CN108344662A - The gas concentration lwevel display device and developer solution managing device of developer solution - Google Patents
The gas concentration lwevel display device and developer solution managing device of developer solution Download PDFInfo
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- CN108344662A CN108344662A CN201711232810.XA CN201711232810A CN108344662A CN 108344662 A CN108344662 A CN 108344662A CN 201711232810 A CN201711232810 A CN 201711232810A CN 108344662 A CN108344662 A CN 108344662A
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- developer solution
- carbon dioxide
- absorbing carbon
- dioxide concentration
- value
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 524
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 261
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 261
- 230000007246 mechanism Effects 0.000 claims abstract description 113
- 238000007726 management method Methods 0.000 claims description 112
- 239000007788 liquid Substances 0.000 claims description 73
- 238000005259 measurement Methods 0.000 claims description 41
- 238000011161 development Methods 0.000 claims description 38
- 210000000056 organ Anatomy 0.000 claims description 36
- 238000010521 absorption reaction Methods 0.000 claims description 22
- 238000004364 calculation method Methods 0.000 claims description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 21
- 229910052799 carbon Inorganic materials 0.000 claims description 21
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 14
- 238000013500 data storage Methods 0.000 claims description 13
- 239000004408 titanium dioxide Substances 0.000 claims description 7
- 230000005540 biological transmission Effects 0.000 claims description 6
- 239000003513 alkali Substances 0.000 abstract description 44
- 239000000203 mixture Substances 0.000 abstract description 40
- 239000004615 ingredient Substances 0.000 abstract description 7
- 239000000243 solution Substances 0.000 description 426
- 229960004424 carbon dioxide Drugs 0.000 description 195
- 239000007789 gas Substances 0.000 description 50
- 229920002120 photoresistant polymer Polymers 0.000 description 49
- 238000000034 method Methods 0.000 description 31
- 239000003795 chemical substances by application Substances 0.000 description 28
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 28
- 239000000523 sample Substances 0.000 description 25
- 239000000470 constituent Substances 0.000 description 21
- 230000006870 function Effects 0.000 description 19
- 238000005070 sampling Methods 0.000 description 19
- 230000008859 change Effects 0.000 description 12
- 238000010586 diagram Methods 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 241000790917 Dioxys <bee> Species 0.000 description 10
- 230000003534 oscillatory effect Effects 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 230000008569 process Effects 0.000 description 9
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 8
- 239000000758 substrate Substances 0.000 description 8
- 239000013589 supplement Substances 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 238000002835 absorbance Methods 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 4
- 239000004973 liquid crystal related substance Substances 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 238000004448 titration Methods 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 230000004888 barrier function Effects 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000001739 density measurement Methods 0.000 description 3
- 230000005251 gamma ray Effects 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- 239000012086 standard solution Substances 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000003556 assay Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229910002090 carbon oxide Inorganic materials 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000010808 liquid waste Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000004088 simulation Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- GCNLQHANGFOQKY-UHFFFAOYSA-N [C+4].[O-2].[O-2].[Ti+4] Chemical compound [C+4].[O-2].[O-2].[Ti+4] GCNLQHANGFOQKY-UHFFFAOYSA-N 0.000 description 1
- 238000002479 acid--base titration Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- OEYIOHPDSNJKLS-UHFFFAOYSA-N choline Chemical compound C[N+](C)(C)CCO OEYIOHPDSNJKLS-UHFFFAOYSA-N 0.000 description 1
- 229960001231 choline Drugs 0.000 description 1
- 230000019771 cognition Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 235000019795 sodium metasilicate Nutrition 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 230000028016 temperature homeostasis Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N9/00—Investigating density or specific gravity of materials; Analysing materials by determining density or specific gravity
- G01N9/36—Analysing materials by measuring the density or specific gravity, e.g. determining quantity of moisture
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
- G01N33/0004—Gaseous mixtures, e.g. polluted air
- G01N33/0009—General constructional details of gas analysers, e.g. portable test equipment
- G01N33/0027—General constructional details of gas analysers, e.g. portable test equipment concerning the detector
- G01N33/0036—General constructional details of gas analysers, e.g. portable test equipment concerning the detector specially adapted to detect a particular component
- G01N33/004—CO or CO2
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Analytical Chemistry (AREA)
- Pathology (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Food Science & Technology (AREA)
- Medicinal Chemistry (AREA)
- Photosensitive Polymer And Photoresist Processing (AREA)
- Exposure Of Semiconductors, Excluding Electron Or Ion Beam Exposure (AREA)
Abstract
The present invention provides the gas concentration lwevel display device and developer solution managing device of developer solution.They have densimeter, the density for measuring developer solution.Independently there is good correspondence between the density of developer solution and absorbing carbon dioxide concentration with the concentration of other ingredients such as alkali composition.Measured value of the gas concentration lwevel display device based on density calculates absorbing carbon dioxide concentration according to the correspondence of the density of developer solution and absorbing carbon dioxide concentration, absorbing carbon dioxide concentration is shown using indication mechanism.Developer solution managing device uses the correspondence of the density and absorbing carbon dioxide concentration of developer solution, the absorbing carbon dioxide concentration value of the density value determined or calculating based on developer solution, by make developer solution absorbing carbon dioxide concentration become defined management value or management value it is below in a manner of to developer solution supply replenisher, thus the absorbing carbon dioxide concentration for managing developer solution shows absorbing carbon dioxide concentration using indication mechanism.
Description
Technical field
The present invention relates in semiconductor or the developing procedure of the circuit board of liquid crystal display panel etc. in order to make photoresist
Film develop and use show alkalinity developer solution gas concentration lwevel display device and developer solution managing device.
Background technology
In the photolithographic developing procedure processed for realizing the fine wiring of semiconductor or liquid crystal display panel etc., as general
The liquid of photoresist dissolving after being film-made on substrate, uses the developer solution (hereinafter referred to as " alkaline development for showing alkalinity
Liquid ").
In the manufacturing process of semiconductor or base plate of liquid crystal panel, in recent years, chip, the enlargement of glass substrate and cloth
The miniaturization and highly integrated continuous development of line processing.In such a case, in order to realize large substrate wiring processing
Miniaturization and highly integrated, need the concentration for further accurately measuring the main component of alkaline-based developer come to developer solution into
Row maintains management.
The measurement of the constituent concentration of existing alkaline-based developer is as described in Patent Document 1, and what is utilized is in alkalinity
The concentration (hereinafter referred to as " alkali composition concentration ") of the alkali composition of developer solution can be obtained between conductivity good linear relation this
One principle and concentration (hereinafter referred to as " dissolving photoresist agent concentration ") in the photoresist for being dissolved in alkaline-based developer
Good linear relation this principle can be obtained between absorbance.
However, alkaline-based developer is easy the carbon dioxide absorbed in air and generates carbonate.At this point, the tool in developer solution
There is the alkali composition of developing activity to be consumed and reduce.Thus, in order to accurately carry out maintenance pipe to the developing performance of developer solution
Reason needs to consider the influence that the carbon dioxide that developed liquid absorbs brings developing performance to carry out developer solution management.
In order to solve the problems, Patent Document 2 discloses following developer solution modulating device etc., the developer solutions
Modulating device is measured the ultrasonic propagation velocity of developer solution, conductivity and absorbance, based on alkali concentration, carbonate concentration
And the pre-made relationship (matrix) of ultrasonic propagation velocity in dissolving resin concentration, conductivity and absorbance is aobvious to detect
Alkali concentration, carbonate concentration and the dissolving resin concentration of shadow liquid, and the alkali concentration based on the developer solution determined, carbonate concentration
With dissolving resin concentration and capable of playing make CD values (critical dimension value) (line width) be fixed value in this way
Solvability alkali concentration, the pre-made relationship of carbonate concentration and dissolving resin concentration, to control developer solution stoste
Confession give adjust alkali concentration.
In addition, in patent document 3, disclosing following alkaline developer management system etc., which manages system
Have：Carbonic acid system salt density measurement device is measured the refractive index, conductivity, absorbance of developer solution, and according to this
A little measured values obtain the carbonic acid system salt density in developer solution；And control unit, dress is measured to the carbonic acid system salt density
It sets and is controlled with the carbonic acid system salt density in developer solution.
Citation
Patent document
Patent document 1：No. 2561578 bulletins of Japanese Patent No.
Patent document 2：Japanese Unexamined Patent Publication 2008-283162 bulletins
Patent document 3：Japanese Unexamined Patent Publication 2011-128455 bulletins
However, the ultrasonic propagation velocity value or refractive index value of alkaline-based developer are to indicate the alkaline-based developer of multicomponent system
Liquid entirety property characteristic value.It is such indicate liquid entirety property characteristic value not usually only in the liquid
The concentration of the specific ingredient contained is related.It is such to indicate that the characteristic value of the property of liquid entirety usually contains with the liquid
The concentration of various composition be respectively provided with relevance.Therefore, in the characteristic value according to such property for indicating liquid entirety
In the case that measured value carrys out the constituent concentration of operation developer solution, if it is only related to certain specific constituent concentration to set certain characteristic value
(for example there is linear relations) and ignore the influence that other ingredients bring the characteristic value, then exist can not be calculated with sufficient precision
The problem of going out the concentration of the special component.
On the other hand, the function of the concentration of the various composition contained in the characteristic value for setting developer solution is developer solution and root
In the case of calculating each constituent concentration according to the measured value of the characteristic value of developer solution, after determining multiple characteristic values, need
Using the operation method appropriate for calculating each constituent concentration according to the measured value of these characteristic values.Suitably, however selection is wanted
It the characteristic value of measurement and finds and can precisely calculate the appropriate of each constituent concentration according to the measured value of characteristic value
Operation method is all very difficult.Therefore, if measured characteristic value and operation method is inappropriate, existing can not be with abundant
Precision calculate each constituent concentration the problem of.
In turn, in the liquid of multicomponent system, the concentration of certain usual ingredient can't be only each other with the concentration of other ingredients
It is vertical.In the liquid of multicomponent system, there is when the variation of the concentration of certain ingredient other constituent concentrations also phase as variation simultaneously
Mutual relation.The calculating for being more difficult to carry out high-precision constituent concentration and high-precision developer solution management are resulted in this way.
In addition, for the concentration (hereinafter referred to as " absorbing carbon dioxide concentration ") for the carbon dioxide that developer solution is absorbed,
And it is unaware of and the characteristic value appropriate there are the developer solution of good relevance between the absorbing carbon dioxide concentration, current hardly possible
Precisely to measure absorbing carbon dioxide concentration.Especially, in the management of developer solution, it is important that the energy such as user
Confirm absorbing carbon dioxide concentration.
Invention content
The subject that the invention solves
The present invention proposes to solve above-mentioned each project.The purpose of the present invention is to provide one kind can be according to multicomponent
The density value of the developer solution of system measures the absorbing carbon dioxide concentration of developer solution and can show absorbing carbon dioxide concentration
Gas concentration lwevel display device and can be so that the gas concentration lwevel of developer solution becomes defined management value or not
The developer solution managing device being managed more than the mode of defined management value.
Solution for solving the problem
The gas concentration lwevel display device of the developer solution of the present invention has：Densimeter；Arithmetical organ, based on by described
What densimeter determined shows the density value of the developer solution of alkalinity, according to the density of the developer solution and absorbing carbon dioxide concentration
Between correspondence calculate the absorbing carbon dioxide concentration of the developer solution；And indication mechanism, it shows by the fortune
Calculate the absorbing carbon dioxide concentration for the developer solution that mechanism calculates.
The gas concentration lwevel display device of the developer solution of the present invention has：Densimeter；Arithmetical organ, based on by described
What densimeter determined shows the density value of the developer solution of alkalinity, according to the density of the developer solution and absorbing carbon dioxide concentration
Between correspondence calculate the absorbing carbon dioxide concentration of the developer solution；And indication mechanism, it shows by described close
The density value for the developer solution that degree instrument determines and the absorbing carbon dioxide of the developer solution calculated by the arithmetical organ
Concentration.
The gas concentration lwevel display device of the developer solution of the present invention has：Densimeter is repeatedly measured and shows alkalinity
The density value of developer solution；Arithmetical organ, when the densimeter measures the density value every time, based on being surveyed by the densimeter
The density value made, according to the correspondence between the density of the developer solution and absorbing carbon dioxide concentration to calculate
State the absorbing carbon dioxide concentration of developer solution；Determination data storing mechanism, the development that will be calculated by the arithmetical organ
The absorbing carbon dioxide concentration of liquid with measure the moment and measure start start by being stored together with either one in the time；
And indication mechanism, by the absorbing carbon dioxide concentration for being stored in the determination data storing mechanism with described in storing together
It measures the moment or the measurement starts being shown for index to carry out chart by the time for start of calculation.
The gas concentration lwevel display device of the developer solution of the present invention has；Densimeter is repeatedly measured and shows alkalinity
The density value of developer solution；Arithmetical organ, when the densimeter measures the density value every time, based on being surveyed by the densimeter
The density value made, according to the correspondence between the density of the developer solution and absorbing carbon dioxide concentration to calculate
State the absorbing carbon dioxide concentration of developer solution；Determination data storing mechanism, the development that will be determined by the densimeter
The absorbing carbon dioxide concentration and measurement moment and measurement of the density value of liquid and the developer solution calculated by the arithmetical organ
Start to start stores together by either one in the time；And indication mechanism, the determination data will be stored in
The institute of the density value of the developer solution of storing mechanism and either one in absorbing carbon dioxide concentration value to store together
It states the measurement moment or the measurement starts being shown for index to carry out chart by the time for start of calculation.
The gas concentration lwevel display device of the developer solution of the present invention is preferably also equipped with display switching mechanism, and the display is cut
Converting mechanism be shown in the indication mechanism chart be switched to the developer solution density value chart or the developer solution
Absorbing carbon dioxide concentration chart.
According to the present invention, since the absorbing carbon dioxide concentration for having pair with developer solution has the close of good correspondence
The densimeter that angle value is measured, therefore the absorption dioxy of developer solution can be calculated according to the density value determined by densimeter
Change concentration of carbon, and can show absorbing carbon dioxide concentration.
The developer solution managing device of the present invention has：Densimeter；Arithmetical organ, based on what is determined by the densimeter
The density value for showing the developer solution of alkalinity, according to the correspondence between the density of the developer solution and absorbing carbon dioxide concentration
To calculate the absorbing carbon dioxide concentration of the developer solution；Indication mechanism, display are calculated described aobvious by the arithmetical organ
The absorbing carbon dioxide concentration value of shadow liquid；And control mechanism, based on the developer solution calculated by the arithmetical organ
Absorbing carbon dioxide concentration value so that the absorbing carbon dioxide concentration of the developer solution become defined management value or management value with
Under mode send control signal to control valve, the pipe of replenisher fed to the developer solution in conveying is arranged in the control valve
On the road.
The developer solution managing device of the present invention has：Densimeter；Arithmetical organ, based on what is determined by the densimeter
The density value for showing the developer solution of alkalinity, according to the correspondence between the density of the developer solution and absorbing carbon dioxide concentration
To calculate the absorbing carbon dioxide concentration value of the developer solution；Indication mechanism, described in display is determined by the densimeter
The absorbing carbon dioxide concentration of the density value of developer solution and the developer solution calculated by the arithmetical organ；And control machine
Structure, based on the absorbing carbon dioxide concentration of the developer solution calculated by the arithmetical organ, so that the suction of the developer solution
Receiving gas concentration lwevel becomes defined management value or management value mode below to control valve transmission control signal, the control
Valve is arranged on the pipeline for the replenisher that conveying is fed to the developer solution.
The developer solution managing device of the present invention has：Densimeter is repeatedly measured the density value for the developer solution for showing alkalinity；
Arithmetical organ, when the densimeter measures the density value every time, based on the density determined by the densimeter
Value, the absorption of the developer solution is calculated according to the correspondence between the density of the developer solution and absorbing carbon dioxide concentration
Carbon dioxide concentration value；Determination data storing mechanism, by the absorption dioxy of the developer solution calculated by the arithmetical organ
Change concentration of carbon value with measure the moment and measure start start by being stored together with either one in the time；Indication mechanism,
Its measurement moment for storing the absorbing carbon dioxide concentration value for being stored in the determination data storing mechanism together or
What the measurement started to start shows for index to carry out chart by the time；And control mechanism, based on by the operation
The absorbing carbon dioxide concentration value for the developer solution that mechanism calculates, so that the absorbing carbon dioxide concentration of the developer solution becomes
Defined management value or management are worth mode below and send control signal to control valve, and the control valve setting is being conveyed to described
On the pipeline of the replenisher of developer solution supply.
The developer solution managing device of the present invention has：Densimeter is repeatedly measured the density value for the developer solution for showing alkalinity；
Arithmetical organ, when the densimeter measures the density value every time, based on the density determined by the densimeter
Value, the absorption of the developer solution is calculated according to the correspondence between the density of the developer solution and absorbing carbon dioxide concentration
Carbon dioxide concentration value；Determination data storing mechanism, by the density value of the developer solution determined by the densimeter and
The absorbing carbon dioxide concentration value of the developer solution calculated by the arithmetical organ and start of calculation measuring the moment and measuring
It is stored together by either one in the time；Indication mechanism will be stored in described in the determination data storing mechanism
The density value of developer solution and either one in absorbing carbon dioxide concentration value are with the measurement moment stored together or institute
It states to measure and starts being shown for index to carry out chart by the time for start of calculation；And control mechanism, based on by the calculating machine
The absorbing carbon dioxide concentration value for the developer solution that structure calculates, so that the absorbing carbon dioxide concentration of the developer solution becomes rule
Fixed management value or management are worth mode below and send control signal to control valve, and the control valve setting is being conveyed to described aobvious
On the pipeline of the replenisher of shadow liquid supply.
The developer solution managing device of the present invention is preferably also equipped with display switching mechanism, and the display switching mechanism is shown in
The chart of the indication mechanism is switched to the chart of the density value of the developer solution or the absorbing carbon dioxide of the developer solution
The chart of concentration.
According to the present invention, since the absorbing carbon dioxide concentration for having pair with developer solution has the close of good correspondence
The densimeter that angle value is measured, therefore the absorption dioxy of developer solution can be calculated according to the density value determined by densimeter
Change concentration of carbon, and can show absorbing carbon dioxide concentration, it can be so that the absorbing carbon dioxide concentration of developer solution becomes rule
Fixed management value or management value mode below feeds replenisher to be managed.
The developer solution managing device of the present invention has densimeter and operation control mechanism, and the operation control mechanism has：
Operational part, based on the density value of the developer solution for showing alkalinity determined by the densimeter, according to the close of the developer solution
It spends and calculates the absorbing carbon dioxide concentration of the developer solution the correspondence between absorbing carbon dioxide concentration；Display unit,
It shows the absorbing carbon dioxide concentration value of the developer solution calculated by the operational part；And control unit, based on by institute
The absorbing carbon dioxide concentration value for stating the developer solution of operational part calculating, so that the absorbing carbon dioxide concentration of the developer solution
Be worth mode below as defined management value or management and send control signal to control valve, the control valve setting conveying to
On the pipeline of the replenisher of the developer solution supply.
The developer solution managing device of the present invention has densimeter and operation control mechanism, and the operation control mechanism has：
Operational part, based on the density value of the developer solution for showing alkalinity determined by the densimeter, according to the close of the developer solution
It spends and calculates the absorbing carbon dioxide concentration of the developer solution the correspondence between absorbing carbon dioxide concentration；Display unit,
It shows the density value of the developer solution determined by the densimeter and the developer solution that is calculated by the operational part
Absorbing carbon dioxide concentration value；And control unit, the absorption titanium dioxide based on the developer solution calculated by the operational part
Concentration of carbon value, by make the developer solution absorbing carbon dioxide concentration become defined management value or management value it is below in a manner of to
Control valve sends control signal, and the control valve is arranged on the pipeline for the replenisher that conveying is fed to the developer solution.
The present invention developer solution managing device have be repeatedly measured show alkalinity developer solution density value densimeter and
Operation control mechanism, the operation control mechanism have：Operational part, when the densimeter measures the density value every time,
Based on the density value determined by the densimeter, according between the density of the developer solution and absorbing carbon dioxide concentration
Correspondence calculate the absorbing carbon dioxide concentration value of the developer solution；Determination data storage part, will be by the operation
Portion calculate the developer solution absorbing carbon dioxide concentration value with measure the moment and measure start start by the time
Either one is stored together；Display unit will be stored in the absorbing carbon dioxide concentration of the determination data storage part with one
The process time that the measurement moment of storage or the measurement start to start carries out chart for index and shows；And control
Portion, based on the absorbing carbon dioxide concentration value of the developer solution calculated by the operational part, so that the suction of the developer solution
Receiving gas concentration lwevel becomes defined management value or management value mode below to control valve transmission control signal, the control
Valve is arranged on the pipeline for the replenisher that conveying is fed to the developer solution.
The present invention developer solution managing device have be repeatedly measured show alkalinity developer solution density value densimeter and
Operation control mechanism, the operation control mechanism have：Operational part, when the densimeter measures the density value every time,
Based on the density value of the developer solution determined by the densimeter, according to the density and absorbing carbon dioxide of the developer solution
Correspondence between concentration calculates the absorbing carbon dioxide concentration of the developer solution；Determination data storage part, will be by institute
State the density value for the developer solution that densimeter determines and the absorption titanium dioxide of the developer solution calculated by the operational part
Concentration of carbon value with measure the moment and measure start start by being stored together with either one in the time；Display unit, will
It is stored in the density value of the developer solution of the determination data storage part and at least any in absorbing carbon dioxide concentration value
Side is shown as index to carry out chart using the time of passing through that the measurement moment stored together or the measurement start to start；With
And control unit, based on the absorbing carbon dioxide concentration value of the developer solution calculated by the operational part, so that the development
The absorbing carbon dioxide concentration of liquid becomes defined management value or management is worth mode below and sends control signal, institute to control valve
Control valve is stated to be arranged on the pipeline for the replenisher that conveying is fed to the developer solution.
The developer solution managing device of the present invention is preferably also equipped with display switching mechanism, and the display switching mechanism is shown in
The chart of the display unit is switched to the chart of the density of the developer solution or the absorbing carbon dioxide concentration of the developer solution
Chart.
According to the present invention, since the absorbing carbon dioxide concentration for having pair with developer solution has the close of good correspondence
The densimeter that angle value is measured, therefore the absorption dioxy of developer solution can be calculated according to the density value determined by densimeter
Change concentration of carbon, and can show absorbing carbon dioxide concentration, it can be so that the absorbing carbon dioxide concentration of developer solution becomes rule
Fixed management value or management value mode below feeds replenisher to be managed.
Invention effect
It was difficult to the absorbing carbon dioxide concentration of the developer solution measured in the past in accordance with the invention it is possible to measure, and can be shown
Show the absorbing carbon dioxide concentration.In addition, can based on the absorbing carbon dioxide concentration value of the density value or calculating determined, with
So that the absorbing carbon dioxide concentration of developer solution is become defined management value or management value mode below and feeds supplement to developer solution
Liquid is managed.
Description of the drawings
Fig. 1 is the chart of the relationship of the absorbing carbon dioxide concentration and density that indicate developer solution.
Fig. 2 is the schematic diagram of the gas concentration lwevel display device of first embodiment.
Fig. 3 is the schematic diagram of the representative configurations of oscillatory type densimeter.
Fig. 4 is the schematic diagram of the gas concentration lwevel display device of second embodiment.
Fig. 5 is the schematic diagram of the development treatment process for the developer solution managing device for including third embodiment.
Fig. 6 is the schematic diagram of the development treatment process for the developer solution managing device for including the 4th embodiment.
Fig. 7 is the schematic diagram of the development treatment process for the developer solution managing device for including the 5th embodiment.
Drawing reference numeral explanation：
A ... gas concentration lwevels display device, B ... developing procedures equipment, C ... replenishers reservoir, D ... circulation stirring machines
Structure, E ... developer solution managing devices
1 ... determination part
11 ... densimeters, 12,13 ... measuring means, 14 ... sampling pumps, 15 ... sampling pipings, 16 ... outlet side lines
2 ... operational parts
21 ... computing modules, 22 ... indication mechanisms
23 ... calculation control units (such as computer)
3 ... control units
31 ... control modules
41~43 ... control valves, 44,45,46,47 ... valves,
51 ... sample cells, 52 ... thermometers, 53 ... Peltier's elements, 54 ... thermostat modules, 55 ... thermal insulation barriers, 56 ... shake
Son, 61 ... developer solution storagetanks, 62 ... overflow launders, 63 ... liquid level meters, 64 ... developing room shields, 65 ... roller conveyors, 66 ...
Substrate, 67 ... developer solution spray nozzles, 71 ... waste drains pumps, 72,74 ... circulating pumps, 73,75 ... filters, 80 ... development liquid pipelines,
81,82 ... replenishers (development stoste and/or new liquid) pipeline, 83 ... pure water pipelines, 84 ... interflow pipelines, 85 ... circulation pipes
Road, 86 ... nitrogen pipelines, 91,92 ... replenisher storagetanks
10 ... determination data storing mechanisms
101 ... memory modules.
Specific implementation mode
Hereinafter, suitably referring to attached drawing, the preferred embodiments of the present invention is described in detail.Wherein, as long as no
It is particularly limited to, shape, size, size ratio, its relative configuration of device recorded in these embodiments etc. etc. just not only limit
Due to the example for illustrating the scope of the present invention.These examples be merely possible to illustrate example and schematically illustrated and
.
In addition, in the following description, as the concrete example of developer solution, suitably having used in semiconductor or liquid crystal display panel base
Main 2.38wt% tetramethylammonium hydroxide aqueous solutions to be used are (hereinafter, tetramethylammonium hydroxide is claimed in the manufacturing process of plate
Make TMAH) it illustrates.But it's not limited to that for the developer solution of the invention that can be applicable in.Developer solution as the present invention
Gas concentration lwevel display device or the example of other developer solutions that can be applicable in such as developer solution managing device, can also enumerate
The aqueous solution or trimethyl monoethanol base hydroxide of the inorganic compounds such as potassium hydroxide, sodium hydroxide, sodium phosphate, sodium metasilicate
The aqueous solution of the organic compounds such as ammonium (choline).
In addition, in the following description, alkali composition concentration, dissolving photoresist agent concentration, absorbing carbon dioxide concentration etc.
Constituent concentration is the concentration based on weight percent concentration (wt%)." dissolving photoresist agent concentration " refer to will dissolve it is photic
Resist is converted into the concentration in the case of the amount of photoresist, and " absorbing carbon dioxide concentration " refers to by absorbed dioxy
Change carbon is converted into the concentration in the case of the amount of carbon dioxide.
In development process, developer solution dissolves the unnecessary portion of the photoresist film after exposure-processed, by
This develops.It is dissolved between the photoresist of developer solution and the alkali composition of developer solution and will produce photoresist salt.Cause
This, if not being managed suitably to developer solution, with the progress of development treatment, in developer solution with developing activity
Alkali composition is consumed and deteriorates, and developing performance deteriorates.Meanwhile it being dissolved in the photoresist in developer solution and being sent out with alkali composition
Life is reacted and is constantly accumulated in the form of photoresist salt.
The photoresist for being dissolved in developer solution shows interfacial activity effect in developer solution.Therefore, it is dissolved in developer solution
Photoresist can improve the wellability relative to developer solution of the photoresist film for being used to development treatment so that development
The compatibility of liquid and photoresist film improves.Thus, in the developer solution moderately containing photoresist, developer solution is good
Ground spreads all in the fine recess portion of photoresist film, so as to implement the concave-convex photoresist for having fine well
The development treatment of agent film.
In addition, in development treatment in recent years, with the enlargement of substrate, a large amount of developer solution of Reusability, therefore it is aobvious
The chance that shadow liquid is exposed to air increases.However, alkaline-based developer can absorb the carbon dioxide in air if being exposed to air.
Carbonate is will produce between absorbed carbon dioxide and the alkali composition of developer solution.Therefore, if inadequately managing developer solution,
Carbon dioxide-depleted that the alkali composition with developing activity in developer solution is absorbed and reduce.Meanwhile it being inhaled in developer solution
The carbon dioxide of receipts is reacted with alkali composition and is constantly accumulated in the form of carbonate.
Carbonate in developer solution shows alkalinity in developer solution, therefore has development effect.For example, by using 2.38%
In the case of TMAH aqueous solutions, if carbon dioxide in developer solution be about 0.4wt% degree hereinafter, if can develop.
In this way, different from " carbon dioxide that the photoresist dissolved in developer solution or developed liquid absorb to development at
Unwanted for reason " as existing cognition, in fact, the photoresist dissolved in developer solution or developed liquid absorb
Carbon dioxide contribute to the developing performance of developer solution.Therefore, be not into be about to dissolve photoresist or absorb two
Carbonoxide excludes such developer solution management completely, but needs to carry out following developer solution management, that is, allows in developer solution
It is slightly molten to have photoresist or absorbing carbon dioxide and maintain management at best concentration them.
Based on above-mentioned point, inventor constantly carefully studies, and obtains following opinion.That is, the alkali composition with developer solution is dense
Degree, dissolving photoresist agent concentration it is unrelated, developer solution density value compared with it can be obtained between absorbing carbon dioxide concentration value
Good correspondence (linear relation).If in addition, using the correspondence (linear relation), surveyed by using densimeter
Determine the density of developer solution, it will be able to which measurement was difficult to the absorbing carbon dioxide concentration measured in the past.If moreover, using the correspondence
(linear relation) then can pass through the benefit of replenisher based on the absorbing carbon dioxide concentration value of the density value or calculating determined
It gives to be managed to the absorbing carbon dioxide concentration of developer solution.
Inventor assumes the case where carrying out the management of 2.38%TMAH aqueous solutions, and alkali composition concentration, dissolving will be made photic anti-
Erosion agent concentration, absorbing carbon dioxide concentration occur the TMAH aqueous solutions obtained by various change and are modulated into simulation developer solution sample.Hair
A person of good sense's forming substantially using 2.38%TMAH aqueous solutions as developer solution modulates alkali composition concentration (TMAH concentration) of sening as an envoy to, dissolving
11 calibration standard solution obtained by various change occur for photoresist agent concentration, absorbing carbon dioxide concentration.
Inventor is tested as follows：For these simulation developer solution sample, measure alkali composition concentration (TMAH concentration),
Absorbing carbon dioxide concentration and density confirm the correlation of constituent concentration and density.
Measurement is carried out by the way that the temperature for correcting standard solution is adjusted to 25.0 DEG C.Temperature adjusts in the following way：
The bottle for being put into calibration standard solution is immersed in for a long time in the thermostatic water bath that temperature is managed as near 25 DEG C, from the bottle
It is sampled in son, then, 25.0 DEG C is adjusted to again using temperature controller before horse back will be measured.Density measurement, which has used, adopts
With the densimeter of self-oscillation method, the self-oscillation method is according to the intrinsic vibration number measured into row energization to U-shaped pipe flow cell
To solve density.The unit of the density value determined is g/cm3。
The constituent concentration of each sample and the measurement result of density are shown in table 1 below.
【Table 1】
Absorbing carbon dioxide is easy in view of TMAH aqueous solutions because of strong basicity thus to deteriorate, the constituent concentration of table 1 makes
It is separately right that alkali composition concentration (TMAH concentration), the analysis by titration of absorbing carbon dioxide concentration can be accurately analyzed with utilization
Each sample is measured the value of gained.Wherein, about dissolving photoresist agent concentration, weight modulation value has been used.
Titration is using hydrochloric acid as the acid-base titration of titer reagent.Mitsubishi Chemical's analytical technology has been used as titration outfit
The automatic titration device GT-200 of corporation.
The absorbing carbon dioxide concentration of each sample shown in table 1 and the chart of density is shown in FIG. 1.The chart is will to inhale
It receives gas concentration lwevel (wt%) and is taken as horizontal axis and by density (g/cm3) it is taken as the longitudinal axis, it draws and schemes obtained from the value of each sample
Table.According to each point drawn out and find out regression straight line using least square method.
According to Fig. 1 it is to be understood that the absorbing carbon dioxide concentration of developer solution and alkali composition concentration or dissolving photoresist
It is unrelated why agent concentration is worth, and there are good straight line passes between the absorbing carbon dioxide concentration and the density of developer solution of developer solution
System.Inventor has found according to the experimental result：If using corresponding between the absorbing carbon dioxide concentration and density of the developer solution
Relationship (linear relation) then can calculate the absorbing carbon dioxide concentration of developer solution by measuring the density of developer solution.
Thus, it is possible to realize the gas concentration lwevel display device of following developer solution：(TMAH is dense with alkali composition concentration
Degree) or dissolving photoresist agent concentration it is unrelated and utilize and the correspondence (linear relation) and measure developer solution using densimeter
Absorbing carbon dioxide concentration.
In addition, in development treatment process in the alkaline-based developer of Reusability, developer solution managing device pair is usually utilized
Alkali composition concentration (TMAH concentration), dissolving photoresist agent concentration are managed.Compared with the experiment of above-mentioned analog sample, make
What the linearity between the density and absorbing carbon dioxide concentration of developer solution deteriorated will be because less.Thus, of the invention can survey
Determining the gas concentration lwevel display device of the absorbing carbon dioxide concentration of developer solution, be also adaptable as can be to absorbing carbon dioxide
One component of the developer solution managing device that concentration is monitored or managed uses.
Moreover, for alkaline-based developer, there is the increased trend of absorbing carbon dioxide, therefore absorb two by supplementing
Aoxidizing the small replenisher (such as stoste of developer solution or new liquid etc.) of concentration of carbon, act as a supplement liquid, and thus, it is possible to by developer solution
Absorbing carbon dioxide concentration management is at defined management value or manages below at defined management value.
In addition, because there is the corresponding pass being increased monotonically in the absorbing carbon dioxide concentration with density of the developer solution as Fig. 1
It is (linear relation), therefore it is just equivalent so that the absorbing carbon dioxide concentration of developer solution is become defined management value or management value or less
In make the density value of developer solution become corresponding as defined in below management value or management value.Thus, if will be with absorbing carbon dioxide
The management of concentration is worth the management value that corresponding density value is set as density, by measuring the density of developer solution and so that this was determined
Density value becomes its management value or management value mode below is managed, then also can be to make developer solution by developer solution management
Absorbing carbon dioxide concentration become defined management value or management value or less.
Here, it is specified that management value refer to, as can make developer solution play well developing performance developer solution two
The upper limit of the concentration value of carbonoxide and the concentration value or density value corresponding with the concentration value being previously validated.In theory below
It is also the same in bright.
Then, specific embodiment is illustrated with reference to attached drawing.
(first embodiment)
Fig. 2 is the schematic diagram of the gas concentration lwevel display device of the developer solution of present embodiment.
The gas concentration lwevel display device A of the developer solution of present embodiment has determination part 1, operational part 2 and display machine
Structure 22.
Determination part 1 has the densimeter of density for measuring developer solution and other characteristic values for measuring developer solution
Other measuring means (11~13 in figure), sampling pump 14 and for the temperature of the developer solution of sampling to be adjusted to before the assay
The thermostat (not shown) etc. of defined measuring temperature (such as 25 DEG C).
In the case where gas concentration lwevel display device A only measures density, the measuring means 11 as determination part 1
~13, have densimeter (such as 11), the measuring means (such as 12,13) of other characteristic values need not be measured.However, big
In the case of more, as the gas concentration lwevel display device of alkaline-based developer, absorbing carbon dioxide concentration not only measured, is also wanted
It measures the concentration of alkali composition, be dissolved in the photoresist agent concentration of developer solution.Therefore, in fig. 2, describing will be in order to measure alkali
Constituent concentration, dissolving photoresist agent concentration etc. and other measuring means for needing be also included in measuring means 11,12,
13.One of these measuring means are densimeter.In the explanation of gas concentration lwevel display device A below, by the measurement of Fig. 2
Measuring means 11 in mechanism 11~13 is set as densimeter.
Operational part 2 has the computing module 21 that absorbing carbon dioxide concentration value is calculated according to the density value determined.
Pre-entered in computing module 21 between the density of developer solution and absorbing carbon dioxide concentration correspondence (such as Fig. 1 that
The linear relation of sample).Computing module 21, which has, solves corresponding absorption titanium dioxide according to the density value of the developer solution determined
The function of concentration of carbon value.In addition, gas concentration lwevel display device A is connect by sampling piping 15 with the slot of storage developer solution.
The gas concentration lwevel display device A of embodiment has indication mechanism 22, therefore can show the development of calculating
The absorbing carbon dioxide concentration of liquid.In addition, the density of the developer solution determined by the densimeter 11 of determination part 1 can be shown.It inhales
Indication mechanism 22 can be shown in simultaneously by receiving gas concentration lwevel and density, can also be shown by image switching.
The assay method that absorbing carbon dioxide concentration is measured to the gas concentration lwevel display device A of present embodiment carries out
Explanation.Developer solution is conveyed by sampling pump 14 into determination part 1.The developer solution of determination part 1 is transported to first in thermostat
In be adjusted temperature and become defined measuring temperature (such as 25 DEG C).Temperature be adjusted after developer solution to densimeter 11 and its
Its measuring means 12,13 conveys.Densimeter 11 measures the density of developer solution.Other measuring means 12,13 also measure development respectively
The characteristic value of liquid.Developer solution after measurement is discharged from outlet side line 16 to outside gas concentration lwevel display device A.
Densimeter 11 and other measuring means 12,13 are connect by signal wire with the computing module 21 of operational part 2.By density
The measurement number of the characteristic value of the density value for the developer solution that instrument 11 determines and the developer solution determined by other measuring means 12,13
It is sent to computing module 21 according to via signal wire.
Have received the computing module 21 of the density value of developer solution and the determination data of other characteristic values based on determination data come
Calculate the constituent concentration of developer solution.Use correspondence (such as Fig. 1 between the density and absorbing carbon dioxide concentration of developer solution
Such linear relation) calculate the absorbing carbon dioxide concentration of developer solution.That is, according to the density of developer solution and absorption titanium dioxide
Correspondence between concentration of carbon obtains absorbing carbon dioxide concentration value corresponding with the density value of the developer solution determined, and
The value is set as to the measured value of the absorbing carbon dioxide concentration of developer solution.
In this way, the gas concentration lwevel display device A of the developer solution of present embodiment can be based on the density of developer solution
Measured value measures the absorbing carbon dioxide of developer solution according to the correspondence of the density of developer solution and absorbing carbon dioxide concentration
Concentration, and can show absorbing carbon dioxide concentration.
For the gas concentration lwevel display device A of present embodiment, in addition to determination part 1, operational part as shown in Figure 2
2 and indication mechanism 22 as one device and the case where constitute except, can also be by determination part 1, operational part 2 and indication mechanism
22 are constituted seperatedly.In the case of seperated composition, determination part 1 and the signal wire of operational part 2 etc. are connect, so that
The determination data determined by the densimeter 11 and other measuring means 12,13 of determination part 1 is connect by the computing module 21 of operational part 2
It receives.Can wirelessly determination data be transmitted and received between determination part 1 and operational part 2.In addition, by indication mechanism 22
It is connect with operational part 2, so that indication mechanism 22 receives the data from operational part 2.
The gas concentration lwevel display device A and its determination part 1 of present embodiment can also be with the storages of storage developer solution
Slot connects, and enables to be sampled developer solution from storagetank.Alternatively, gas concentration lwevel display device A and its survey
Determining portion 1 can directly or with bypassing be connected on the recycle circuit for the development treatment process for recycling developer solution.
In addition, in fig. 2, it is illustrated that the mode that each measuring means 11~13 including densimeter is connected in series with, but
It's not limited to that for the connection of each measuring means.It can be connected in parallel, can also have liquor charging path independently of one another to carry out
It measures.The measurement of densimeter and other measuring means sequence is paid no attention to successively.Can according to the feature of each measuring means and suitably with
Best sequence is measured.
In the structure of determination part 1 shown in Fig. 2, sampling pump 14 is not necessary.It is being directly connected in recycle circuit
In the case of, sampling pump 14 need not be set in determination part 1.In addition, the case where being sampled to developer solution from storagetank
Under, sampling pump 14 can not also be set in determination part 1.On the other hand, although not shown, but it is preferred for developer solution being adjusted to
The thermostat of defined measuring temperature is arranged in the immediately front of measuring means.
The computing module 21 of operational part 2 is in addition to having the work(for calculating absorbing carbon dioxide concentration according to the measured value of density
Except energy, can also have the work(of other constituent concentrations such as the alkali composition concentration for calculating developer solution, dissolving photoresist agent concentration
Energy.In such manner, it is possible to realize the alkali composition concentration that can measure developer solution, dissolving photoresist agent concentration and absorbing carbon dioxide concentration
Gas concentration lwevel display device.
The densimeter 11 of gas concentration lwevel display device A as present embodiment may be used and utilize the floating of buoyancy
Mark formula densimeter, using the different point-to-point transmission of the height in liquid pressure difference differential pressure density instrument, utilize gamma ray
The various densimeters such as the gamma ray density instrument of transmissivity.It is further preferred that using the intrinsic of the pipeline to being filled with liquid
Vibration number is detected to obtain the oscillatory type densimeter of density.
Fig. 3 schematically shows the representative configurations of oscillatory type densimeter.
The determination part of oscillatory type densimeter, which has, bends to the sample cell 51 of U-shaped, to the liquid in sample cell 51
The thermostat module 54 for the thermometer 52, encirclement sample cell 51 that the temperature of sample is measured and setting are in thermostat module 54
Periphery thermal insulation barriers 55.Thermostat module 54 is provided with the Peltier's element 53 of the temperature for adjusting sample.In sample list
The front end of bending section of member 51 is provided with oscillator 56, by close in a manner of oscillator 56 configured with to oscillator 56 into the driving of row energization
The test section of the vibration frequency of portion and detection oscillator 56.
Energized sample cell 51 is vibrated with the intrinsic vibration number of the quality association of the liquid internal with it.Pass through
The intrinsic vibration number is detected, thus knows the quality of the liquid in sample cell 51, therefore can be according in sample cell 51
Volume measures the density of liquid.
Oscillatory type densimeter has following feature：Measurement that is highly sensitive and stablizing can be carried out, and can be connected
It is continuous to measure.Oscillatory type densimeter passes through thermometer, temperature adjusting mechanism (Peltier's element 53 in Fig. 3) and heat-shield mechanism (Fig. 3
In thermal insulation barriers 55) and can realize the measurement based on good temperature condition and temperature stability.In addition, oscillatory type densimeter
Only the density of sample can be measured by conveying the liquid of sample to sample cell.In density measurement, need not be tried
The addition etc. of agent, also without waste liquid.
Various measuring means 11~13 in the gas concentration lwevel display device of the developer solution of present embodiment, especially
The set-up mode of densimeter is not limited to mode shown in Fig. 2.
Densimeter has various measuring principles and mensuration mode, thus with the setting method mutually fitted therewith respectively.It is adopting
It uses float type densimeter, differential pressure density instrument as in the case of densimeter, the buoy portion of densimeter, probe portion is impregnated in
The mode density of setting instrument of the storagetank of developer solution is preferably.It, can be in developer solution using gamma ray density instrument
Direct density of setting instrument on the pipeline of flowing.Using oscillatory type densimeter in the case of, as shown in Fig. 2, by storagetank with it is close
If degree instrument is connected by sampling line, it will be able to be sampled to developer solution to carry out METHOD FOR CONTINUOUS DETERMINATION.
Oscillatory type densimeter is suitable for continuous only by the way that developer solution can be measured density to sample cell conveying
And online use.In addition, being suitable for steadily being managed the determination conditions such as liquid temperature, can carry out stable and highly sensitive
Measurement.It, also can be with 0.001 (g/cm even the oscillatory type densimeter of engineering3) left and right precision be measured, according to
The linear relation of Fig. 1, the gas concentration lwevel display device of present embodiment can reach the dioxy of the left and right about 0.15 (wt%)
Change Carbon analysis precision.If the alkali composition concentration of developer solution, dissolving photoresist agent concentration are in the situation being managed, density
Become raising that is more good, but also can expecting the measurement accuracy of densimeter with the linearity of absorbing carbon dioxide concentration,
Therefore can also expect more precisely to measure the absorbing carbon dioxide concentration of gas concentration lwevel display device.
The gas concentration lwevel display device of the developer solution of present embodiment utilizes the absorption dioxy that can measure developer solution
This characteristic of change concentration of carbon, can be efficiently applied to developer solution management as managing the component of absorbing carbon dioxide concentration
Device.By combining following control mechanism with the gas concentration lwevel display device of present embodiment, and can constitute can
To the developer solution managing device that absorbing carbon dioxide concentration is managed, the control mechanism is based on gas concentration lwevel display dress
The absorbing carbon dioxide concentration of the developer solution determined is set, so that the absorbing carbon dioxide concentration of developer solution becomes defined management
Value or management value mode below feed replenisher to be controlled to developer solution.
In addition, the gas concentration lwevel display device of the developer solution using present embodiment, by the developer solution determined
Absorbing carbon dioxide concentration is compared with the permissible value of the absorbing carbon dioxide concentration of developer solution, is sent out when more than permissible value
Signal makes emergency warning lamp flicker or make buzzer call, in this case can also constitute the constituent concentration monitoring arrangement of developer solution.
(second embodiment)
Fig. 4 is the schematic diagram of the gas concentration lwevel display device of the developer solution of the other manner of present embodiment.
The gas concentration lwevel display device A of the developer solution of present embodiment has determination part 1, operational part 2, indication mechanism
22 and the determination data storage part 10 with memory module 101.Determination data storage part 10 will be determined by determination part 1
The density of developer solution and the absorbing carbon dioxide concentration calculated by operational part 2 and when passing through of start of calculation measuring the moment and measuring
Between in either one stored together.
Indication mechanism 22 can by be stored in determination data storage part 10 density and absorbing carbon dioxide concentration in extremely
It is few either one using be stored in the measurements moment of determination data storage part 10 or measure the process time for starting to start as index come into
Row chart is shown.In embodiments, indication mechanism 22 can utilize the display switching machine being set on the picture of display unit DP
Structure, that is, switching push button BT carries out the switching that the chart of characteristic value and constituent concentration is shown.
Indication mechanism 22 can be the display monitor being electrically connected with gas concentration lwevel display device A, can also be group
Enter the touching control panel computer in gas concentration lwevel display device A.It is touching control panel computer in indication mechanism 22
In the case of, indication mechanism, operational part and determination data storage part can be integrally formed in indication mechanism 22.
It should be noted that a pair structure same as first embodiment marks same drawing reference numeral and omits the description.
(third embodiment)
Fig. 5 is the schematic diagram of following developer solution managing device, which is based on being determined by densimeter
Developer solution density value, using the correspondence between the density of developer solution and absorbing carbon dioxide concentration come to developer solution mend
To replenisher, the absorbing carbon dioxide concentration of developer solution is thus managed.For convenience of description, by developer solution managing device E with
The mode of developing procedure equipment B connections illustrates together with developing procedure equipment B, replenisher reservoir C, circulation stirring mechanism D.
First, developing procedure equipment B is simply illustrated.
Developing procedure equipment B mainly by developer solution storagetank 61, overflow launder 62, developing room shield 64, roller conveyor 65,
Developer solution spray nozzles 67 etc. are constituted.It is stored with developer solution in developer solution storagetank 61.Developer solution by supplement replenisher come into
Row composition management.Developer solution storagetank 61 has liquid level meter 63 and overflow launder 62, the increasing to liquid measure caused by supply replenisher
Add and is managed.Developer solution storagetank 61 is connect with developer solution spray nozzle 67 by developing liquid pipeline 80.It is stored in developer solution
Developer solution in storagetank 61 is sprayed via filter 73 to developer solution under the action of set on circulating pump 72 of development liquid pipeline 80
Mouth 67 is drenched to convey.Roller conveyor 65 is arranged in the top of developer solution storagetank 61, has photoresist film for conveying to make
Substrate 66.Developer solution drips from developer solution spray nozzle 67.The substrate 66 conveyed by roller conveyor 65 passes through the development dripped
Developed liquid infiltration among liquid.Later, the developed liquid storagetank 61 of developer solution recycles, and stores again.In this way, developer solution exists
It recycles and is used repeatedly in developing procedure.It should be noted that in the developing room of small-sized glass substrate, sometimes through filling
The modes such as full nitrogen are handled to implement to prevent to absorb as the carbon dioxide in air
Then, the developer solution managing device E of present embodiment is illustrated.The developer solution managing device of present embodiment
E is the developer solution managing device such as under type：The density that developer solution is measured using densimeter, the density using developer solution and suction
The correspondence (such as linear relation as Fig. 1) for receiving gas concentration lwevel, so that the absorbing carbon dioxide concentration of developer solution
It is worth mode below based on the density value determined as defined management value or management to feed replenisher to developer solution.
Developer solution managing device E has determination part 1, operational part 2, control unit 3 and indication mechanism 22, and is piped by sampling
15 and outlet side line 16 and connect with developer solution storagetank 61.Determination part 1, operational part 2 and control unit 3 are connected by signal wire
It connects.
Determination part 1 have sampling pump 14, densimeter 11 and other characteristic values for measuring developer solution measuring means 12,
13.Measuring means 12,13 is, for example, the measuring machine for measuring the alkali composition concentration of developer solution, dissolving photoresist agent concentration
Structure.Densimeter 11 and measuring means 12,13 and the back segment of sampling pump 14 are connected in series with.It is preferred that determination part 1 is also equipped with after making sampling
Developer solution stabilize to as defined in the thermoregulation mechanism (not shown) of temperature improve measurement accuracy.At this point, preferable temperature tune
Section mechanism is arranged in the immediately front of measuring means.Sampling piping 15 connect with the sampling pump 14 of determination part 1, export side line 16 and
The piping of measuring means end connects.
Operational part 2 includes the operation mould for calculating the alkali composition concentration of such as developer solution, dissolving photoresist agent concentration
Block 21.Computing module 21 is connect by signal wire with the measuring means 12,13 that determination part 1 has.It is filled in developer solution management
It sets E only and has the function of and measure the density of developer solution in the case of controlling absorbing carbon dioxide concentration, need not measure
Mechanism 12,13 and operational part 2.
Control unit 3 is connect by signal wire with the densimeter 11 of determination part 1.In addition, control unit 3 by signal wire with
Control valve 41~43 on the pipeline for conveying from replenisher to developer solution connects.In Figure 5, control valve 41~43 is as development
The internal part of liquid managing device E and be illustrated, but control valve 41~43 be not be present embodiment developer solution managing device E
Necessary parts.As long as control unit 3 feeds replenisher can be controlled the action of control valve 41~43 to developer solution
Mode and control valve 41~43 get in touch with.Control valve 41~43 can also exist on except developer solution managing device E.
Then, the action of the developer solution managing device of present embodiment is illustrated.
It is adjusted from the developer solution after the sampling of developer solution storagetank 61 by trip temperature of going forward side by side is conveyed into determination part 1.Developer solution
Later density value is measured by being conveyed to densimeter 11.The determination data of density is sent to control unit 3.
Control unit 3 be set with density based on developer solution and absorbing carbon dioxide concentration correspondence (such as Fig. 1 that
The linear relation of sample) and the management value for being worth corresponding density with the management of absorbing carbon dioxide concentration of decision.Control unit 3 utilizes
The measured value of the density of the developer solution received from determination part 1 is controlled as follows.
In the case where being managed in a manner of so that the absorbing carbon dioxide concentration of developer solution is become defined management value,
Carry out following management.That is, so that the density value of the developer solution determined becomes the management value pair with absorbing carbon dioxide concentration
The mode of the management value for the density answered feeds replenisher to developer solution.In view of if without concentration management, if developer solution tend to
Carbon dioxide absorption is made absorbing carbon dioxide concentration increase this case, the replenisher of supply is with the suction of dilute development liquid
Receive the replenisher that the mode of gas concentration lwevel acts on.
By make the absorbing carbon dioxide concentration of developer solution become defined management be worth it is below in a manner of the feelings that are managed
Under condition, following management is carried out.That is, since the correspondence of the density and absorbing carbon dioxide concentration of developer solution is as shown in Figure 1
It is the relationship being increased monotonically like that, therefore so that the density value of the developer solution determined becomes the pipe with absorbing carbon dioxide concentration
The management value mode below that reason is worth corresponding density feeds replenisher to developer solution.The replenisher of supply is with dilute development liquid
Absorbing carbon dioxide concentration the replenisher that acts on of mode.
Here, " defined management value " refers to absorption titanium dioxide when can play best developing performance as developer solution
Concentration of carbon value and the management value known in advance.Such as it is commented using the line width or residual film thickness that are obtained by development treatment
When the liquid properties of valence developer solution, " defined management value " is to refer to that line width or residual film thickness is made to become desired optimum value
Developer solution absorbing carbon dioxide concentration value.It is also the same in the following description.
The management of absorbing carbon dioxide concentration as developer solution, for example using 2.38%TMAH aqueous solutions as development
In the case of liquid, preferably by the absorbing carbon dioxide concentration management of developer solution be 0.40 (wt%) below.It more preferably manages and is
0.25 (wt%) is below.
It should be noted that in developer solution managing device E, usually to alkali composition concentration, dissolving photoresist agent concentration
It is measured and manages, therefore have the measuring means 12,13 being measured to the characteristic value of developer solution required thus.By surveying
The characteristic value for determining the developer solution that mechanism 12,13 determines is sent to operational part 2.Operational part 2 is according to the developer solution determined
Characteristic value calculates alkali composition concentration, dissolving photoresist agent concentration, and its result is sent to control unit 3.Control unit 3 is based on
The alkali composition concentration of developer solution, dissolving photoresist concentration management are best shape by the measurement result or operation result
State.
As the replenisher fed to developer solution, such as stoste or new liquid, the pure water etc. that have developer solution.These replenishers are
The replenisher of absorbing carbon dioxide concentration for dilute development liquid.These replenishers can also in order to manage the alkali of developer solution at
Point concentration, dissolving photoresist agent concentration and be recharged.
Replenisher is stored in the replenisher storagetank 91,92 of replenisher reservoir C.Replenisher storagetank 91,92 with have
The nitrogen of valve 46,47 is connected with pipeline 86, is pressurizeed by the nitrogen supplied via the pipeline.In addition, in replenisher storagetank
91, replenisher pipeline 81,82 is connected separately on 92, replenisher is conveyed via the valve 44,45 of normally open.In replenisher
It is controlled out by control unit 3 with pipeline 81,82 and pure water with control valve 41~43, control valve 41~43 is provided on pipeline 83
It closes.It is acted, is thus conveyed the supplement hydraulic coupling for being stored in replenisher storagetank 91,92, and convey by control valve
Pure water.Later, replenisher collaborates via interflow pipeline 84 and with circulation stirring mechanism D, to the supply of developer solution storagetank 61 and quilt
Stirring.
If make because of supply the replenisher being stored in replenisher storagetank 91,92 reduce, interior drops and cause
Supply amount becomes unstable, therefore suitably opens valve 46,47 to supply nitrogen, to maintain to ensure to mend according to the reduction of replenisher
The internal pressure of filling liquid storagetank 91,92.When replenisher storagetank 91,92 is emptying, valve 44,45 is closed, is changed to and is filled with supplement
The new replenisher storagetank of liquid, or the replenisher separately supplied is refilled in empty replenisher storagetank 91,92.
The control of control valve 41~43 for example carries out as follows.The flow flowed through when being opened to adjustment control valve, then fight each other
The time for opening control valve is managed, and thus, it is possible to the replenishers for the liquid measure to be fed.Measurement of the control unit 3 based on density
Value and management are worth sends control signal so that control valve opens the stipulated time, to make the supplement for the liquid measure to be fed to control valve
Liquid stream mistake.
In addition, various controlling parties used in the control for keeping controlled quentity controlled variable consistent with desired value may be used in the mode of control
Method.Especially preferred proportion control (P controls) (Proportional Control), integration control (I controls) (Integral
Control), differential control (D controls) (Differential Control) and control (the PI controls for being composed them
Deng) (Proportional-Integral Control).More preferably applicable PID control (Proportional-Integral-
Differential Control)。
As described above, the developer solution managing device of present embodiment can so that developer solution absorbing carbon dioxide concentration at
It is worth mode below for defined management value or management and feeds replenisher to developer solution, to the absorbing carbon dioxide to developer solution
Concentration is managed.In addition, various data and chart can be shown by indication mechanism 22.
(the 4th embodiment)
Fig. 6 is the schematic diagram of following developer solution managing device, which is based on being determined by densimeter
Developer solution density value, absorption two is calculated according to the correspondence between the density of developer solution and absorbing carbon dioxide concentration
Concentration of carbon is aoxidized, and the absorbing carbon dioxide concentration of the developer solution based on calculating feeds replenisher to developer solution, thus to aobvious
The absorbing carbon dioxide concentration of shadow liquid is managed.For convenience of description, developer solution managing device E with developing procedure equipment B
The mode of connection is illustrated together with developing procedure equipment B, replenisher reservoir C, circulation stirring mechanism D.
The developer solution managing device of present embodiment is the developer solution managing device such as under type：According to the density of developer solution
Measured value calculate the operational part of absorbing carbon dioxide concentration and the absorbing carbon dioxide concentration of developer solution controlled
Control unit is implemented as the built-in function of the operation control mechanism (such as computer) of one.
The developer solution managing device E of present embodiment has determination part 1, calculation control unit 23 and indication mechanism 22.It measures
Portion 1 has densimeter 11 and other measuring means 12,13.Calculation control unit 23 has computing module 21 and control module 31.
In determination part 1, the density value of the developer solution after sampling is measured by densimeter 11.The density value determined passes through
Signal wire is sent to calculation control unit 23.In addition, the details of determination part 1 is due to same as second embodiment, thus
It omits.
The calculation control unit 23 of the measured value of the density of developer solution is received using computing module 21 and based on developer solution
Correspondence (such as linear relation of Fig. 1) between density and absorbing carbon dioxide concentration, is calculated according to the measured value of density
Go out the absorbing carbon dioxide concentration of corresponding developer solution.Absorption titanium dioxide of the absorbing carbon dioxide concentration of calculating as developer solution
The measured value of concentration of carbon and sent to control module 31.
Calculation control unit 23 can also have dense for calculating the alkali composition concentration of such as developer solution, dissolving photoresist
The computing module of degree is used as calculation function.
Control module 31 based on the absorbing carbon dioxide concentration determined so that the absorbing carbon dioxide concentration of developer solution at
It is worth mode below for defined management value or management and sends control signal to control valve 41~43.Developer solution tends to dioxy
Change carbon absorption and gas concentration lwevel is made to increase, therefore has the function of the supplement of dilution absorbing carbon dioxide concentration by supply
Liquid is controlled.The details of control is same as the explanation in third embodiment, therefore omits.
Control unit 3 can also have for controlling the alkali composition concentration of such as developer solution, dissolving photoresist agent concentration
Control module is used as control function.
As described above, developer solution managing device E according to the present embodiment, can so that alkaline-based developer absorption dioxy
Change concentration of carbon to be managed as defined management value or management value mode below.In addition, can by indication mechanism 22 come
Show various data and chart.
(the 5th embodiment)
Fig. 7 is the schematic diagram of following developer solution managing device, which is based on being determined by densimeter
Developer solution density value, absorption two is calculated according to the correspondence between the density of developer solution and absorbing carbon dioxide concentration
Concentration of carbon is aoxidized, the absorbing carbon dioxide concentration of the developer solution based on calculating feeds replenisher to developer solution, thus to developer solution
Absorbing carbon dioxide concentration be managed.For convenience of description, developer solution managing device E with developing procedure equipment B to connect
Mode be illustrated together with developing procedure equipment B, replenisher reservoir C, circulation stirring mechanism D.
The developer solution managing device of present embodiment is the developer solution managing device such as under type：According to the density of developer solution
Measured value controlled with the absorbing carbon dioxide concentration to developer solution to calculate the arithmetical organ of absorbing carbon dioxide concentration
Control mechanism constitute seperatedly.
The developer solution managing device E of present embodiment has determination part 1, operational part 2, control unit 3 and indication mechanism 22.It surveys
Determine portion 1 and has densimeter 11 and other measuring means 12,13.Operational part 2 has computing module 21, and the computing module 21 is according to close
The measured value of degree is simultaneously developed based on the correspondence (such as linear relation of Fig. 1) of density and absorbing carbon dioxide concentration to calculate
The absorbing carbon dioxide concentration of liquid.Control unit 3 has control module 31, the absorbing carbon dioxide of the control module 31 based on calculating
Concentration, by make developer solution absorbing carbon dioxide concentration become defined management value or management value it is below in a manner of to developer solution benefit
It is controlled to replenisher.
In determination part 1, the density value of the developer solution after sampling is measured by densimeter 11.The density value determined passes through letter
Number line is sent to operational part 2.In addition to this, the details of determination part 1 is same as second embodiment, therefore omits.
Receive the operational part 2 of the measured value of the density of developer solution using computing module 21 and the density based on developer solution with
Correspondence (such as linear relation of Fig. 1) between absorbing carbon dioxide concentration, correspondence is calculated according to the measured value of density
Developer solution absorbing carbon dioxide concentration.Absorbing carbon dioxide concentration of the absorbing carbon dioxide concentration of calculating as developer solution
Measured value and sent to control unit 3.
Operational part 2 can also have for calculating the alkali composition concentration of such as developer solution, dissolving photoresist agent concentration
Computing module is used as calculation function.
Control unit 3 is based on the absorbing carbon dioxide concentration determined, so that the absorbing carbon dioxide concentration of developer solution becomes
Defined management value or management are worth mode below and send control signal to control valve 41~43.Developer solution tends to titanium dioxide
Carbon absorption and so that gas concentration lwevel is increased, therefore by supply have the function of dilution absorbing carbon dioxide concentration replenisher
To be controlled.The details of control is same as the explanation in second embodiment, therefore omits.
Control unit 3 can also have for controlling the alkali composition concentration of such as developer solution, dissolving photoresist agent concentration
Control module is used as control function.
As described above, developer solution managing device E according to the present embodiment, can so that alkaline-based developer absorption dioxy
Change concentration of carbon to be managed as defined management value or management value mode below.In addition, indication mechanism 22 can be utilized aobvious
Show various data and chart.
Then, the variation of the developer solution managing device E of present embodiment is illustrated.
In Fig. 5~7, the determination part 1 and operational part 2, control unit 3 of drawing out developer solution managing device are integrally formed
Developer solution managing device, but it's not limited to that by the developer solution managing device E of present embodiment.Determination part 1 can also be arranged
At the structure seperated with operational part 2 and control unit 3.
Each measuring means 11~13 including densimeter according to the measuring principle respectively used and there are best setting sides
Method, it may be thus possible, for example, to by determination part 1 and development 80 on-line joining process of liquid pipeline, or can will measure side of the probe to impregnate
Formula is set to developer solution storagetank 61.Each measuring means 11~13 can also be separately arranged.With regard to the aobvious of present embodiment
For shadow liquid managing device E, as long as each measuring means 11~13 with operational part 2, control unit 3 can be measured data
The scheme that the mode of exchange is mutually got in touch with, it will be able to realize.
Equally, in Fig. 5~7, densimeter is depicted and the development of mode that other measuring means 11~13 are connected in series with
Liquid managing device E, but it's not limited to that by the developer solution managing device E of present embodiment.Each measuring means 11~13 can also
It is connected in parallel, can also configure independently of one another.According to measuring principle used by each measuring means, reagent is if desired added,
Then each measuring means can have the piping for adding reagent, if desired liquid waste, then each measuring means can have use
In the pipeline of liquid waste.Even if each measuring means is not connected in series with, the developer solution management dress of present embodiment can be also realized
Set E.
The operational part 2 of the developer solution managing device E of present embodiment is in addition to having density and absorption two according to developer solution
The measured value of the correspondence (such as linear relation as Fig. 1) and the density based on developer solution between concentration of carbon is aoxidized to calculate
Go out other than the calculation function of absorbing carbon dioxide concentration, can also have other calculation functions.For example, can have for calculating
The alkali composition concentration of developer solution, the calculation function for dissolving other constituent concentrations such as photoresist agent concentration.
The control unit 3 of the developer solution managing device E of present embodiment is in addition to having the absorbing carbon dioxide so that developer solution
Concentration is worth mode below as defined management value or management and feeds replenisher to developer solution come the control function that is controlled
Except, can also have other control functions.For example, can have alkali composition concentration, dissolving photoresist so that developer solution
Other constituent concentrations such as agent concentration become defined management value or management value or less or fall into the side in defined range of management
The control function that formula is controlled.The control carried out thus is in addition to being the control carried out by feeding replenisher to developer solution
In addition, can also suitably add by developer solution discard control, it is additional make to filter out impurity by filter etc. and after regenerating again
The various controls such as the control that raw developer solution returns.
In Fig. 5~7, depict in a manner of making internal part of the control valve 41~43 as developer solution managing device E
The scheme that developer solution managing device E is connect with replenisher pipeline 81,82 and pure water pipeline 83, wherein control valve 41~
43 are arranged on the pipeline of replenisher that conveying is fed to developer solution, but the developer solution managing device E of present embodiment and unlimited
Due to this.Developer solution managing device can not also by control valve 41~43 as internal part be arranged, can not also with for
The pipeline 81~83 that developer solution feeds replenisher connects.
For the developer solution managing device E of present embodiment, as long as control unit 3 with set on for feeding replenisher
Control valve 41~43 on pipeline is so that control valve 41~43 receives the control sent by the control unit 3 of developer solution managing device E
The scheme that signal and the mode that is controlled mutually are got in touch with.Even if control valve does not become the inside portion of developer solution managing device E
Part can also realize the developer solution managing device E of present embodiment.
The control unit 3 of developer solution managing device E can not also be integrally formed with determination part 1, operational part 2, can be with survey
Determine portion 1, operational part 2 is constituted seperatedly.Determination part 1, operational part 2 and control unit 3 can exist as device independent of each other.
As long as being got in touch in a manner of being exchanged with each other determination data, operation result, control signal etc. by signal wire etc., then all
It can realize the developer solution managing device E of present embodiment.
It is preferred that the function that absorbing carbon dioxide concentration is controlled of control unit 3 with to alkali composition concentration, dissolving it is photic
The function that other ingredients such as agent concentration against corrosion are controlled is realized by shared control mechanism, but each function can also pass through
Seperated control mechanism is realized.Replenisher, the pipeline for conveying replenisher and control valve etc. used in control can be according to wanting
The object component of the developer solution of control and prepare respectively, but as long as being commonly to use, then preferably share.
Although the developer solution managing device of the present invention allows above-mentioned various variation, needs to be configured to have density
Instrument uses the correspondence (such as linear relation as Fig. 1) between the density and absorbing carbon dioxide concentration of developer solution, base
It is calculated in the density value of the developer solution determined by densimeter or according to the density value of the developer solution determined by densimeter
Developer solution absorbing carbon dioxide concentration value so that the absorbing carbon dioxide concentration of developer solution become defined management value or pipe
Reason value mode below feeds replenisher to be controlled to developer solution.
As described above, developer solution managing device according to the present invention, it can be dense by the absorbing carbon dioxide of alkaline-based developer
Degree management is defined management value or management value or less.Thus, developer solution managing device according to the present embodiment can be by alkali
Property developer solution be maintained play best developing performance absorbing carbon dioxide concentration state, can realize desired line width
Or residual film thickness.
The developer solution managing device of the present invention can also be to the alkali composition concentration of alkaline-based developer, dissolving photoresist
In the case that concentration is managed, each constituent concentration of alkaline-based developer is managed as defined state.Therefore, with can not to inhale
It receives the existing developer solution management that gas concentration lwevel is managed to compare, developer solution managing device according to the present invention can
The developing performance of alkaline-based developer is further precisely maintained to management to fix.Thus, it is possible to expect following effect：
Developing powder stabilization when developing to photoresist turns to fixation, and line width or residual film thickness based on development treatment are consolidated
Fixedization, product quality are improved, and help to realize further miniaturization and highly integrated.
In turn, developer solution managing device according to the present invention, development liquid energy automatically maintain into best developability always
Can, therefore can expect following effect：Finished product rate is improved, and does not need the replacement operation of developer solution, helps to run
The reduction of cost and waste liquid cost.
Claims (15)
1. a kind of gas concentration lwevel display device of developer solution, wherein
The gas concentration lwevel display device of the developer solution has：
Densimeter；
Arithmetical organ, based on the density value of the developer solution for showing alkalinity determined by the densimeter, according to the development
Correspondence between the density and absorbing carbon dioxide concentration of liquid calculates the absorbing carbon dioxide concentration of the developer solution；With
And
Indication mechanism shows the absorbing carbon dioxide concentration of the developer solution calculated by the arithmetical organ.
2. a kind of gas concentration lwevel display device of developer solution, wherein
The gas concentration lwevel display device of the developer solution has：
Densimeter；
Arithmetical organ, based on the density value of the developer solution for showing alkalinity determined by the densimeter, according to the development
Correspondence between the density and absorbing carbon dioxide concentration of liquid calculates the absorbing carbon dioxide concentration of the developer solution；With
And
Indication mechanism shows the density value of the developer solution determined by the densimeter and is calculated by the arithmetical organ
The developer solution absorbing carbon dioxide concentration.
3. a kind of gas concentration lwevel display device of developer solution, wherein
The gas concentration lwevel display device of the developer solution has：
Densimeter is repeatedly measured the density value for the developer solution for showing alkalinity；
Arithmetical organ, when the densimeter measures the density value every time, described in being determined by the densimeter
Density value calculates the developer solution according to the correspondence between the density of the developer solution and absorbing carbon dioxide concentration
Absorbing carbon dioxide concentration；
Determination data storing mechanism, by the absorbing carbon dioxide concentration of the developer solution calculated by the arithmetical organ and survey
Timing, which is carved and measured, starts being stored together by either one in the time for start of calculation；And
Indication mechanism, by the absorbing carbon dioxide concentration for being stored in the determination data storing mechanism with described in storing together
It measures the moment or the measurement starts being shown for index to carry out chart by the time for start of calculation.
4. a kind of gas concentration lwevel display device of developer solution, wherein
The gas concentration lwevel display device of the developer solution has：
Densimeter is repeatedly measured the density value for the developer solution for showing alkalinity；
Arithmetical organ, when the densimeter measures the density value every time, described in being determined by the densimeter
Density value calculates the developer solution according to the correspondence between the density of the developer solution and absorbing carbon dioxide concentration
Absorbing carbon dioxide concentration；
Determination data storing mechanism, by the density value of the developer solution determined by the densimeter and by the calculating machine
Structure calculate the developer solution absorbing carbon dioxide concentration with measure the moment and measure start start by the time extremely
Either one is stored together less；And
Indication mechanism will be stored in the density value and absorbing carbon dioxide of the developer solution of the determination data storing mechanism
Either one time of passing through for starting start of calculation with the measurement moment stored together or the measurement in concentration value is to refer to
Mark shows to carry out chart.
5. the gas concentration lwevel display device of developer solution according to claim 4, wherein
The gas concentration lwevel display device of the developer solution is also equipped with display switching mechanism, and the display switching mechanism will be shown
The chart of the density value of the developer solution or the absorption titanium dioxide of the developer solution are switched in the chart of the indication mechanism
The chart of concentration of carbon.
6. a kind of developer solution managing device, wherein
The developer solution managing device has：
Densimeter；
Arithmetical organ, based on the density value of the developer solution for showing alkalinity determined by the densimeter, according to the development
Correspondence between the density and absorbing carbon dioxide concentration of liquid calculates the absorbing carbon dioxide concentration of the developer solution；
Indication mechanism shows the absorbing carbon dioxide concentration value of the developer solution calculated by the arithmetical organ；And
Control mechanism, based on the absorbing carbon dioxide concentration value of the developer solution calculated by the arithmetical organ, so that institute
Stating the absorbing carbon dioxide concentration of developer solution becomes defined management value or management value mode below to control valve transmission control
Signal, the control valve are arranged on the pipeline for the replenisher that conveying is fed to the developer solution.
7. a kind of developer solution managing device, wherein
The developer solution managing device has：
Densimeter；
Arithmetical organ, based on the density value of the developer solution for showing alkalinity determined by the densimeter, according to the development
Correspondence between the density and absorbing carbon dioxide concentration of liquid calculates the absorbing carbon dioxide concentration value of the developer solution；
Indication mechanism shows the density value of the developer solution determined by the densimeter and is calculated by the arithmetical organ
The developer solution absorbing carbon dioxide concentration；And
Control mechanism, based on the absorbing carbon dioxide concentration of the developer solution calculated by the arithmetical organ, so that described
The absorbing carbon dioxide concentration of developer solution becomes defined management value or management is worth mode below and sends control letter to control valve
Number, the control valve is arranged on the pipeline for the replenisher that conveying is fed to the developer solution.
8. a kind of developer solution managing device, wherein
The developer solution managing device has：
Densimeter is repeatedly measured the density value for the developer solution for showing alkalinity；
Arithmetical organ, when the densimeter measures the density value every time, described in being determined by the densimeter
Density value calculates the developer solution according to the correspondence between the density of the developer solution and absorbing carbon dioxide concentration
Absorbing carbon dioxide concentration value；
Determination data storing mechanism, by the absorbing carbon dioxide concentration value of the developer solution calculated by the arithmetical organ with
It measures the moment and measures and start being stored together by either one in the time for start of calculation；
Indication mechanism, by the absorbing carbon dioxide concentration for being stored in the determination data storing mechanism with described in storing together
It measures the moment or the measurement starts being shown for index to carry out chart by the time for start of calculation；And
Control mechanism, based on the absorbing carbon dioxide concentration value of the developer solution calculated by the arithmetical organ, so that institute
Stating the absorbing carbon dioxide concentration of developer solution becomes defined management value or management value mode below to control valve transmission control
Signal, the control valve are arranged on the pipeline for the replenisher that conveying is fed to the developer solution.
9. a kind of developer solution managing device, wherein
The developer solution managing device has：
Densimeter is repeatedly measured the density value for the developer solution for showing alkalinity；
Arithmetical organ, when the densimeter measures the density value every time, described in being determined by the densimeter
Density value calculates the developer solution according to the correspondence between the density of the developer solution and absorbing carbon dioxide concentration
Absorbing carbon dioxide concentration value；
Determination data storing mechanism, by the density value of the developer solution determined by the densimeter and by the calculating machine
Structure calculate the developer solution absorbing carbon dioxide concentration value with measure the moment and measure start start by the time
Either one is stored together；
Indication mechanism will be stored in the density value and absorbing carbon dioxide of the developer solution of the determination data storing mechanism
Either one time of passing through for starting start of calculation with the measurement moment stored together or the measurement in concentration value is to refer to
Mark shows to carry out chart；And
Control mechanism, based on the absorbing carbon dioxide concentration value of the developer solution calculated by the arithmetical organ, so that institute
Stating the absorbing carbon dioxide concentration of developer solution becomes defined management value or management value mode below to control valve transmission control
Signal, the control valve are arranged on the pipeline for the replenisher that conveying is fed to the developer solution.
10. developer solution managing device according to claim 9, wherein
The developer solution managing device is also equipped with display switching mechanism, and the display switching mechanism is shown in the indication mechanism
Chart be switched to the developer solution density value chart or the developer solution absorbing carbon dioxide concentration chart.
11. a kind of developer solution managing device, has densimeter and operation control mechanism, wherein
The operation control mechanism has：
Operational part, based on the density value of the developer solution for showing alkalinity determined by the densimeter, according to the developer solution
Density and absorbing carbon dioxide concentration between correspondence calculate the absorbing carbon dioxide concentration of the developer solution；
Display unit shows the absorbing carbon dioxide concentration value of the developer solution calculated by the operational part；And
Control unit, based on the absorbing carbon dioxide concentration value of the developer solution calculated by the operational part, so that described aobvious
The absorbing carbon dioxide concentration of shadow liquid becomes defined management value or management is worth mode below and sends control signal to control valve,
The control valve is arranged on the pipeline for the replenisher that conveying is fed to the developer solution.
12. a kind of developer solution managing device, has densimeter and operation control mechanism, wherein
The operation control mechanism has：
Operational part, based on the density value of the developer solution for showing alkalinity determined by the densimeter, according to the developer solution
Density and absorbing carbon dioxide concentration between correspondence calculate the absorbing carbon dioxide concentration of the developer solution；
Display unit, the institute for showing the density value of the developer solution determined by the densimeter and being calculated by the operational part
State the absorbing carbon dioxide concentration value of developer solution；And
Control unit, based on the absorbing carbon dioxide concentration value of the developer solution calculated by the operational part, so that described aobvious
The absorbing carbon dioxide concentration of shadow liquid becomes defined management value or management is worth mode below and sends control signal to control valve,
The control valve is arranged on the pipeline for the replenisher that conveying is fed to the developer solution.
13. a kind of developer solution managing device has the densimeter and fortune of the density value for being repeatedly measured the developer solution for showing alkalinity
Calculate control mechanism, wherein
The operation control mechanism has：
Operational part, it is described close based on being determined by the densimeter when the densimeter measures the density value every time
Angle value calculates the suction of the developer solution according to the correspondence between the density of the developer solution and absorbing carbon dioxide concentration
Receive carbon dioxide concentration value；
Determination data storage part, by the absorbing carbon dioxide concentration value of the developer solution calculated by the operational part and measurement
What moment and measurement started to start stores together by either one in the time；
Display unit, the measurement by the absorbing carbon dioxide concentration for being stored in the determination data storage part to store together
What moment or the measurement started to start shows for index to carry out chart by the time；And
Control unit, based on the absorbing carbon dioxide concentration value of the developer solution calculated by the operational part, so that described aobvious
The absorbing carbon dioxide concentration of shadow liquid becomes defined management value or management is worth mode below and sends control signal to control valve,
The control valve is arranged on the pipeline for the replenisher that conveying is fed to the developer solution.
14. a kind of developer solution managing device has the densimeter and fortune of the density value for being repeatedly measured the developer solution for showing alkalinity
Calculate control mechanism, wherein
The operation control mechanism has：
Operational part, it is described close based on being determined by the densimeter when the densimeter measures the density value every time
Angle value calculates the suction of the developer solution according to the correspondence between the density of the developer solution and absorbing carbon dioxide concentration
Receive gas concentration lwevel；
Determination data storage part is calculated by the density value of the developer solution determined by the densimeter and by the operational part
The absorbing carbon dioxide concentration value of the developer solution gone out with measure the moment and measure start to start by the time at least
Either one is stored together；
Display unit will be stored in the density value and absorbing carbon dioxide concentration of the developer solution of the determination data storage part
Either one in value is come using the time of passing through that the measurement moment stored together or the measurement start to start as index
Chart is carried out to show；And
Control unit, based on the absorbing carbon dioxide concentration value of the developer solution calculated by the operational part, so that described aobvious
The absorbing carbon dioxide concentration of shadow liquid becomes defined management value or management is worth mode below and sends control signal to control valve,
The control valve is arranged on the pipeline for the replenisher that conveying is fed to the developer solution.
15. developer solution managing device according to claim 14, wherein
The developer solution managing device is also equipped with display switching mechanism, and the display switching mechanism is shown in the display unit
Chart is switched to the chart of the density value of the developer solution or the chart of the absorbing carbon dioxide concentration of the developer solution.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2017009833A JP6763608B2 (en) | 2017-01-23 | 2017-01-23 | Carbon dioxide concentration display device for developer and developer management device |
| JP2017-009833 | 2017-01-23 |
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| Publication Number | Publication Date |
|---|---|
| CN108344662A true CN108344662A (en) | 2018-07-31 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201711232810.XA Pending CN108344662A (en) | 2017-01-23 | 2017-11-29 | The gas concentration lwevel display device and developer solution managing device of developer solution |
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| Country | Link |
|---|---|
| JP (1) | JP6763608B2 (en) |
| KR (1) | KR20180087121A (en) |
| CN (1) | CN108344662A (en) |
| TW (1) | TW201827808A (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2018120897A (en) * | 2017-01-23 | 2018-08-02 | 株式会社平間理化研究所 | Device for monitoring concentration of developer, and developer management device |
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- 2017-11-29 CN CN201711232810.XA patent/CN108344662A/en active Pending
- 2017-11-29 KR KR1020170161406A patent/KR20180087121A/en active IP Right Grant
- 2017-11-30 TW TW106141772A patent/TW201827808A/en unknown
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Also Published As
| Publication number | Publication date |
|---|---|
| KR20180087121A (en) | 2018-08-01 |
| JP2018120896A (en) | 2018-08-02 |
| TW201827808A (en) | 2018-08-01 |
| JP6763608B2 (en) | 2020-09-30 |
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Application publication date: 20180731 |