe value and the conductivity determined In the case of identical, substantially replenisher is not added to developer solution.It is surveyed in addition, being more than in the conductivity for being set as control targe value In the case of the conductivity made, the replenisher acted in a manner of improving conductivity can be fed to developer solution.In addition, setting Be set to control targe value conductivity be less than the conductivity that determines in the case of, can be fed to developer solution to reduce conductivity The replenisher that acts on of mode.
Here, as the replenisher fed to developer solution, such as have the stoste of developer solution, the new liquid of developer solution, pure water etc..
Replenisher is stored in the replenisher storagetank 91,92 of replenisher reservoir B.It is connected on replenisher storagetank 91,92 There is the nitrogen pipeline 86 for having valve 46,47, the nitrogen pressurization that replenisher storagetank 91,92 is supplied via the pipeline.In addition, It is connected separately with replenisher pipeline 81,82 on replenisher storagetank 91,92, is conveyed via the valve 44,45 of normally open Replenisher.In replenisher pipeline 81,82 and pure water with control valve 41~43 is provided on pipeline 83, control valve 41~43 is by controlling Portion 31 processed is opened and closed to control.It is acted by control valve, thus will be stored in the supplement hydraulic coupling of replenisher storagetank 91,92 Conveying, and convey pure water.Later, replenisher collaborates via interflow pipeline 84 and circulation stirring mechanism C, to developer solution storagetank 61 feed and are stirred.
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.
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 feed the replenisher for the liquid measure for needing to feed.Control unit 31 is based on from measurement Portion 1 receive the conductivity determined and the conductivity for being set as control targe value, to control valve send control signal so that Control valve opens the stipulated time, to flow through the replenisher for the liquid measure for needing to feed.
Various control methods used in the control for keeping controlled quentity controlled variable consistent with desired value may be used in the mode of control.Especially It is 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, developer solution managing device D according to the present embodiment, no matter developer solution dissolving photoresist it is dense What degree and absorbing carbon dioxide concentration becomes, and can carry out pipe to developer solution by using the conductivity in developer solution Reason maintains to act on development active ingredient, therefore can realize and can maintain desired developing performance and can maintain base The desired line width of wiring pattern on plate and the development treatment of residual film thickness.
In addition, developer solution managing device D according to the present embodiment, uses the developer solution that confirmed developing performance in advance The conductivity data of conductivity values sets control targe management value, even the thus dissolving photoresist agent concentration of developer solution For 0.0~0.40 (wt%) (being equivalent to 0.0~1.3 (abs)) and absorbing carbon dioxide a concentration of 0.0~1.3 (wt%), also can Enough used as the developer solution with desired developing activity.That is, developer solution managing device D according to the present embodiment, Even more than the dissolving photoresist a concentration of 0.25 (wt%) of developer solution (being equivalent to 0.8 (abs)) and absorbing titanium dioxide Concentration of carbon is 0.6 (wt%) or more, can be continuing with without discarded developer solution, can reduce the waste liquid amount of developer solution.
This concludes the description of using the conductivity of developer solution, absorbing carbon dioxide concentration and dissolving photoresist agent concentration and The example of conductivity data.But not limited to this, can use the alkali composition concentration of developer solution, absorbing carbon dioxide concentration and Absorbance and alkali composition concentration data manage developer solution.In this case, alert mechanism WD developer solution alkali composition concentration, Alarm is sent out when the range of management of either one deviation setting in absorbance and absorbing carbon dioxide concentration.
(second embodiment)
Fig. 2 is the schematic diagram of the developing procedure of the developer solution managing device D for illustrating present embodiment.The present invention's is aobvious Shadow liquid managing device D and developing procedure device A, replenisher reservoir B, circulation stirring mechanism C etc. are illustrated together.It needs to illustrate , sometimes pair same as the structure of a first embodiment structure mark same drawing reference numeral and omit the description.
The determination part 1 of developer solution managing device D has conductivity meter 11 and the dissolving photoresist pair with developer solution Characteristic value of the concentration with associated developer solution and with the absorbing carbon dioxide concentration of developer solution with the spy of associated developer solution Multiple measurement devices that property value is measured.For example, as pair there is associated developer solution with dissolving photoresist agent concentration The first characteristic value measuring means 12A that characteristic value is measured, and be arranged and the absorbance under such as λ=560nm is measured Extinction photometer.There is the second spy that the characteristic value of associated developer solution is measured with absorbing carbon dioxide concentration as pair Property value measuring means 13A, and the densimeter that is measured to the density of developer solution is set.
Here, it refers to that the characteristic value has relationship with the constituent concentration " to have associated " characteristic value of developer solution, in spy Property value changes such relationship according to the variation of the constituent concentration.For example, at least ingredient in the constituent concentration of developer solution It refers to solving characteristic value as the function of variable using using constituent concentration that concentration A, which has the characteristic value a of associated developer solution, When a, one in variable includes at least constituent concentration A.Characteristic value a can be only with the relevant functions of constituent concentration A, but usually As the multi-variable function also by constituent concentration B or C etc. as variable other than constituent concentration A, at this point, using multivariable solution The meaning of analysis method (such as multiple regression analysis method) is just very big.
Control mechanism 21 has data store 23, control unit 31 and operational part 32.Operational part 32 is surveyed according to by determination part 1 Multiple characteristic values of the developer solution made and the dissolving photoresist agent concentration that developer solution is calculated using multiple-regression analysis The measured value of measured value and absorbing carbon dioxide concentration.
In the present embodiment, the developer solution sampled from developer solution storagetank 61 is conveyed and is conditioned into determination part 1 Temperature.Later, developer solution is by defeated to conductivity meter 11, the first characteristic value measuring means 12A and the second characteristic value measuring means 13A It sends and measures conductivity, absorbance and density.Each determination data is sent to control mechanism 21.
Operational part 32 calculates development according to the absorbance and density determined by determination part 1 and using multiple-regression analysis The measured value of the dissolving photoresist agent concentration of liquid and the measured value of absorbing carbon dioxide concentration.At this point, can also be according to conduction Rate, absorbance and density simultaneously calculate the measured value of dissolving photoresist agent concentration using multiple-regression analysis and absorb titanium dioxide The measured value of concentration of carbon.
Control unit 31 is based on the dissolving photoresist agent concentration and absorbing carbon dioxide concentration calculated by operational part 32, to ask Solution be stored in it is in the conductivity data of data store 23, according to the dissolving photoresist agent concentration that determines and determine The conductivity values of absorbing carbon dioxide concentration and the concentration range of determination.The conductivity values found out are set as to the conduction of developer solution The control targe value of rate.
The developer solution managing device D of present embodiment has alert mechanism WD.Alert mechanism WD being capable of leading in developer solution It is sent out when the range of management of either one deviation setting in electric rate, dissolving photoresist agent concentration and absorbing carbon dioxide concentration Go out alarm.
Other structures, action etc. are same as first embodiment, therefore omit.
Then, dense to calculating dissolving photoresist according to multiple characteristic values of developer solution and using multiple-regression analysis The measured value of degree and the method for absorbing carbon dioxide concentration illustrate.
Inventor has found：If operation method uses multiple-regression analysis (for example, multiple regression analysis method), and use The case where existing method, is compared, and the concentration of each ingredient of developer solution can be precisely calculated, moreover, existing skill can be measured Art is difficult to the absorbing carbon dioxide concentration measured.If being calculated using using multiple-regression analysis (for example, multiple regression analysis method) The constituent concentration (dissolving photoresist agent concentration and absorbing carbon dioxide concentration) of the developer solution gone out, then can confirm according to advance The dissolving photoresist agent concentration and absorbing carbon dioxide concentration of developing performance and the conductivity data with conductivity values come It is readily available the conductivity values of target.
Assuming that the case where carrying out the management of 2.38%TMAH aqueous solutions, will make alkali composition concentration, dissolving photoresist dense TMAH aqueous solutions modulation obtained by various change, which occurs, for degree, absorbing carbon dioxide concentration becomes simulation developer solution sample.Inventor Following experiment is carried out：According to the various characteristics value that these simulation developer solution samples are measured with gained, multiple regression is utilized Analytic approach solves its constituent concentration.Hereinafter, the common operation method based on multiple regression analysis method is illustrated, later, Based on the experiment that inventor is carried out, the operation method of the constituent concentration of the developer solution to having used multiple regression analysis method carries out Explanation.
Multiple regression analysis method is by correcting and predicting that two stages are constituted.In the multiple regression analysis of n ingredients system, prepare M calibration standard solution.The concentration for j-th of the ingredient that will be present in i-th of solution is expressed as Cij.Here, i=1~m, j= 1~n.For m standard solution, p characteristic value (for example, the characteristic values such as absorbance or conductivity under certain wavelength) is measured respectively Aik(k=1~p).Concentration data and performance data are able to summarize and (C, A) is indicated with a matrix type.
【Formula 1】
It will be known as correction matrix to matrix obtained from these matrix opening relationships, and use symbol S (S hereinkj；K=1~p, j =1~n) it indicates.
【Formula 2】
C=AS
(it can be not only the measured value of homogeneity for the content of A, can also be heterogeneous survey according to known C and A Definite value mixes.For example, conductivity, absorbance and density.) and calculate the stage of S using matrix operation as calibration phase. At this time, it is necessary to be p >=n and m >=np.The all unknown numbers of each element of S, therefore preferably m ＞ np, in this case as follows Carry out least square operation.
【Formula 3】
S=(ATA)-1(ATC)
Here, upper target T indicates that transposed matrix, upper target -1 indicate inverse matrix.
P characteristic value is measured for the unknown sample liquid of concentration, if they are set as Au (Auk；K=1~p), then will Its concentration C u (Cu that can obtain requiring out that are multiplied with Sj；J=1~n).
【Formula 4】
Cu=AuS
This is forecast period.
The alkaline-based developer used (2.38%TMAH aqueous solutions) is considered as photic anti-by alkali composition, dissolving by inventor The multicomponent system (n=3) of agent and absorbing carbon dioxide these three ingredients composition is lost, and has been carried out according to the spy as the developer solution Three characteristic values (p=3) of property value, i.e., the absorbance value under the conductivity values of developer solution, specific wavelength and density value simultaneously utilize Above-mentioned multiple regression analysis method calculates the experiment of each constituent concentration.Inventor is using 2.38%TMAH aqueous solutions as developer solution Basic composition is modulated alkali composition concentration (TMAH concentration) of sening as an envoy to, dissolving photoresist agent concentration, absorbing carbon dioxide concentration and is occurred 11 calibration standard solution obtained by various change (m=11 meets p >=n and m ＞ np).
Experiment is following to be carried out：For 11 calibration standard solution, the absorbance under conductivity values, wavelength X=560nm is measured The characteristic value of value and density value as developer solution, and utilize multi-element linear regression method (Multiple Linear Regression-Inverse Least Squares；MLR-ILS) each constituent concentration is calculated.
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, moreover, being adjusted to 25.0 DEG C again using temperature controller when horse back will be measured.Conductivity meter uses this The conductivity meter of corporation.It is determined using the conductivity flow cell of the our company for implementing platinum black processing.Guide The electrode constant for the conductivity flow cell that electric rate instrument input separately confirmed using correction operation.Extinction photometer also uses The equipment of our company.Extinction photometer is the suction in the light source portion, photometric measurer and glass flow cell that have wavelength X=560nm Light photometer.Density measurement has used the densimeter using self-oscillation method, the self-oscillation method according to U-shaped pipe flow cell into Row energization and the intrinsic vibration number that measures solve density.Conductivity values, absorbance value, the unit of the density value difference determined For mS/cm, Abs. (Absorbance), g/cm3。
Operation (stays a cross-validation method based on following method；Leave-One-Out methods) it carries out：By 11 correcting marks One in quasi- solution solves correction matrix as unknown sample using remaining 10 calibration standard solution, calculates and assumes Unknown sample concentration and (concentration values that analysis methods determine other accurately or weight is utilized to modulate with known value Value) it is compared.
Having carried out MLR-ILS calculating, the results are shown in Table 1.
【Table 1】
In MLR-ILS calculating, absorbing carbon dioxide is easy for strong basicity to deteriorate in view of TMAH aqueous solutions, In the concentration matrix used in operation, use using can accurately analyze alkali composition concentration or absorbing carbon dioxide concentration Analysis by titration is separately measured calibration standard solution the value of gained.Wherein, it about dissolving photoresist agent concentration, uses Weight modulation value.
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.
Hereinafter, indicating concentration matrix in table 2.
【Table 2】
The measurement result of the characteristic value of calibration standard solution at this time is as shown in table 3.This column of absorbance expression wavelength X= Absorbance value (optical path length d=10mm) under 560nm.
【Table 3】
It is as shown in table 4 to correct ranks.
【Table 4】
0.040187 -0.0028690.000171
-0.130547 -0.0614410.300422
432.787314 144.6545312.02483
Table 5 indicates the comparison of the concentration measurement of table 2 and the MLR-ILS calculated values of table 1.
【Table 5】
As shown in table 5, the TMAH concentration that is found out using multiple regression analysis method, absorbs two at dissolving photoresist agent concentration Oxidation concentration of carbon is and the TMAH concentration, the absorbing carbon dioxide concentration and according to modulation weight that are determined using titrimetry Measure either one very approximate value in the dissolving photoresist agent concentration found out.
In this way, it is to be understood that by measuring absorbance under the conductivity of alkaline-based developer, specific wavelength and density simultaneously It is photic thus, it is possible to measure the alkali composition concentration of developer solution, dissolving using multiple-regression analysis (such as multiple regression analysis method) Agent concentration and absorbing carbon dioxide concentration against corrosion.
Multiple-regression analysis (such as multiple regression analysis method) is for operation and to solve the concentration of multiple ingredients be effective. Can measure multiple characteristic value a, b of developer solution, c ..., according to the measured value of these characteristic values and utilize multiple-regression analysis (such as multiple regression analysis method) come solve constituent concentration A, B, C ....At this point, for the constituent concentration each to be solved, At least there is with the constituent concentration associated characteristic value to need at least to be measured one and be used for operation.
In addition, constituent concentration is the scale for indicating the ingredient relative to whole relative quantity.The developer solution being used repeatedly The constituent concentration for the mixed liquor that such ingredient increases and decreases as time goes by is not determined individually by the ingredient, usually becomes it The function of the concentration of its ingredient.Therefore, the relationship of the characteristic value of developer solution and constituent concentration be difficult to mostly with the chart of plane come It indicates.In this case, in using operation method of calibration curve etc., ingredient can not be calculated according to the characteristic value of developer solution Concentration.
However, according to multiple-regression analysis (such as multiple regression analysis method), prepare one group and the constituent concentration to be calculated Measured value with associated multiple characteristic values, and they are used for operation, calculate one group of constituent concentration.Based on multivariable solution Analysis method (such as multiple regression analysis method) in the component concentration measuring that carries out, can obtain following remarkable result：Even root It is at first sight difficult to the constituent concentration measured according to existing cognition, it can also be by measuring characteristic value come measuring component concentration.
As described above, operation method according to the present invention, characteristic value that can be based on developer solution is (for example, conductivity, specific Absorbance under wavelength and density) measured value calculate alkali composition concentration, the dissolving photoresist agent concentration and suction of developer solution Receive gas concentration lwevel.It is dense can accurately to calculate each ingredient compared with the conventional method for operation method according to the present invention Degree.
In addition, in the present invention, having used multiple-regression analysis (such as multiple regression analysis method), therefore develop calculating The developer solution not in linear relation with the specific constituent concentration of developer solution can also be used in the operation of the constituent concentration of liquid Characteristic value.
In addition, according to the present invention, needed very more in the invention of patent document 2 in order to realize high-precision measuring The preparation of sample and measured in advance are unwanted.(experimental example as the aforementioned is such, if the developer solution of component number n=3, The number for the characteristic value that will then measure is set as being p=3, and the sample number m (such as m=11 sample) for preparing to meet m >=np is carried out It measures just enough.If component number n=2, sample number can be further reduced).
In turn, due to the present invention use multiple-regression analysis (such as multiple regression analysis method), can precision it is good Ground calculates the absorbing carbon dioxide concentration that the prior art is difficult to the developer solution measured.
In the present embodiment, there is the characteristic of associated developer solution as the dissolving photoresist agent concentration with developer solution Value, instantiates the absorbance under λ=560nm, but not limited to this.Can also using the absorbance under other specific wavelengths as Characteristic value utilizes, the absorbance under other specific wavelengths be refer to visible light region, be more highly preferred to the wavelength of 360~600nm Absorbance under the specific wavelength in region, and then the absorbance under optimal wavelength λ=480nm.This is because being included in above-mentioned wave Absorbance under the specific wavelength in long region has relatively better correspondence with agent concentration against corrosion is dissolved.
In addition, being instantiated close as the characteristic value with the absorbing carbon dioxide concentration of developer solution with associated developer solution Degree, but not limited to this.As with developer solution dissolving photoresist agent concentration or absorbing carbon dioxide concentration have be associated with Developer solution characteristic value, in the characteristic value that the characteristic value for combining to measure in the conductivity with developer solution can use, in addition to Except absorbance, density under above-mentioned specific wavelength, for example, ultrasonic propagation velocity, refractive index, titration end-point, pH Deng.
(third embodiment)
Fig. 3 is the schematic diagram of the developing procedure of the developer solution managing device D for illustrating present embodiment.The present invention's is aobvious Shadow liquid managing device D and developing procedure device A, replenisher reservoir B, circulation stirring mechanism C etc. are illustrated together.It needs to illustrate , sometimes pair same as the structure of a first embodiment and second embodiment structure mark same drawing reference numeral and omit Explanation.
The developer solution managing device D of present embodiment has determination part 1, control mechanism 21 and arithmetical organ 36.In this reality It applies in mode, unlike second embodiment, control mechanism 21 is with the arithmetical organ 36 of progress operation by seperated device To constitute.
Determination part 1 has conductivity meter 11, the first characteristic value measuring means 12A and the second characteristic value measuring means 13A.Fortune Mechanism 36 is calculated according to the absorbance that is determined by the first characteristic value measuring means 12A and the second characteristic value measuring means 13A and close It spends and the measured value and absorbing carbon dioxide for calculating the dissolving photoresist agent concentration of developer solution using multiple-regression analysis is dense The measured value of degree.At this point, it is photic anti-to calculate dissolving according to conductivity, absorbance and density and using multiple-regression analysis Lose the measured value and absorbing carbon dioxide concentration of agent concentration.
Control unit 31 is based on the dissolving photoresist agent concentration and absorbing carbon dioxide concentration calculated by arithmetical organ, to ask Solution be stored in it is in the conductivity data of data store 23, according to the dissolving photoresist agent concentration that determines and determine The conductivity values of absorbing carbon dioxide concentration and the concentration range of determination.The conductivity values found out are set as to the conduction of developer solution The control targe value of rate.
The developer solution managing device D of present embodiment has alert mechanism WD.Alert mechanism WD being capable of leading in developer solution It is sent out when the range of management of either one deviation setting in electric rate, dissolving photoresist agent concentration and absorbing carbon dioxide concentration Go out alarm.
Other structures, action etc. are same as second embodiment, therefore omit.
(the 4th embodiment)
Fig. 4 is the schematic diagram of the developing procedure of the developer solution managing device D for illustrating present embodiment.The present invention's is aobvious Shadow liquid managing device D and developing procedure device A, replenisher reservoir B, circulation stirring mechanism C etc. are illustrated together.It needs to illustrate , sometimes same to structure mark same as the structure of first embodiment, second embodiment and third embodiment Drawing reference numeral and omit the description.
The determination part 1 of present embodiment has conductivity meter 11, the first concentration mensuration mechanism 12 and densimeter 13B.Control Mechanism 21 has data store 23 and operational part 33.Absorbing carbon dioxide concentration of the operational part 33 based on developer solution and density it Between correspondence, it is dense come the absorbing carbon dioxide for calculating developer solution according to the density of the developer solution determined by densimeter 13B Degree.
Control unit 31 is based on the dissolving photoresist agent concentration determined by determination part 1 and the absorption calculated by operational part 33 Gas concentration lwevel, come solve be stored in it is in the conductivity data of data store 23, photic anti-according to the dissolving that determines Lose the conductivity values of agent concentration and the absorbing carbon dioxide concentration determined and the concentration range of determination.The conductivity values that will be found out It is set as the control targe value of the conductivity of developer solution.
The developer solution managing device D of present embodiment has alert mechanism WD.Alert mechanism WD being capable of leading in developer solution It is sent out when the range of management of either one deviation setting in electric rate, dissolving photoresist agent concentration and absorbing carbon dioxide concentration Go out alarm.
Other structures, action etc. are same as first embodiment, therefore omit.
The relationship of the density value and absorbing carbon dioxide concentration value of developer solution is illustrated.It is careful that inventor constantly carries out Research is found as follows as a result, obtaining.That is, it is unrelated with the alkali composition concentration of developer solution, dissolving photoresist agent concentration, aobvious Relatively better correspondence (linear relation) can be obtained between the density value and absorbing carbon dioxide concentration value of shadow liquid.Separately Outside, if using the correspondence (linear relation), the density of developer solution can be measured using densimeter, thus, it is possible to measure The prior art is difficult to the absorbing carbon dioxide concentration measured.
Inventor will use 11 correcting marks used in the operation of the constituent concentration of the developer solution of multiple-regression analysis Quasi- solution has carried out following experiment as simulation developer solution sample, and for simulation developer solution sample：Measure alkali composition concentration (TMAH concentration), dissolving photoresist agent concentration, absorbing carbon dioxide concentration and density, and confirm phase of the constituent concentration with density Guan Xing.
The constituent concentration of each sample and the measurement result of density are shown in table 6 below.Table 6 is to survey the concentration of table 5 Density (the g/cm of definite value (wt%) and table 33) table obtained from comparison.
【Table 6】
The absorbing carbon dioxide concentration of each sample shown in table 6 and the chart of density is shown in FIG. 5.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.Regression straight line is found out according to each point drawn out and using least square method.
According to Fig. 5 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 unrelated with alkali composition concentration (TMAH concentration) or dissolving agent concentration against corrosion and utilize the correspondence (linear relation) and the absorbing carbon dioxide concentration that developer solution is measured using densimeter.
Operational part 33 and can be easily determined by using the relationship of the density and absorbing carbon dioxide concentration of developer solution The absorbing carbon dioxide concentration of developer solution.
(the 5th embodiment)
Fig. 6 is the schematic diagram of the developing procedure of the developer solution managing device D for illustrating present embodiment.The present invention's is aobvious Shadow liquid managing device D and developing procedure device A, replenisher reservoir B, circulation stirring mechanism C etc. are illustrated together.It needs to illustrate , sometimes pair same as the structure of a first embodiment and second embodiment structure mark same drawing reference numeral and omit Explanation.
The developer solution managing device D of present embodiment has determination part 1, control mechanism 21 and arithmetical organ 37.In this reality It applies in mode, unlike the 4th embodiment, the arithmetical organ 37 of control mechanism 21 and progress operation is by not androgynous dress Set composition.The determination part 1 of present embodiment has conductivity meter 11, the first concentration mensuration mechanism 12 and densimeter 13B.Calculating machine Absorbing carbon dioxide concentration of the structure 37 based on developer solution and the correspondence between density, according to what is determined by densimeter 13B The density of developer solution calculates the absorbing carbon dioxide concentration of developer solution.
Control unit 31 is based on the dissolving photoresist agent concentration determined by determination part 1 and the suction calculated by arithmetical organ 37 Receive gas concentration lwevel, come solve be stored in it is in the conductivity data of data store 23, photic according to the dissolving that determines Agent concentration against corrosion and the absorbing carbon dioxide concentration that determines and the conductivity values of the concentration range of determination.The conductivity that will be found out Value is set as the control targe value of the conductivity of developer solution.
Other structures, action etc. are same as the 4th embodiment, therefore omit.
As described above, developer solution managing device D according to the present embodiment, no matter developer solution dissolving photoresist it is dense What degree and absorbing carbon dioxide concentration becomes, and can be maintained active ingredient is acted on to development in developer solution At fixation, therefore it can realize the desired line that can be maintained desired developing performance and the wiring pattern on substrate can be maintained Wide and residual film thickness development treatment.
Then, the variation of the developer solution managing device D of present embodiment is illustrated.
In Fig. 1~4,6, the determination part 1 and control mechanism 21, arithmetical organ 36,37 of developer solution managing device D are depicted The developer solution managing device D being integrally formed, but it's not limited to that by the developer solution managing device D of present embodiment.It can also incite somebody to action Determination part 1 is set as not androgynous structure.
In determination part 1, according to the measuring principle being respectively adopted, there are best setting methods, for example, can will survey Determine portion 1 and development 80 on-line joining process of liquid pipeline, or can will measure probe and be set to developer solution storagetank in a manner of impregnating 61.Conductivity meter 11, the first concentration mensuration mechanism 12, the first characteristic value measuring means 12A, the second concentration mensuration mechanism 13, Each measuring means of two characteristic value measuring means 13A and densimeter 13B can be separately arranged.With regard to the aobvious of present embodiment For shadow liquid managing device D, as long as each measuring means with control mechanism 21, arithmetical organ 36,37 can be measured number According to exchange the scheme mutually got in touch with of mode, it will be able to realize.
According to measuring principle used by each measuring means, reagent is if desired added, then each measuring means can have use In the piping of addition reagent, if desired liquid waste, then each measuring means can have the pipeline for liquid waste.Even if each Measuring means is not connected in series with, and can also realize the developer solution managing device D of present embodiment.
In Fig. 1~4,6, following scheme is drawn out：To be arranged on the pipeline for the replenisher that conveying is fed to developer solution Control valve 41~43 as developer solution managing device D internal part mode, developer solution managing device D and replenisher are used Pipeline 81,82 and pure water are connected with pipeline 83, but it's not limited to that by the developer solution managing device D of present embodiment.Developer solution Managing device may not possess control valve 41~43 and be used as internal part, developer solution managing device can not also with for aobvious The pipeline 81~83 that shadow liquid feeds replenisher connects.
As long as following scheme：Control mechanism 21 in the developer solution managing device D of present embodiment exists with setting For feeding control of the control valve 41~43 on the pipeline of replenisher with the reception of control valve 41~43 by developer solution managing device D Control signal that mechanism 21 is sent out and the mode that is controlled mutually are got in touch with.Even if control valve does not become developer solution managing device D's Internal part can also realize the developer solution managing device D of present embodiment.
Although the developer solution managing device of the present invention allows above-mentioned various variation, needs to be configured to：Has conduction Rate data, the conductivity data according to a concentration of index of dissolving photoresist agent concentration and absorbing carbon dioxide with developer solution and Determining concentration range has the conductivity values of the developer solution of developing performance as defined in confirmed to realize in advance, by basis Developer solution dissolving photoresist agent concentration measured value and absorbing carbon dioxide concentration measured value and determination concentration range Conductivity data conductivity values as control targe value so that the conductivity of developer solution becomes the side of the control targe value Formula conveys the replenisher fed to the developer solution.
As described above, the management method and developer solution managing device of developer solution according to the present invention, no matter developer solution it is molten What solution photoresist agent concentration and absorbing carbon dioxide concentration becomes, and can will have to development effect in developer solution Active ingredient is maintained into fixation, therefore can realize the wiring diagram that can be maintained desired developing performance and can maintain on substrate The desired line width of case and the development treatment of residual film thickness.
As the preferred mode of developer solution managing device, it is dense to calculate dissolving photoresist using multiple-regression analysis Degree, absorbing carbon dioxide concentration, therefore it is dense precisely to calculate dissolving photoresist agent concentration, absorbing carbon dioxide Degree.Based on above-mentioned dissolving photoresist agent concentration and absorbing carbon dioxide concentration and mesh can be solved according to conductivity data Target conductivity values.
Moreover, the preferred mode as developer solution managing device, absorbing carbon dioxide concentration based on developer solution with it is close Correspondence between degree is dense come the absorbing carbon dioxide for calculating developer solution according to the density of the developer solution determined by densimeter Degree.Thereby, it is possible to more easily solve the absorbing carbon dioxide concentration of developer solution.It can be based on the absorbing carbon dioxide concentration And the dissolving photoresist agent concentration separately found out and the conductivity values that target is solved according to conductivity data.

Claims (16)

1. a kind of developer solution managing device, wherein
The developer solution managing device has control mechanism and alert mechanism,
The control mechanism has：
Data store is stored with conductivity data, the conductivity data according to Reusability and show alkalinity development The concentration range for dissolving photoresist agent concentration and a concentration of index of absorbing carbon dioxide and determination of liquid, has and confirmed in advance The conductivity values of the developer solution of developing performance as defined in realizing；And
Control unit, will be according to the measured value and absorbing carbon dioxide concentration of the dissolving photoresist agent concentration of the developer solution Measured value and the conductivity values for being stored in the data store of the concentration range of determination as control targe value so that The mode that the conductivity of the developer solution becomes the control targe value sends control signal, the control valve setting to control valve On the pipeline for the replenisher that conveying is fed to the developer solution,
The alert mechanism is in the conductivity of the developer solution, dissolving photoresist agent concentration and absorbing carbon dioxide concentration Either one sends out alarm when deviateing the range of management of setting.
2. developer solution managing device according to claim 1, 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 extremely Either one is used as the alert mechanism less.
3. developer solution managing device according to claim 1 or 2, wherein
The developer solution managing device is also equipped with multiple measurement devices, the multiple measurement device to comprising with the developer solution Dissolving photoresist agent concentration has the characteristic value of the associated developer solution and dense with the absorbing carbon dioxide of the developer solution The multiple characteristic values for the developer solution spent including the characteristic value with the associated developer solution are measured,
The control mechanism is also equipped with operational part, and the operational part is according to the development determined by the multiple measurement device Multiple characteristic values of liquid and the measured value for dissolving photoresist agent concentration that the developer solution is calculated using multiple-regression analysis And the measured value of absorbing carbon dioxide concentration.
4. developer solution managing device according to claim 1 or 2, wherein
The developer solution managing device is also equipped with：
Multiple measurement devices, to there is the associated developer solution comprising the dissolving photoresist agent concentration with the developer solution Characteristic value and there is institute including the characteristic value of the associated developer solution with the absorbing carbon dioxide concentration of the developer solution The multiple characteristic values for stating developer solution are measured；And
Arithmetical organ, according to multiple characteristic values of the developer solution determined by the multiple measurement device and using changeable Analytic method is measured to calculate the measured value for dissolving photoresist agent concentration of the developer solution and the measurement of absorbing carbon dioxide concentration Value.
5. developer solution managing device according to claim 1 or 2, wherein
The developer solution managing device has densimeter,
The control mechanism is also equipped with operational part, absorbing carbon dioxide concentration and density of the operational part based on the developer solution Between correspondence, the suction of the developer solution is calculated according to the density value of the developer solution determined by the densimeter Receive carbon dioxide concentration value.
6. developer solution managing device according to claim 1 or 2, wherein
The developer solution managing device is also equipped with：
Densimeter；And
Arithmetical organ, the correspondence between absorbing carbon dioxide concentration and density based on the developer solution, according to by institute The density value for the developer solution that densimeter determines is stated to calculate the absorbing carbon dioxide concentration value of the developer solution.
7. a kind of developer solution managing device, wherein
The developer solution managing device has control mechanism,
The control mechanism has：
Data store is stored with conductivity data, the conductivity data according to Reusability and show alkalinity development The concentration range for dissolving photoresist agent concentration and a concentration of index of absorbing carbon dioxide and determination of liquid, has and confirmed in advance The conductivity values of the developer solution of developing performance as defined in realizing；And
Control unit, will be according to the measured value and absorbing carbon dioxide concentration of the dissolving photoresist agent concentration of the developer solution Measured value and the conductivity values for being stored in the data store of the concentration range of determination as control targe value so that The mode that the conductivity of the developer solution becomes the control targe value sends control signal, the control valve setting to control valve On the pipeline for the replenisher that conveying is fed to the developer solution,
In the developer solution managing device, according to the conductivity of the developer solution, dissolving photoresist agent concentration and absorption two Oxidation concentration of carbon be provided with alert mechanism, the alert mechanism the developer solution conductivity, dissolving photoresist agent concentration and Alarm is sent out when the range of management of absorbing carbon dioxide deviation of concentration setting.
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 extremely Either one is used as the alert mechanism less.
9. developer solution managing device according to claim 7 or 8, wherein
The developer solution managing device is also equipped with multiple measurement devices, the multiple measurement device to comprising with the developer solution Dissolving photoresist agent concentration has the characteristic value of the associated developer solution and dense with the absorbing carbon dioxide of the developer solution The multiple characteristic values for the developer solution spent including the characteristic value with the associated developer solution are measured,
The control mechanism is also equipped with operational part, and the operational part is according to the development determined by the multiple measurement device Multiple characteristic values of liquid and the measured value for dissolving photoresist agent concentration that the developer solution is calculated using multiple-regression analysis And the measured value of absorbing carbon dioxide concentration.
10. developer solution managing device according to claim 7 or 8, wherein
The developer solution managing device is also equipped with：
Multiple measurement devices, to there is the associated developer solution comprising the dissolving photoresist agent concentration with the developer solution Characteristic value and there is institute including the characteristic value of the associated developer solution with the absorbing carbon dioxide concentration of the developer solution The multiple characteristic values for stating developer solution are measured；And
Arithmetical organ, according to multiple characteristic values of the developer solution determined by the multiple measurement device and using changeable Analytic method is measured to calculate the measured value for dissolving photoresist agent concentration of the developer solution and the measurement of absorbing carbon dioxide concentration Value.
11. developer solution managing device according to claim 7 or 8, wherein
The developer solution managing device has densimeter,
The control mechanism is also equipped with operational part, absorbing carbon dioxide concentration and density of the operational part based on the developer solution Between correspondence, the suction of the developer solution is calculated according to the density value of the developer solution determined by the densimeter Receive carbon dioxide concentration value.
12. developer solution managing device according to claim 7 or 8, wherein
The developer solution managing device is also equipped with：
Densimeter；And
Arithmetical organ, the correspondence between absorbing carbon dioxide concentration and density based on the developer solution, according to by institute The density value for the developer solution that densimeter determines is stated to calculate the absorbing carbon dioxide concentration value of the developer solution.
13. a kind of developer solution managing device, wherein
The developer solution managing device has control mechanism and alert mechanism,
The control mechanism has：
Data store is stored with alkali composition concentration data, and the alkali composition concentration data is according to Reusability and showing alkali Property developer solution with dissolving photoresist agent concentration there is associated absorbance and a concentration of index of absorbing carbon dioxide and true Fixed concentration range has the alkali composition concentration value of the developer solution of developing performance as defined in confirmed to realize in advance；And
Control unit, by the concentration area of determination according to the measured value of the absorbance of the developer solution and absorbing carbon dioxide concentration The alkali composition concentration value for being stored in the data store in domain as control targe value so that the alkali of the developer solution at The mode that concentration becomes the control targe value is divided to send control signal to control valve, the control valve setting is being conveyed to described On the pipeline of the replenisher of developer solution supply,
The alert mechanism is at least any in the alkali composition concentration, absorbance and absorbing carbon dioxide concentration of the developer solution Side sends out alarm when deviateing the range of management of setting.
14. developer solution managing device according to claim 13, 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 extremely Either one is used as the alert mechanism less.
15. a kind of developer solution managing device, wherein
The developer solution managing device has control mechanism,
The control mechanism has：
Data store is stored with alkali composition concentration data, and the alkali composition concentration data is according to Reusability and showing alkali Property developer solution with dissolving photoresist agent concentration there is associated absorbance and a concentration of index of absorbing carbon dioxide and true Fixed concentration range has the alkali composition concentration value of the developer solution of developing performance as defined in confirmed to realize in advance；And
Control unit, by the concentration area of determination according to the measured value of the absorbance of the developer solution and absorbing carbon dioxide concentration The alkali composition concentration value for being stored in the data store in domain as control targe value so that the alkali of the developer solution at The mode that concentration becomes the control targe value is divided to send control signal to control valve, the control valve setting is being conveyed to described On the pipeline of the replenisher of developer solution supply,
It is dense according to the alkali composition concentration, absorbance and absorbing carbon dioxide of the developer solution in the developer solution managing device Degree is provided with alert mechanism, alkali composition concentration, absorbance and absorbing carbon dioxide concentration of the alert mechanism in the developer solution Alarm is sent out when the range of management for deviateing setting.
16. developer solution managing device according to claim 15, 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 extremely Either one is used as the alert mechanism less.
CN201711234783.XA 2017-01-23 2017-11-29 Developer solution managing device Pending CN108345186A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2017009837A JP2018120900A (en) 2017-01-23 2017-01-23 Developer management device
JP2017-009837 2017-01-23

Publications (1)

Publication Number Publication Date
CN108345186A true CN108345186A (en) 2018-07-31

Family

ID=62962987

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201711234783.XA Pending CN108345186A (en) 2017-01-23 2017-11-29 Developer solution managing device

Country Status (4)

Country Link
JP (1) JP2018120900A (en)
KR (1) KR20180087125A (en)
CN (1) CN108345186A (en)
TW (1) TW201827948A (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102262358B1 (en) * 2020-04-08 2021-06-08 주식회사 에이치에스테크놀로지 Developer control system having concentration measurement apparatus and gas supply

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003295470A (en) * 2002-03-29 2003-10-15 Matsushita Environment Airconditioning Eng Co Ltd Method for measuring concentration of alkali developer liquid and preparation device of developer
JP2005070351A (en) * 2003-08-22 2005-03-17 Nagase & Co Ltd Method and apparatus for supplying developing solution
JP2006235070A (en) * 2005-02-23 2006-09-07 Fuji Photo Film Co Ltd Development control method for automatic developing apparatus for photosensitive planographic printing plate, and its automatic developing apparatus
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
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
JP2012256496A (en) * 2011-06-08 2012-12-27 Japan Unix Co Ltd Cartridge heater

Family Cites Families (1)

* 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

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003295470A (en) * 2002-03-29 2003-10-15 Matsushita Environment Airconditioning Eng Co Ltd Method for measuring concentration of alkali developer liquid and preparation device of developer
JP2005070351A (en) * 2003-08-22 2005-03-17 Nagase & Co Ltd Method and apparatus for supplying developing solution
JP2006235070A (en) * 2005-02-23 2006-09-07 Fuji Photo Film Co Ltd Development control method for automatic developing apparatus for photosensitive planographic printing plate, and its automatic developing apparatus
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
CN103852978A (en) * 2006-11-30 2014-06-11 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
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
JP2012256496A (en) * 2011-06-08 2012-12-27 Japan Unix Co Ltd Cartridge heater

Also Published As

Publication number Publication date
TW201827948A (en) 2018-08-01
JP2018120900A (en) 2018-08-02
KR20180087125A (en) 2018-08-01

Similar Documents

Publication Publication Date Title
CN103852978B (en) Concentration regulating method, modulating device and the developer solution of developer solution
CN106371296A (en) Component concentration measuring method and apparatus for developing solution and developing solution managing method and apparatus
JP6713658B2 (en) Component concentration measuring device for developer, component concentration measuring method, developer controlling device, and developer controlling method
TWI676086B (en) Managing method and apparatus for developing solution
CN108345183A (en) Developer solution managing device
CN108345186A (en) Developer solution managing device
CN108345169A (en) Developing apparatus
CN108345182A (en) The concentration monitoring arrangement and developer solution managing device of developer solution
CN108344662A (en) The gas concentration lwevel display device and developer solution managing device of developer solution
CN108344778A (en) The component concentration measuring device and developer solution managing device of developer solution
CN207502917U (en) The concentration management device of developer solution and the developing system of substrate
JP6624762B2 (en) Method and apparatus for managing developer
CN108345185A (en) The concentration monitoring arrangement and developer solution managing device of developer solution
CN108345168A (en) Developing apparatus
CN108345184A (en) Developing apparatus

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
WD01 Invention patent application deemed withdrawn after publication

Application publication date: 20180731

WD01 Invention patent application deemed withdrawn after publication