CN108345169A - Developing apparatus - Google Patents

Developing apparatus Download PDF

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Publication number
CN108345169A
CN108345169A CN201711234725.7A CN201711234725A CN108345169A CN 108345169 A CN108345169 A CN 108345169A CN 201711234725 A CN201711234725 A CN 201711234725A CN 108345169 A CN108345169 A CN 108345169A
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CN
China
Prior art keywords
developer solution
concentration
reusability
carbon dioxide
value
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Pending
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CN201711234725.7A
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Chinese (zh)
Inventor
中川俊元
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Hirama Rika Kenkyusho Ltd
Hirama Laboratories Co Ltd
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Hirama Rika Kenkyusho Ltd
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Publication of CN108345169A publication Critical patent/CN108345169A/en
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/002—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor using materials containing microcapsules; Preparing or processing such materials, e.g. by pressure; Devices or apparatus specially designed therefor
    • G03F7/0022—Devices or apparatus
    • G03F7/0025—Devices or apparatus characterised by means for coating the developer
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03D—APPARATUS FOR PROCESSING EXPOSED PHOTOGRAPHIC MATERIALS; ACCESSORIES THEREFOR
    • G03D3/00—Liquid processing apparatus involving immersion; Washing apparatus involving immersion
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—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
    • 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

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  • 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

Present invention offer is able to maintain that desired developing performance and maintains the desired line width of the wiring pattern on substrate and the developing apparatus of residual film thickness.Developing apparatus has：Developer solution modulating device mixes the development stoste of the principal component comprising the developer solution for showing alkalinity with pure water, and modulates the developer solution that concentration has been set and be used as the new liquid that develops；Develop new liquid pipeline, conveys the new liquid of the development of the developer solution supply from the developer solution modulating device to Reusability；Develop stoste pipeline, conveys the development stoste fed to the developer solution of the Reusability；Pure water pipeline conveys the pure water fed to the developer solution of the Reusability；And developer solution managing device, it is managed in a manner of so that the alkali composition concentration of the developer solution of the Reusability or the conductivity of the developer solution is become defined management value or falling into defined range of management.

Description

Developing apparatus
Technical field
The present invention relates to developing apparatus, more particularly, to the developing procedure etc. in semiconductor or the circuit board of liquid crystal display panel In in order to make photoresist film develop and the developing apparatus that uses.
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, it is difficult to Desired developing performance is maintained in developing apparatus.
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 developing apparatus of developing performance.
Solution for solving the problem
In order to reach the purpose, developing apparatus of the invention has：Developer solution modulating device will include to show alkalinity The development stoste of principal component of developer solution mixed with pure water, and it is new as development to modulate the developer solution that concentration has been set Liquid；Develop new liquid pipeline, conveys described in the developer solution supply from the developer solution modulating device to Reusability Develop new liquid；Develop stoste pipeline, conveys the development stoste fed to the developer solution of the Reusability；It is pure Water pipeline conveys the pure water fed to the developer solution of the Reusability；And developer solution managing device, so that The alkali composition concentration of the developer solution of the Reusability or the conductivity of the developer solution become defined management value or fall The mode of range of management as defined in entering is managed.
Developing apparatus according to the present invention, no matter the dissolving photoresist agent concentration and absorbing carbon dioxide concentration of developer solution What becomes, can be maintained active ingredient is acted on to development in developer solution into fixation, therefore be able to maintain that Desired developing performance, and can realize the line that can maintain desired developing performance, wiring pattern on such as substrate Wide and residual film thickness development treatment.
In order to reach the purpose, in the developing apparatus of the present invention, the developer solution managing device is also equipped with control machine Structure, the control mechanism have：Data store is stored with conductivity data, the conductivity data according to it is described repeatedly The concentration range for dissolving photoresist agent concentration and a concentration of index of absorbing carbon dioxide and determination of the developer solution used, The conductivity values of the developer solution with the Reusability that confirmed to realize defined developing performance in advance；And control Portion, will be according to the measured value and absorbing carbon dioxide of the dissolving photoresist agent concentration of the developer solution of the Reusability The measured value of concentration and the conductivity values for being stored in the data store of the concentration range of determination are as control targe Value, to set on the development in a manner of making the conductivity of the developer solution of the Reusability become the control targe value The control valve of new liquid pipeline, set on the control valve of the development stoste pipeline and set on the control valve of the pure water pipeline In either one send control signal.
Developing apparatus according to the present invention, no matter the dissolving photoresist agent concentration and absorbing carbon dioxide concentration of developer solution What becomes, can be maintained active ingredient is acted on to development in developer solution into fixation, therefore can realize It can maintain desired developing performance and the desired line width of the wiring pattern on substrate and the development of residual film thickness can be maintained Processing.
The preferred mode of developing apparatus according to the present invention, the developer solution managing device are also equipped with multiple measurement dresses It sets, the multiple measurement device is measured multiple characteristic values of the developer solution of the Reusability, multiple characteristic Value has the associated Reusability comprising the dissolving photoresist agent concentration with the developer solution of the Reusability The characteristic value of the developer solution and there is associated institute with the absorbing carbon dioxide concentration of the developer solution of the Reusability The characteristic value of the developer solution of Reusability is stated, the control mechanism of the developer solution managing device is also equipped with operational part, The operational part is according to multiple characteristic values of the developer solution determined by the multiple measurement device and utilizes multivariable solution Analysis method come calculate the Reusability the developer solution dissolving photoresist agent concentration measured value and absorbing carbon dioxide The measured value of concentration.
The preferred mode of developing apparatus according to the present invention, the developer solution managing device are also equipped with：Multiple measurement dresses Set, multiple characteristic values of the developer solution of the Reusability be measured, multiple characteristic value include with it is described anti- The dissolving photoresist agent concentration of the developer solution used again has the spy of the developer solution of the associated Reusability Property value and there is the institute of the associated Reusability with the absorbing carbon dioxide concentration of the developer solution of the Reusability State the characteristic value of developer solution；And arithmetical organ, according to the Reusability determined by the multiple measurement device Multiple characteristic values of the developer solution and calculated using multiple-regression analysis the Reusability the developer solution dissolving The measured value of photoresist agent concentration and the measured value of absorbing carbon dioxide concentration.
The preferred mode of developing apparatus according to the present invention, the developer solution managing device is also equipped with densimeter, described The control mechanism of developer solution managing device is also equipped with operational part, the development of the operational part based on the Reusability Correspondence between the absorbing carbon dioxide concentration and density of liquid, according to the Reusability determined by the densimeter The density value of the developer solution calculate the absorbing carbon dioxide concentration of the developer solution of the Reusability.
The preferred mode of developing apparatus according to the present invention, the developer solution managing device are also equipped with：Densimeter；And Arithmetical organ, the corresponding pass between the absorbing carbon dioxide concentration and density of the developer solution based on the Reusability System, the Reusability is calculated according to the density value of the developer solution of the Reusability determined by the densimeter The developer solution absorbing carbon dioxide concentration.
Developing apparatus according to the present invention, the developer solution managing device are also equipped with control mechanism, the control mechanism tool It is standby：Data store is stored with alkali composition concentration data, and the alkali composition concentration data is according to described in the Reusability Developer solution has associated absorbance and an a concentration of index of absorbing carbon dioxide and determination with dissolving photoresist agent concentration Concentration range has the alkali composition of the developer solution of the Reusability of developing performance as defined in confirmed to realize in advance dense Angle value；And control unit, it will be according to the absorbance of the developer solution of the Reusability and absorbing carbon dioxide concentration Measured value and the alkali composition concentration value for being stored in the data store of the concentration range of determination as control targe value, To set on described aobvious in a manner of making the alkali composition concentration of the developer solution of the Reusability become the control targe value The control valve of the new liquid pipeline of shadow, set on it is described development stoste pipeline control valve and set on the control of the pure water pipeline Either one in valve sends control signal.
Invention effect
Developing apparatus according to the present invention, no matter the dissolving photoresist agent concentration and absorbing carbon dioxide concentration of developer solution What becomes, can be maintained active ingredient is acted on to development in developer solution into fixation, therefore can realize It can maintain desired developing performance and the desired line width of the wiring pattern on substrate and the development of residual film thickness can be maintained Processing.
Description of the drawings
Fig. 1 is the schematic diagram of the developing apparatus for illustrating first embodiment.
Fig. 2 is the schematic diagram of the developing apparatus for illustrating second embodiment.
Fig. 3 is the schematic diagram of the developing apparatus for illustrating third embodiment.
Fig. 4 is the schematic diagram of the developing apparatus 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 apparatus 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
41~43,48~50 ... 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 ... development stoste pipelines, 82 ... develop new liquid pipeline, 83 ... pure water pipelines, 84 ... interflow pipelines, 85 ... circulation lines, 86 ... nitrogen pipelines
91 ... development stoste storagetanks, 92 ... developer solution modulating devices.
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 .
The developing apparatus of the present invention has：Developer solution modulating device will include the principal component for the developer solution for showing alkalinity Development stoste mixed with pure water, and modulate the developer solution that concentration has been set as the new liquid that develops；Develop new liquid pipe Road conveys the new liquid of the development of the developer solution supply from the developer solution modulating device to Reusability；Development is former Liquid pipeline conveys the development stoste fed to the developer solution of the Reusability；Pure water pipeline, conveying The pure water fed to the developer solution of the Reusability；And developer solution managing device, so that the Reusability The alkali composition concentration of the developer solution or the conductivity of the developer solution become defined management value or fall into defined management model The mode enclosed is managed.
Developer solution managing device included by developing apparatus is illustrated.
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 for illustrating developing apparatus.The developing apparatus of embodiment have developer solution modulating device 92, Develop new liquid pipeline 82, development stoste pipeline 81, pure water pipeline 83 and developer solution managing device D.
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.As long as developing procedure equipment B can be developed, not It is defined in structure shown in FIG. 1.
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.
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 development stoste storagetank 91 and developer solution modulating device 92 of replenisher reservoir B.Development is former The nitrogen pipeline 86 for having valve 46,47 is connected on liquid storagetank 91 and developer solution modulating device 92, develop stoste storagetank 91 and developer solution modulating device 92 supplied via the pipeline nitrogen pressurization.In addition, in development stoste storagetank 91 and development Development stoste pipeline 81 and the new liquid pipeline 82 of development are connected separately on liquid modulating device 92, via the valve of normally open 44,45 replenisher is conveyed.In development stoste pipeline 81, the new liquid pipeline 82 of development and pure water with being provided with control on pipeline 83 Valve 41~43 processed, control valve 41~43 control opening and closing by control unit 31.It is acted, thus will be stored in aobvious by control valve The supplement hydraulic coupling of shadow stoste storagetank 91 and developer solution modulating device 92 conveys, and conveys pure water.Later, replenisher via Collaborate pipeline 84 and circulation stirring mechanism C to collaborate, feeds and be stirred to developer solution storagetank 61.
If reducing the replenisher being stored in development stoste storagetank 91 and developer solution modulating device 92 because of supply, Its interior drops and cause supply amount to become unstable, therefore valve 46,47 is suitably opened to supply according to the reduction of replenisher Nitrogen, to maintain to ensure the internal pressure of development stoste storagetank 91 and developer solution modulating device 92.
In fig. 1 it is shown that developer solution modulating device 92 is pressurizeed by nitrogen and is conveyed from 92 pressure of developer solution modulating device aobvious The mode of the new liquid of shadow, but not limited to this.In developing apparatus, high-rise rank and development are located at developing procedure device A sometimes The mode sublevel that liquid modulating device 92 is located at low layer rank is configured.In this case, aobvious from developer solution modulating device 92 The conveying of the new liquid of shadow is mostly realized by liquid-feeding pump.It is also the same in Fig. 2~4 described below, 6.
As shown in Figure 1, in development stoste supply pipeline of the development connection of stoste storagetank 91 with control valve 48, aobvious Shadow liquid modulating device 92 connects the development stoste supply pipeline with control valve 49 and the pure water pipeline with control valve 50.
When developing stoste storagetank 91 and emptying developer solution modulating device 92, valve 44,45 is closed, to development stoste storage Slot 91 and developer solution modulating device 92 are refilled with.
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, the developing apparatus for including developer solution managing device D according to the present embodiment, no matter developer solution it is molten What solution photoresist agent concentration and absorbing carbon dioxide concentration becomes, and can come by using the conductivity in developer solution Developer solution is managed to maintain to act on development active ingredient, therefore can realize and can maintain desired development Performance and the desired line width of wiring pattern on substrate and the development treatment of residual film thickness can be maintained.
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 also use alkali composition concentration, the absorbing carbon dioxide concentration of developer solution And absorbance and alkali composition concentration data manage developer solution.
(second embodiment)
Fig. 2 is the schematic diagram for illustrating developing apparatus.It should be noted that the structure pair with first embodiment sometimes Same structure marks same drawing reference numeral and omits 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 and the measured value and absorbing carbon dioxide that dissolving photoresist agent concentration is calculated using multivariate analysis The measured value of concentration.
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.
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 method of the measured value of degree and the measured value of absorbing carbon dioxide concentration illustrates.
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 is by correcting and predicting that two stages are constituted.In the multiple regression analysis of n ingredients system, prepare m A 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 -0.002869 0.000171
-0.130547 -0.061441 0.300422
432.787314 144.654531 2.02483
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, divide TMAH concentration that Xin's method finds out using multiple regression, dissolving photoresist agent concentration, absorb two 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 for illustrating developing apparatus.It should be noted that sometimes pair with first embodiment and second The same structure of structure of embodiment marks same drawing reference numeral and omits the description.
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 of agent concentration and the measured value of absorbing carbon dioxide 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.
Other structures, action etc. are same as second embodiment, therefore omit.
(the 4th embodiment)
Fig. 4 is the schematic diagram for illustrating developing apparatus.It should be noted that sometimes pair with first embodiment, second The same structure of the structure of embodiment and third embodiment marks same drawing reference numeral and omits 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.
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 for illustrating developing apparatus.It should be noted that sometimes pair with first embodiment and second The same structure of structure of embodiment marks same drawing reference numeral and omits the description.
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 institute's phase that can be maintained desired developing performance and the wiring pattern being formed on substrate can be maintained The line width of prestige and the development treatment of residual film thickness.
Then, the variation of the developer solution managing device D for the developing apparatus for constituting 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, by developer solution managing device D with development stoste It is connected with pipeline 81, the new liquid pipeline 82 of development and pure water pipeline 83, but the developer solution managing device D of present embodiment is not It is defined in this.Developer solution managing device may not possess control valve 41~43 and be used as internal part, developer solution managing device It can not be with development stoste pipeline 81, the new liquid pipeline 82 of development and the pure water pipeline for feeding replenisher to developer solution 83 connections.
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, to keep the mode that the conductivity of developer solution becomes control targe value defeated It is sent to the replenisher of the developer solution supply.
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 (7)

1. a kind of developing apparatus, wherein
The developing apparatus has：
Developer solution modulating device mixes the development stoste of the principal component comprising the developer solution for showing alkalinity with pure water, and adjusts The developer solution that concentration processed has been set is as the new liquid that develops；
Develop new liquid pipeline, conveys described in the developer solution supply from the developer solution modulating device to Reusability Develop new liquid；
Develop stoste pipeline, conveys the development stoste fed to the developer solution of the Reusability；
Pure water pipeline conveys the pure water fed to the developer solution of the Reusability；And
Developer solution managing device, so that the alkali composition concentration of the developer solution of the Reusability or leading for the developer solution Electric rate becomes defined management value or the mode of range of management as defined in falling into is managed.
2. developing apparatus according to claim 1, wherein
The developer solution managing device is also equipped with control mechanism,
The control mechanism has：
Data store is stored with conductivity data, and the conductivity data is according to the developer solution of the Reusability Dissolving photoresist agent concentration and a concentration of index of absorbing carbon dioxide and determination concentration range, have and confirmed reality in advance The conductivity values of the developer solution of the Reusability of developing performance as defined in existing；And
Control unit, will be according to the measured value of the dissolving photoresist agent concentration of the developer solution of the Reusability and absorption The measured value of gas concentration lwevel and the conductivity values conduct for being stored in the data store of the concentration range of determination Control targe value, by make the conductivity of the developer solution of the Reusability become the control targe value in a manner of to set on The control valve of the new liquid pipeline of the development, set on the control valve of the development stoste pipeline and set on the pure water pipeline Control valve in either one send control signal.
3. developing apparatus according to claim 1, wherein
The developer solution managing device is also equipped with control mechanism,
The control mechanism has：
Data store is stored with alkali composition concentration data, and the alkali composition concentration data is according to the institute of the Reusability That states developer solution has associated absorbance and a concentration of index of absorbing carbon dioxide with dissolving photoresist agent concentration and determines Concentration range, there is the alkali composition of the developer solution of the Reusability of developing performance as defined in confirmed to realize in advance Concentration value；And
Control unit, will be according to the measured value of the absorbance of the developer solution of the Reusability and absorbing carbon dioxide concentration And determine concentration range the alkali composition concentration value for being stored in the data store as control targe value so that institute Stating the alkali composition concentration of the developer solution of Reusability becomes the mode of the control targe value to set on the new liquid of development With the control valve of pipeline, set on the control valve of the development stoste pipeline and in the control valve of the pure water pipeline Either one sends control signal.
4. developing apparatus according to claim 2, wherein
The developer solution managing device is also equipped with multiple measurement devices, and the multiple measurement device is to described in the Reusability Multiple characteristic values of developer solution are measured, and multiple characteristic value includes the dissolving light with the developer solution of the Reusability Cause agent concentration against corrosion have the associated Reusability the developer solution characteristic value and with described in the Reusability The absorbing carbon dioxide concentration of developer solution has the characteristic value of the developer solution of the associated Reusability,
The control mechanism of the developer solution managing device is also equipped with operational part, and the operational part is according to by the multiple measurement The multiple characteristic values for the developer solution that device determines simultaneously are calculated using multiple-regression analysis described in the Reusability The measured value of the dissolving photoresist agent concentration of developer solution and the measured value of absorbing carbon dioxide concentration.
5. developing apparatus according to claim 2, wherein
The developer solution managing device is also equipped with：
Multiple measurement devices are measured multiple characteristic values of the developer solution of the Reusability, multiple characteristic Value has the associated Reusability comprising the dissolving photoresist agent concentration with the developer solution of the Reusability The characteristic value of the developer solution and there is associated institute with the absorbing carbon dioxide concentration of the developer solution of the Reusability State the characteristic value of the developer solution of Reusability；And
Arithmetical organ, according to multiple spies of the developer solution of the Reusability determined by the multiple measurement device Property value and calculated using multiple-regression analysis the Reusability the developer solution dissolving photoresist agent concentration survey The measured value of definite value and absorbing carbon dioxide concentration.
6. developing apparatus according to claim 2, wherein
The developer solution managing device is also equipped with densimeter,
The control mechanism of the developer solution managing device is also equipped with operational part, and the operational part is based on the Reusability Correspondence between the absorbing carbon dioxide concentration and density of the developer solution, according to being determined by the densimeter The density value of the developer solution of Reusability calculates the absorbing carbon dioxide concentration of the developer solution of the Reusability Measured value.
7. developing apparatus according to claim 2, wherein
The developer solution managing device is also equipped with：
Densimeter；And
Arithmetical organ, it is corresponding between the absorbing carbon dioxide concentration and density of the developer solution based on the Reusability Relationship, calculated according to the density value of the developer solution of the Reusability determined by the densimeter described makes repeatedly The measured value of the absorbing carbon dioxide concentration of the developer solution.
CN201711234725.7A 2017-01-23 2017-11-29 Developing apparatus Pending CN108345169A (en)

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