CN106371297A - Component concentration measuring apparatus and method, developing solution managing apparatus and developing solution managing method - Google Patents

Component concentration measuring apparatus and method, developing solution managing apparatus and developing solution managing method Download PDF

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Publication number
CN106371297A
CN106371297A CN201510994050.0A CN201510994050A CN106371297A CN 106371297 A CN106371297 A CN 106371297A CN 201510994050 A CN201510994050 A CN 201510994050A CN 106371297 A CN106371297 A CN 106371297A
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developer solution
value
density
concentration
mentioned
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中川俊元
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Hirama Rika Kenkyusho Ltd
Hirama Laboratories Co Ltd
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Hirama Rika Kenkyusho Ltd
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/30—Imagewise removal using liquid means
    • G03F7/32—Liquid compositions therefor, e.g. developers
    • G03F7/322—Aqueous alkaline compositions
    • G—PHYSICS
    • 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

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  • General Physics & Mathematics (AREA)
  • Immunology (AREA)
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  • Chemical & Material Sciences (AREA)
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  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)
  • Engineering & Computer Science (AREA)
  • Exposure Of Semiconductors, Excluding Electron Or Ion Beam Exposure (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Manufacturing & Machinery (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)

Abstract

A component concentration measuring apparatus and method, a developing solution managing apparatus and a developing solution managing method are provided to measure or manage the concentration of absorbed carbon dioxide the alkaline developing solution. The component concentration measuring apparatus and the developing solution managing apparatus are provided with densitometers to measure the density of the developing solution. The density of the developing solution and the concentration of carbon dioxide have a good corresponding relation not influenced by concentrations of other components such as an alkaline component. The concentration of carbon dioxide is calculated by the component concentration measuring apparatus based on a measured density value and according to the corresponding relation between the density of the developing solution and the concentration of the carbon dioxide. Based on the corresponding relation between the density of the developing solution and the concentration of the carbon dioxide and based on the measured density value or the calculated carbon dioxide concentration value of the developing solution, supplementing liquids are supplemented to the developing solution to allow the carbon dioxide concentration of the developing solution to be a given managing value or below by the developing solution managing apparatus so that the carbon dioxide concentration of the developing solution is managed.

Description

Developer solution component concentration measuring device and method, developer solution managing device and method
Technical field
The present invention relates in the component concentration measuring device of developer solution of alkalescence, component concentration measuring side Method, developer solution managing device and developer solution management method, the circuit base in quasiconductor or liquid crystal panel In developing procedure of plate etc. in order that photoresist film development and use above-mentioned developer solution.
Background technology
In the developing procedure of photoetching of fine pitch wirings processing in realizing quasiconductor or liquid crystal panel etc., As the medicinal liquid being dissolved in the photoresist of film forming on substrate, using in alkaline developer solution (below, Referred to as " alkaline-based developer ").
In the manufacturing process of quasiconductor or base plate of liquid crystal panel, in recent years, chip or glass substrate Maximize and the miniaturization of wiring processing and highly integrated be developed.In this condition, in order to Realize the miniaturization and highly integrated of the wiring processing of large substrate, need more precisely to measure alkalescence The concentration of the main component of developer solution developer solution to be carried out maintain management.
The mensure of the constituent concentration of existing alkaline-based developer as described in Patent Document 1 as, profit With following 2 points: can be in the concentration (hereinafter referred to as " alkaline components of the alkaline components of alkaline-based developer Concentration ") obtain good linear relationship and conductivity between；And, alkaline development can be dissolved in The concentration (hereinafter referred to as " dissolving photoresist agent concentration ") of the photoresist in liquid and absorbance Between obtain good linear relationship.
But, the carbon dioxide in the easy absorption air of alkaline-based developer and form carbonate.Now, The alkaline components in developer solution with developing activity are consumed and reduce.Therefore, in order to developer solution Developing performance accurately carries out maintaining management, needs to have considered the titanium dioxide that developer solution is absorbed The developer solution management of the impact that carbon brings to developing performance.
In order to solve this problem, patent document 2 discloses that following developer solution modulating device etc., should Developer solution modulating device measures ultrasonic propagation velocity, conductivity and the absorbance of developer solution, based on alkali Ultrasonic propagation velocity under concentration, carbonate concentration and dissolving resin concentration, conductivity, absorbance Between pre-production relation (matrix), the detection alkali concn of developer solution, carbonate concentration and dissolving Resin concentration, and the alkali concn based on the developer solution being measured, carbonate concentration and dissolving resin concentration, With can play the dissolving enabling cd value (cd:critical dimension) (live width) to become steady state value The alkali concn of power, carbonate concentration, the relation of the pre-production of dissolving resin concentration, control developer solution The supply of stock solution is adjusting alkali concn.
Additionally, patent document 3 discloses that the refractive index of mensure developer solution, conductivity, absorbance, and The carbonic acid system salt density that measured value according to them obtains the carbonic acid system salt density in developer solution is surveyed Determine device and possess this carbonic acid system salt density mensure device and control the carbonic acid system salt in developer solution Alkaline-based developer management system of the control unit of concentration etc..
Patent documentation 1: No. 2561578 publications of Japanese Patent No.
Patent documentation 2: Japanese Unexamined Patent Publication 2008-283162 publication
Patent documentation 3: Japanese Unexamined Patent Publication 2011-128455 publication
But, the ultrasonic propagation velocity value of alkaline-based developer or refractive index value are to be denoted as multicomponent The characteristic value of the overall property of the liquid of the alkaline-based developer of system.This property representing that liquid is overall Characteristic value generally not only concentration dependent with the special component contained by this liquid.This expression Usual each concentration with the various composition contained by this liquid respectively of characteristic value of the overall property of liquid Related.Therefore, the measured value in the characteristic value according to this property representing that liquid is overall shows come computing In the case of the constituent concentration of shadow liquid, if thinking, a certain characteristic value is only related to a certain specific component concentration (for example there is linear relationship) and ignore the impact that other compositions are brought to this characteristic value, then exist cannot Go out the problem of the concentration of this special component with enough accuracy computation.
On the other hand, in the characteristic value thinking developer solution be the various composition contained by developer solution concentration Function and in the case that each constituent concentration is calculated according to the measured value of the characteristic value of developer solution, need On the basis of measuring multiple characteristic values, using for being calculated according to the measured value of these characteristic values The suitable operation method of each constituent concentration.But, suitably select the characteristic value that should measure and find out That can accurately calculate the suitable computing of each constituent concentration according to the measured value of characteristic value Method is all extremely difficult.Accordingly, there exist problems with, i.e. if the characteristic value being measured and fortune Calculation method is incorrect, then cannot be with enough each constituent concentrations of accuracy computation.
In addition, it is generally the case that the concentration of certain composition is become with other in the liquid of multicomponent system The concentration divided is not independent of each other.In the liquid of multicomponent system, there is the concentration of a certain composition The mutual relation that during change, other compositions concentration also changes simultaneously.This leads to be more difficult to realize high-precision The calculating of constituent concentration of degree and the management of high-precision developer solution.
Additionally, the concentration of the carbon dioxide being absorbed with regard to developer solution (hereinafter referred to as " absorbs dioxy Change concentration of carbon ") assume the suitable characteristic of the developer solution of good dependency relation it is impossible to learn with it Value, is difficult to accurately measure absorbing carbon dioxide concentration in the prior art.
Content of the invention
The present invention makes to solve above-mentioned many problems.It is an object of the invention to, provide A kind of titanium dioxide that can determine developer solution according to the density value of the developer solution as multicomponent system The component concentration measuring device of the developer solution of concentration of carbon and component concentration measuring method, also provide to enter The gas concentration lwevel of row developer solution becomes given management value or the pipe less than given management value The developer solution managing device of reason and developer solution management method.
The component concentration measuring device of the 1st scheme of the present invention, possesses: densimeter；And computing list Unit, based on the density value being determined by densimeter in alkaline developer solution, close according to developer solution Corresponding relation between angle value and carbon dioxide concentration value, calculates the gas concentration lwevel of developer solution.
According to the component concentration measuring device of above-mentioned 1st scheme, due to possessing to the dioxy with developer solution Change concentration of carbon and there is the densimeter that the density value of good corresponding relation is measured, therefore, it is possible to basis The density value being determined by densimeter, calculates the absorbing carbon dioxide concentration of developer solution.
The component concentration measuring method of the 2nd scheme of the present invention, comprising: measure the developer solution in alkalescence Density step；And the density based on the above-mentioned developer solution being measured, according to above-mentioned developer solution Corresponding relation between density and gas concentration lwevel, calculates the gas concentration lwevel of above-mentioned developer solution Step.
According to the component concentration measuring method of above-mentioned 2nd scheme, to the gas concentration lwevel with developer solution The density value with good corresponding relation is measured, and can be calculated according to the density value being measured Go out the absorbing carbon dioxide concentration of developer solution.
The developer solution managing device of the 3rd scheme of the present invention, possesses: densimeter；And control unit, Based on the density value being determined by densimeter in alkaline developer solution, using developer solution density value with Corresponding relation between carbon dioxide concentration value, is fed to the replenisher in developer solution to being arranged on conveying Stream on control valve send control signal so that the gas concentration lwevel of developer solution becomes given Below management value or management value.
According to the developer solution managing device of above-mentioned 3rd scheme, by density and the carbon dioxide of developer solution The corresponding relation of concentration, the density value of the developer solution measuring out from densimeter just may know that and should feed The amount of replenisher, to be managed the absorption titanium dioxide so that developer solution therefore, it is possible to feed replenisher Concentration of carbon becomes below given management value or management value.
The developer solution management method of the 4th scheme of the present invention, comprising: measure in alkaline developer solution The step of density；And, based on the density of the above-mentioned developer solution being measured, using above-mentioned developer solution Corresponding relation between density and gas concentration lwevel, makes above-mentioned to above-mentioned developer solution supply replenisher The gas concentration lwevel of developer solution becomes given management value or management value below step.
According to the developer solution management method of above-mentioned 4th scheme, by density and the carbon dioxide of developer solution The corresponding relation of concentration, just may know that, from the density value of the developer solution measuring out, the replenisher that should feed Amount, to be managed the absorbing carbon dioxide concentration so that developer solution therefore, it is possible to feed replenisher Become below given management value or management value.
The developer solution managing device of the 5th scheme of the present invention, possesses: densimeter and Operations Analysis, This Operations Analysis possesses: operational part, based on being determined by densimeter in alkaline developer solution Density value, the corresponding relation between the density value according to developer solution and carbon dioxide concentration value, calculate The gas concentration lwevel of developer solution；And control unit, two based on the developer solution being calculated by operational part Carbonoxide is dense, is fed to the control valve transmission on the stream of the replenisher in developer solution to being arranged on conveying Control signal is so that the gas concentration lwevel of developer solution becomes below given management value or management value.
According to the developer solution managing device of above-mentioned 5th scheme, due to possessing to the titanium dioxide with developer solution Concentration of carbon has the densimeter that the density value of good corresponding relation is measured, therefore, it is possible to according to by The density value that densimeter determines, to calculate the absorbing carbon dioxide concentration of developer solution, can feed benefit Topping up is being managed so that the absorbing carbon dioxide concentration of developer solution becomes given management value or pipe Below reason value.
The developer solution managing device of the 6th scheme of the present invention possesses: densimeter；Arithmetic element, is based on The density value in alkaline developer solution being determined by densimeter, the density value according to developer solution and dioxy Change the corresponding relation between concentration of carbon value, calculate the gas concentration lwevel of developer solution；And control unit, Based on the gas concentration lwevel of the developer solution being calculated by arithmetic element, to be arranged on conveying be fed to aobvious Control valve on the stream of the replenisher in shadow liquid sends control signal so that the carbon dioxide of developer solution Concentration becomes below given management value or management value.
According to the developer solution managing device of above-mentioned 6th scheme, due to possessing to the titanium dioxide with developer solution Concentration of carbon has the densimeter that the density value of good corresponding relation is measured, therefore, it is possible to according to by The density value that densimeter determines, to calculate the absorbing carbon dioxide concentration of developer solution, can feed benefit Topping up is being managed so that the absorbing carbon dioxide concentration of developer solution becomes given management value or pipe Below reason value.
The developer solution management method of the 7th scheme of the present invention, comprising: measure in alkaline developer solution The step of density；Based on the density of the above-mentioned developer solution being measured, the density according to above-mentioned developer solution with Corresponding relation between gas concentration lwevel, the step calculating the gas concentration lwevel of above-mentioned developer solution； And, the gas concentration lwevel of the above-mentioned developer solution that replenisher makes to calculate is fed to above-mentioned developer solution Become below given management value or management value.
According to the developer solution management method of above-mentioned 7th scheme, to the gas concentration lwevel tool with developer solution The density value having good corresponding relation is measured, and can calculate the suction of developer solution according to density value Receive gas concentration lwevel, replenisher can be fed to be managed the absorption titanium dioxide so that developer solution Concentration of carbon becomes below given management value or management value.
Invention effect
In accordance with the invention it is possible to determine the absorption titanium dioxide of the developer solution that prior art is difficult to determine Concentration of carbon.Additionally, based on the density value being measured or the absorbing carbon dioxide concentration value that calculated, energy Enough to be managed so that the gas concentration lwevel of developer solution becomes given to developer solution supply replenisher Management value or management value below.
Brief description
Fig. 1 is the chart with the relation of density for the gas concentration lwevel representing developer solution.
Fig. 2 is the schematic diagram of the component concentration measuring device of developer solution.
Fig. 3 is the schematic diagram of the typical structure of vibrating densimeter.
Fig. 4 is the signal of the development treatment operation of the developer solution managing device including second embodiment Figure.
Fig. 5 is the signal of the development treatment operation of the developer solution managing device including the 3rd embodiment Figure.
Fig. 6 is the signal of the development treatment operation of the developer solution managing device including the 4th embodiment Figure.
Symbol description
A... component concentration measuring device；B... developing procedure equipment；C... replenisher storage portion；d... Circulation stirring mechanism；E... developer solution managing device；1... determination part；11... densimeter；12、13... Determination unit；14... sampling pump；15... sampling pipe arrangement；16... export side line；2... operational part； 21... computing module；22... display unit；23... calculation control unit (such as computer)；3... control Portion；31... control module；41～43... control valve；44th, 45,46,47... valve；51... sample cell； 52... thermometer；53... Peltier element；54... thermostat module；55... thermal insulation barriers；56... oscillator； 61... developer solution storage tank；62... overflow launder；63... liquid level meter；64... developing room cover；65... roll-type Conveyer；66... substrate；67... developer solution shower nozzle；71... waste drains pump；72nd, 74... circulating pump； 73rd, 75... filter；80... develop liquid pipeline；81st, 82... replenisher (development stock solution and/or new liquid) Use pipeline；83... pure water pipeline；84... collaborate pipeline；85... circulation line；86... nitrogen pipe Road；91st, 92... replenisher storage tank.
Specific embodiment
Hereinafter, suitably referring to the drawings, describe the preferred embodiment of the present invention in detail.Wherein, these The shape of the device described in embodiment etc., size, size ratio, relative configuration etc. be not especially In the case of record, it is not limited to the scope illustrated in the present invention.These are merely possible to explanation example and enter The indicative icon of row.
Additionally, in the following description, as the concrete example of developer solution, suitably using in quasiconductor or liquid In the manufacturing process of crystal panel substrate, 2.38% primary tetramethylammonium hydroxide aqueous solution (below, will Tetramethylammonium hydroxide is referred to as tmah) illustrating.But, present invention developer solution applicatory It is not limited to this.As the component concentration measuring device of the developer solution of the present invention, developer solution managing device Deng the example of other developer solutions that can be suitable for, potassium hydroxide, sodium hydroxide, phosphoric acid can be enumerated The aqueous solution of the inorganic compound such as sodium, sodium silicate, hydroxide hydroxyethyl ammonium (choline) etc. are organic The aqueous solution of compound.
Additionally, in the following description, alkaline components concentration, dissolving photoresist agent concentration, absorption two The constituent concentrations such as oxidation concentration of carbon are the concentration based on weight percent concentration (wt%)." dissolving is photic anti- Erosion agent concentration " refers to, the photoresist being dissolved is changed as the amount of photoresist Concentration during calculation, " absorbing carbon dioxide concentration " refers to, using the carbon dioxide being absorbed as dioxy The amount changing carbon is come concentration when being converted.
In development treatment operation, developer solution is by the photoresist film after exposure-processed without part Dissolve, thus being developed.It is dissolved in the photoresist of developer solution and the alkaline components of developer solution Produce photoresist salt.Therefore, if inappropriate management developer solution, with the carrying out of development treatment, The alkaline components in developer solution with developing activity are consumed and are deteriorated, and developing performance can gradually be disliked Change.Meanwhile, the photoresist being dissolved in developer solution can be used as the photoresist salt with alkaline components And gone down by gradually accumulation.
The photoresist being dissolved in developer solution assumes surface-active action in developer solution.Therefore, molten Solution improves photoresist film to development treatment supply with respect to aobvious in the photoresist of developer solution The wellability (wettability) of shadow liquid, makes developer solution and the affinity of photoresist film become good. Therefore, in the developer solution moderately comprising photoresist, developer solution can also enter into photoresist In the trickle recess of agent film, the photoresist film that can implement well there are fine irregularities aobvious Shadow is processed.
Additionally, in development treatment in recent years, along with the maximization of substrate, substantial amounts of developer solution Recycled, therefore developer solution is exposed to the chance of air and increases.If however, alkaline-based developer It is exposed in the air, the carbon dioxide in meeting absorption air.The carbon dioxide being absorbed and developer solution Alkaline components produce carbonate.Therefore, if inadequately managing developer solution, have aobvious in developer solution The carbon dioxide-depleted that the alkaline components of shadow activity can be absorbed, therefore can reduce.Meanwhile, aobvious In shadow liquid, under the carbon dioxide that absorbed gradually can be accumulated as the carbonate with alkaline components Go.
Carbonate in developer solution assumes alkalescence in developer solution, therefore has development effect.For example, In the case of 2.38%tmah aqueous solution, if the content of carbon dioxide is about in developer solution 0.4wt% about following, then can be developed.
So, for the photoresist being dissolved in developer solution and the carbon dioxide being absorbed, with Development treatment does not need the such existing viewpoint difference of these compositions, and these compositions actually can be to development The developing performance of liquid is contributed.Therefore, should not enter to be about to dissolve photoresist and absorbing carbon dioxide Completely exclusion developer solution management, but need a kind of allow they be dissolved on a small quantity same in developer solution When enter exercise they maintain the management in optium concentration developer solution management.
Based on these, inventor has obtained following opinion in the result persistently carrying out research with keen determination.That is, With the alkaline components concentration of developer solution and dissolving photoresist agent concentration independently, in the density of developer solution Can obtain between value and carbon dioxide concentration value comparing good corresponding relation (linear relationship).This Outward, if using this corresponding relation (linear relationship), measure the density of developer solution by using densimeter, The absorbing carbon dioxide concentration being in the past difficult to measure can be measured.Further, if using this corresponding relation (linear relationship), then can be led to based on the density value being measured or the carbon dioxide concentration value being calculated Cross the supply of the replenisher gas concentration lwevel to manage developer solution.
Inventor assume that the situation of the management carrying out 2.38%tmah aqueous solution, modulates alkalescence Constituent concentration, dissolving photoresist agent concentration, absorbing carbon dioxide concentration are changed into different value and are obtained Various tmah aqueous solutions, as simulation developer solution sample.Inventor is by 2.38%tmah water Solution, as the basic composition of developer solution, has modulated alkaline components concentration (tmah concentration), molten Solution photoresist agent concentration, absorbing carbon dioxide concentration change into 11 corrections obtained from different value Standard solution.
Inventor be directed to these simulations developer solution sample determinations alkaline components concentration (tmah concentration), Absorbing carbon dioxide concentration and density, have carried out confirming the reality of constituent concentration and the dependency relation of density Test.
Mensure is correction standard solution to be adjusted to after 25.0 DEG C of temperature carry out.Temperature adjustment be with Under type: temperature treatment is being in 25 DEG C about of thermostatic water bath, long-time immersion encloses correction The bottle of standard solution, from wherein being sampled, passed through temperature control further before will being measured Device processed is adjusted to 25.0 DEG C once again.The densimeter using self-oscillation method is employed in density measurement, The natural frequency that self-oscillation method measures according to exciting u word pipe flow cell obtains density.Surveyed The unit of fixed density value is g/cm3.
Table 1 below represents the constituent concentration of each sample and the measurement result of density.
[table 1]
The constituent concentration of table 1 consider tmah aqueous solution for strong basicity easy absorbing carbon dioxide Situation about deteriorating afterwards, employs by can accurately analyzing alkaline components concentration (tmah concentration) and absorbing The titrimetry of gas concentration lwevel separately measures value obtained from each sample.Wherein, with regard to dissolving Photoresist agent concentration, employs weight modulation value.
Titration be using hydrochloric acid as titer reagent acid-base titration.As titration appratuss, employ Rhizoma Sparganii The automatic titration device gt-200 that chemical analyses company manufactures.
Fig. 1 represents the absorbing carbon dioxide concentration of each sample shown in table 1 and the chart of density.This figure Table is that gas concentration lwevel (wt%) is set to transverse axis, by density (g/cm3) it is set to the longitudinal axis, to each sample Value described obtained from chart.According to each point described, obtained back by method of least square Return straight line.
According to Fig. 1, different unrelated with alkaline components concentration and dissolving photoresist agent concentration , between the absorbing carbon dioxide concentration of developer solution and the density of developer solution, there is good linear pass in ground System.Learnt by this experimental result inventor, if using gas concentration lwevel and the density of this developer solution Between corresponding relation (linear relationship), by measure developer solution density, developer solution can be calculated Absorbing carbon dioxide concentration.
Unrelated with alkaline components concentration (tmah concentration) and dissolving agent concentration against corrosion therefore, it is possible to realize Ground can be close by employing of the gas concentration lwevel of this corresponding relation (linear relationship) mensure developer solution The component concentration measuring device of the developer solution of degree meter.
Additionally, it is generally the case that alkali in the alkaline-based developer of Reusability in development treatment operation Property constituent concentration (tmah concentration) and dissolve agent concentration against corrosion be to be managed by developer solution managing device Reason.Make linear deterioration between the density of developer solution and gas concentration lwevel will because with above-mentioned mould The experiment intending sample is compared, less.Therefore, the absorption two of measured developer solution involved in the present invention The component concentration measuring device of oxidation concentration of carbon can also be used as well can be to absorbing carbon dioxide The part of developer solution managing device that concentration is monitored or manages.
Further, alkaline-based developer has the trend that absorbing carbon dioxide increases, therefore as replenisher Supplement the little replenisher (for example, the stock solution of developer solution, new liquid etc.) of gas concentration lwevel such that it is able to The absorbing carbon dioxide concentration management of developer solution is become given management value, or manages into given management Value is following.
Additionally, as shown in figure 1, the gas concentration lwevel of developer solution has the corresponding of monotone increasing with density Relation (linear relationship), therefore make the absorbing carbon dioxide concentration of developer solution become given management value or It is equal to below management value and make the density value of developer solution become corresponding given management value or management value Below.Therefore, if the management of density will be set to the corresponding density value of management value of gas concentration lwevel Value, then pass through to measure the density of developer solution, and the density value that this is measured manage into its management value or pipe The absorbing carbon dioxide concentration of developer solution is made to become given it is also possible to manage into developer solution below reason value Management value or management value below.
Here, given management value refers to, the aobvious of developing performance can be played well as developer solution The upper limit of the concentration value of the carbon dioxide of shadow liquid and predetermined concentration value or corresponding close Angle value.Also identical in the following description.
Then, it is described with reference to specific embodiment.
(first embodiment)
Fig. 2 is the schematic diagram of the component concentration measuring device of the developer solution involved by present embodiment.
The component concentration measuring device a of the developer solution of present embodiment possesses determination part 1 and operational part 2.
Determination part 1 possesses the densimeter of the density for measuring developer solution and for measuring developer solution Other determination units (the 11～13 of in figure) of other characteristic values, sampling pump 14, for will be sampled Developer solution be adjusted to the temperature chamber (not shown) of given temperature of the measurement (such as 25 DEG C) before measurement Deng.
As long as in the case that component concentration measuring device a measures density, as determination part 1 Determination unit 11～13, can it is not necessary to measure it as long as possessing densimeter (being for example set to 11) The determination unit (such as 12,13) of his characteristic value.But, the constituent concentration as alkaline-based developer is surveyed Determine device, except measure gas concentration lwevel in addition to alkaline components also to be measured concentration, be dissolved in aobvious The situation of the photoresist agent concentration in shadow liquid is more.Therefore, in fig. 2, describe and also include surveying Determine the mensure of other determination units when alkaline components concentration and dissolving photoresist agent concentration etc. required Unit 11,12,13.One of them is densimeter.Following component concentration measurement apparatus a's In explanation, the determination unit 11 in the determination unit 11～13 of Fig. 2 is set to densimeter.
Operational part 2 possesses the computing mould calculating carbon dioxide concentration value according to the density value being measured Block 21.Pre-enter corresponding between the density of developer solution and gas concentration lwevel to computing module 21 Relation (for example, linear relationship as shown in Figure 1).Computing module 21 possesses aobvious according to measured The density value of shadow liquid obtains the function of corresponding carbon dioxide concentration value.Furthermore it is preferred that operational part 2 Possesses the display unit 22 for showing calculated gas concentration lwevel.Additionally, constituent concentration is surveyed The groove that determining device a has developer solution by sampling pipe arrangement 15 with storage is connected.
The component concentration measuring method of the component concentration measuring device a of present embodiment is described.Pass through Sampling pump 14 delivers to developer solution in determination part 1.The developer solution delivering to determination part 1 is first in constant temperature It is adjusted to given temperature of the measurement (such as 25 DEG C) in groove.Developer solution after temperature adjustment is sent to close Degree meter 11, other determination units 12,13.Densimeter 11 measures the density of developer solution.Other measure Unit 12,13 also measures the characteristic value of developer solution respectively.Survey to constituent concentration from outlet side line 16 Determine outside device a, to discharge the developer solution after measuring.
Densimeter 11 and other determination units 12, the 13 computing mould with operational part 2 by holding wire Block 21 connects.The density value of the developer solution being determined by densimeter 11 and pass through other determination units 12nd, the determination data of the characteristic value of 13 developer solutions determining is sent to computing mould via holding wire Block 21.
Accept the density value of developer solution and the computing module 21 of the determination data of other characteristic values has been based on Determination data, calculates the constituent concentration of developer solution.The gas concentration lwevel of developer solution is using development Corresponding relation (linear relationship as such as Fig. 1) between the density of liquid and gas concentration lwevel is counting Calculate.That is, the corresponding relation between the density according to developer solution and gas concentration lwevel, obtain with The corresponding carbon dioxide concentration value of density value of the developer solution being measured, as the dioxy of developer solution Change the measured value of concentration of carbon.
So, the component concentration measuring device a of the developer solution of present embodiment can be based on developer solution Density measured value, the corresponding relation of the density according to developer solution and gas concentration lwevel, measure aobvious The gas concentration lwevel of shadow liquid.
The component concentration measuring device a of present embodiment is except as shown in Figure 2 by determination part 1 It is also possible to be separately constructed these parts beyond constituting as the device of one with operational part 2.Dividing In the case of opening composition, can be by the densimeter using determination part 1 as long as being connected to by holding wire etc. 11 and the determination data that measures of other determination units 12,13 be delivered to the computing module 21 of operational part 2 In.Determination data can also wirelessly be received and dispatched.
The component concentration measuring device a of present embodiment and its determination part 1 are except being connected with storage tank Cheng Kecong storage have developer solution storage tank sample developer solution beyond it is also possible to recycle developer solution Development treatment operation circular route directly or by bypass connect.
Additionally, in fig. 2 it is illustrated that including densitometric each determination unit 11～13 by series connection even Situation about connecing, but the connection not limited to this of each determination unit.Both can be connected in parallel it is also possible to distinguish Independently possess liquor charging path to be measured.Densimeter and other determination units are measured Sequentially, also it is not particularly limited its sequencing.As long as according to the feature of each determination unit, suitably pressing Optimal order is measured.
In the structure of determination part 1 shown in Fig. 2, sampling pump 14 is not required.With circular route It is not necessary to arrange sampling pump 14 in determination part 1 in the case of being directly connected to.Even if additionally, It is also possible to sampling pump 14 is not arranged on mensure in the case that storage tank is sampled to developer solution In portion 1.On the other hand although not illustrating, but it is preferred for for developer solution being adjusted to given survey The temperature chamber of constant temperature degree is arranged on the positive prime of determination unit.
The computing module 21 of operational part 2 calculates carbon dioxide except the measured value possessing according to density Beyond the function of concentration, can also possess alkaline components concentration, the dissolving photoresist calculating developer solution The function of the other compositions concentration such as agent concentration.In such manner, it is possible to realize measuring the alkaline components of developer solution The component concentration measuring device of concentration, dissolving photoresist agent concentration and gas concentration lwevel.
As the densimeter 11 of the component concentration measuring device a of present embodiment, can be using utilization The float type densimeter of buoyancy, make use of 2 points of differing heights in liquid between pressure differential differential pressure Formula densimeter, make use of the various densimeter such as gamma-ray densimeter of transmitance of gamma ray.More Preferably employ the vibrating densimeter to obtain density for the natural frequency detecting the pipeline being filled with liquid.
Fig. 3 schematically show the typical structure of vibrating densimeter.
The determination part of vibrating densimeter possesses and is bent to the sample cell 51 of u shape, surrounds this sample The thermostat module 54 in product pond 51, the thermal insulation barriers 55 positioned at thermostat module periphery.In thermostat module 54 In be provided with the Peltier element 53 of temperature for adjusting sample.In sample cell 51, in bending The front end in portion is provided with oscillator 56, near oscillator 56 and be configured with excitation oscillator 56 drive division and The test section of the frequency of vibration of detection oscillator 56.
The natural frequency that energized sample cell 51 is associated with the quality of the liquid internal with it is shaken Dynamic.By detecting this natural frequency it is known that the quality of liquid in sample cell 51, therefore according to sample The internal capacity in product pond 51 is measuring the density of liquid.
Vibrating densimeter possesses to enter the high and stable mensure of line sensitivity and can carry out continuous The feature measuring.Vibrating densimeter can be together with thermometer, by temperature adjustment unit and heat-insulated list Unit, can be measured under conditions of good temperature conditionss, temperature stability.Additionally, vibration Formula densimeter only passes through to convey the liquid of sample it becomes possible to the density of determination sample to sample cell.Surveying Determine during density it is not necessary to carry out interpolation of reagent etc., so also without waste liquid.
Various determination units 11～13 in the component concentration measuring device of the developer solution of present embodiment, Especially densitometric set-up mode is not limited to the mode shown in Fig. 2.
Density in respect of various measuring principles and mensuration mode, is had and is adapted with each principle and mode Method to set up.In the situation employing float type densimeter or differential pressure densimeter as densimeter Under, arrange close in the way of in the storage tank that densitometric float portion or probe portion be impregnated in developer solution Degree is calculated as.In the case of using gamma-ray densimeter, can be on the pipeline of developer solution flowing Directly density of setting meter.In the case of using vibrating densimeter, as long as shown in Fig. 2 will store up Hide tank and densimeter is attached by sample lines it becomes possible to carry out sampling come the company of realization to developer solution Continuous mensure.
As long as vibrating densimeter just can measure density due to developer solution is delivered to sample cell, therefore suitable Together in the use under the conditions of continuous and online.Additionally, being suitable for stably managing the mensure such as temperature of liquid The situation of condition, can carry out stable and highly sensitive mensure.By the vibration type density of technique Meter also can be with 0.001 (g/cm3) about precision be measured, according to the linear relationship of Fig. 1, this The component concentration measuring device of embodiment is capable of the survey of the carbon dioxide of about about 0.15 (wt%) Determine precision.If the alkaline components concentration to developer solution or dissolving photoresist agent concentration are managed Situation, then linearly more preferable between density and gas concentration lwevel, but also can expect densitometric The raising of measurement accuracy, therefore can expect can also more precisely measure component concentration measuring device Gas concentration lwevel.
The component concentration measuring device of the developer solution of present embodiment is by using can measure developer solution Gas concentration lwevel this point, can be acted effectively as the developer solution managing device of management gas concentration lwevel Part.By the component concentration measuring device of control unit and present embodiment is combined, from And the developer solution managing device that can manage gas concentration lwevel can be constituted, wherein, control unit is carried out Following control: the gas concentration lwevel of the developer solution being measured based on component concentration measuring device, Xiang Xian Shadow liquid supply replenisher is so that the gas concentration lwevel of developer solution becomes given management value or management value Below.
If additionally, the development measuring the component concentration measuring device of the developer solution using present embodiment The gas concentration lwevel of liquid is compared with the feasible value of the gas concentration lwevel of developer solution, when exceeding this Sending signal during feasible value, or so that emergency warning lamp is flashed, or make buzzer rings, then can also constitute aobvious The constituent concentration monitoring arrangement of shadow liquid.
(second embodiment)
Fig. 4 is the density value based on the developer solution being determined by densimeter, using developer solution density with Corresponding relation between gas concentration lwevel, feeds replenisher to developer solution, thus two to developer solution The schematic diagram of the developer solution managing device that oxidation concentration of carbon is managed.For convenience of description, developer solution Managing device e is in the way of being connected with developing procedure equipment b, and developing procedure equipment b, supplement Liquid storage portion c, circulation stirring mechanism d are illustrated together.
First, briefly describe developing procedure equipment b.
Developing procedure equipment b mainly include developer solution storage tank 61, overflow launder 62, developing room cover 64, Roller path 65, developer solution shower nozzle 67 etc..In developer solution storage tank 61 storage have aobvious Shadow liquid.Developer solution is to carry out composition management by supplementing replenisher.Developer solution storage tank 61 has Standby liquid level meter 63 and overflow launder 62, the increase of the liquid measure that supply replenisher is caused is managed. Developer solution storage tank 61 and developer solution shower nozzle 67 are connected by development liquid pipeline 80.? In developer solution storage tank 61, the developer solution of storage is by being arranged on the circulating pump on development liquid pipeline 80 72 are sent to developer solution shower nozzle 67 via filter 73.Roller path 65 is arranged on The top of developer solution storage tank 61, transmission is formed with the substrate 66 of photoresist film.Developer solution from Developer solution shower nozzle 67 drips.The substrate 66 being transmitted by roller path 65 is through drippage Among developer solution, thus developed immersion stain.Then, developer solution is recycled to developer solution storage tank 61, it is stored again.So, circulate in developing procedure repeatedly using developer solution.In addition, having When be implemented in small-sized glass substrate development interior fill up nitrogen etc. to prevent two in absorption air The process of carbonoxide.
Then, developer solution managing device e of present embodiment is described.The development liquid pipe of present embodiment Reason device e is the developer solution managing device of in the following manner, i.e. measure developer solution by densimeter Density, using the corresponding relation between the density of developer solution and gas concentration lwevel (for example, as Fig. 1 Shown linear relationship), based on the density value being measured, feed replenisher to developer solution so that showing The gas concentration lwevel of shadow liquid becomes below given management value or management value.
Developer solution managing device e possesses determination part 1, operational part 2 and control unit 3, is joined by sampling Pipe 15 and outlet side line 16 and be connected with developer solution storage tank 61.Connected by holding wire and measure Portion 1, operational part 2 and control unit 3.
Determination part 1 possesses sampling pump 14, densimeter 11 and other characteristic values for measuring developer solution Determination unit 12,13.Determination unit 12,13 is e.g. used for measuring the alkaline components of developer solution Concentration and the device of dissolving photoresist agent concentration.It is connected in series densimeter in the rear class of sampling pump 14 11 and determination unit 12,13.In order to improve measurement accuracy further, preferably determination part 1 is also equipped with Make the stable thermostat unit (not shown) in given temperature of sampled developer solution.Now, Preferably thermostat unit is arranged on the positive prime of determination unit.Sampling pipe arrangement 15 and determination part 1 Sampling pump 14 connect, outlet side line 16 be connected with the pipe arrangement of determination unit end.
Operational part 2 includes alkaline components concentration and the dissolving photoresist being for example used for calculating developer solution The computing module 21 of agent concentration.Computing module 21 by holding wire with the survey being arranged at determination part 1 Order unit 12,13 connects.As long as only possessing, in developer solution managing device e, the density measuring developer solution Come in the case of controlling the function of gas concentration lwevel it is not necessary to determination unit 12 and 13 and fortune Calculation portion 2.
Control unit 3 is connected with the densimeter 11 of determination part 1 by holding wire.Additionally, control unit 3 by holding wire be arranged on to developer solution convey replenisher stream on control valve 41～43 Connect.In the diagram, control valve 41～43 has been depicted as the inside portion of developer solution managing device e Part, but control valve 41～43 is not the necessary portion of developer solution managing device e of present embodiment Part.As long as control unit 3 can be got in touch with control valve 41～43 to be controlled control valve 41～43 Action come to developer solution feed replenisher.Control valve 41～43 can also be arranged on developer solution The outside of managing device e.
Then, the action of the developer solution managing device of present embodiment is described.
It is sent in determination part 1 from the developer solution of developer solution storage tank 61 sampling, carry out temperature wherein Degree is adjusted.Then, developer solution is sent to densimeter 11, measures density value wherein.The survey of density Fixed number evidence is sent to control unit 3.
It is right and the density based on developer solution and gas concentration lwevel between to be set with control unit 3 The management value phase of (for example, linear relationship as shown in Figure 1) and the gas concentration lwevel of determination should be related to The management value of corresponding density.The survey of the density according to the developer solution accepting from determination part 1 for the control unit 3 Definite value, is carried out as follows control.
The mode becoming given management value in the gas concentration lwevel according to developer solution is managed In the case of, it is carried out as follows management.That is, feed replenisher to developer solution so that the developer solution that measured Density value become the management value of the density corresponding with the management value of gas concentration lwevel.In view of not entering During row concentration management, developer solution is understood absorbing carbon dioxide and gas concentration lwevel is increased, as needs The replenisher of supply, as long as supply performance makes the supplement of the thinning effect of the gas concentration lwevel of developer solution Liquid.
Become the following mode of given management value in the gas concentration lwevel according to developer solution and enter line pipe In the case of reason, carry out following management.That is, due between the density of developer solution and gas concentration lwevel Corresponding relation be as shown in Figure 1 monotone increasing relation, therefore, to developer solution feed supplement Liquid is so that the density value of the developer solution being measured becomes corresponding with the management value of gas concentration lwevel Below the management value of density.As the replenisher needing supply, as long as supply plays makes the two of developer solution The replenisher of the thinning effect of oxidation concentration of carbon.
Here, " given management value " refers to, play two during optimal developing performance as developer solution Carbonoxide concentration value and management value known in advance.For example, using the line being obtained by development treatment Wide and residual film thickness come to evaluate developer solution liquid properties when, be to refer to make these live widths and remaining film Thickness becomes the carbon dioxide concentration value of the developer solution of desired optimum.It is also same in the following description Sample.
As the management of the gas concentration lwevel of developer solution, for example, using as developer solution In the case of 2.38%tmah aqueous solution, the gas concentration lwevel preferred administration of developer solution becomes 0.40 (wt%) is below.More preferably manage into 0.25 (wt%) below.
In addition, it is generally the case that measuring and to manage alkaline components dense in developer solution managing device e Degree and dissolving photoresist agent concentration, therefore possess the survey of the characteristic value being determined as this required developer solution Order unit 12,13.The characteristic value of the developer solution being determined by determination unit 12,13 is sent to fortune Calculation portion 2.Operational part 2 according to the characteristic value of the developer solution being measured, calculates alkaline components concentration and molten Solution photoresist agent concentration, its result is delivered to control unit 3.Control unit 3 be based on this measurement result or Operation result, the alkaline components concentration of developer solution and dissolving photoresist concentration management are become optimal State.
As the replenisher being fed in developer solution, for example, there are the stock solution of developer solution, new liquid, pure water etc.. These replenishers are used for making the gas concentration lwevel of developer solution thinning.Also for managing the alkalescence of developer solution Constituent concentration and dissolving photoresist agent concentration, feed these replenishers.
Replenisher is stored in the replenisher storage tank 91,92 of replenisher storage portion c.Replenisher stores up Hide tank 91,92 to be connected with the nitrogen pipeline 86 possessing valve 46,47, by supplying via this pipeline The nitrogen given is pressurized.Additionally, replenisher storage tank 91,92 respectively with replenisher pipeline 81, 82 connections, convey replenisher via the valve 44,45 being generally in the state opened.In replenisher With being provided with control valve 41～43 on pipeline 81,82 and pure water pipeline 83, by control unit 3 To control being turned on and off of control valve 41～43.By the action of control valve 41～43, replenisher The pressurized conveying of replenisher stored in storage tank 91,92, additionally conveys pure water.Then, Replenisher is collaborated with circulation stirring mechanism d via interflow pipeline 84, is recharged developer solution storage In tank 61, it is stirred wherein.
If lead to the replenisher stored in replenisher storage tank 91,92 to reduce because of supply, its Intrinsic pressure can decline, lead to quantity delivered to become unstable, therefore suitably opened according to the minimizing of replenisher Valve 46,47, to supply nitrogen, maintains the intrinsic pressure state being maintained of replenisher storage tank 91,92. When replenisher storage tank 91,92 is drained, shutoff valve 44,45, change and be filled with replenisher New replenisher storage tank, or the replenisher separately preparing is again filled with the replenisher storage emptying Hide in tank 91,92.
The control of control valve 41～43 is for example carried out as follows.If the flow flowing when control valve is opened obtains To adjustment, then pass through management and open the time of control valve such that it is able to feed the supplement of the amount that should feed Liquid.The measured value based on density for the control unit 3 and management value, send control signal to control valve, so that Control valve is opened the scheduled time makes the replenisher of the amount that should feed flow through.
The mode controlling can be using the various controls making the control that controlled quentity controlled variable meets desired value be used Method.It is particularly preferred to ratio control (p control) (p:proportional), integration control (i control) (i: Integral), differential controls (d control) (d:derivative) and the control that these control combinations are got up (pi control etc.).More have choosing is pid control.
Thus, the developer solution managing device involved by present embodiment can feed replenisher to developer solution The gas concentration lwevel making developer solution becomes below given management value or management value, thus manages aobvious The gas concentration lwevel of shadow liquid.
(the 3rd embodiment)
Fig. 5 be based upon densimeter mensure developer solution density value, the density according to developer solution with Corresponding relation between gas concentration lwevel, calculates gas concentration lwevel, based on the developer solution being calculated Gas concentration lwevel, to developer solution feed replenisher, thus entering to the gas concentration lwevel of developer solution The schematic diagram of the developer solution managing device of line pipe reason.For convenience of description, developer solution managing device e In the way of being connected with developing procedure equipment b, and developing procedure equipment b, replenisher storage portion c, Circulation stirring mechanism d is illustrated together.
The developer solution managing device of present embodiment is that the measured value of the density according to developer solution calculates two The control unit of the gas concentration lwevel of the operational part of oxidation concentration of carbon and control developer solution is implemented as one The developer solution managing device of the built-in function of Operations Analysis (such as computer) of body.
Developer solution managing device e of present embodiment possesses determination part 1 and calculation control unit 23.Survey Determine portion 1 and possess densimeter 11 and other determination units 12,13.Calculation control unit 23 possesses computing Module 21 and control module 31.
The density value of sampled developer solution in determination part 1, is measured by densimeter 11.Surveyed Fixed density value is sent to calculation control unit 23 via holding wire.In addition, determination part 1 Details is identical with second embodiment, therefore omits the description.
The calculation control unit 23 having accepted the measured value of the density of developer solution utilizes computing module 21, base Corresponding relation (for example, the linear relationship of Fig. 1) between the density of developer solution and gas concentration lwevel, Measured value according to density is calculating the gas concentration lwevel of corresponding developer solution.The titanium dioxide calculating Concentration of carbon is sent to control module 31 as the measured value of the gas concentration lwevel of developer solution.
Calculation control unit 23 can also possess as calculation function for example for calculating the alkali of developer solution Property constituent concentration and dissolving photoresist agent concentration computing module.
Control module 31, based on the gas concentration lwevel being measured, sends to control valve 41～43 and controls Signal is so that the gas concentration lwevel of developer solution becomes below given management value or management value.Development Liquid meeting absorbing carbon dioxide, therefore gas concentration lwevel can increase, so controlling is to be had by supply The replenisher of the thinning effect of gas concentration lwevel is made to carry out.The details controlling and second is in fact The explanation applied in mode is identical, therefore omits the description.
Calculation control unit 23 can also possess as control function for example for controlling the alkali of developer solution Property constituent concentration and dissolving photoresist agent concentration control module.
Thus, developer solution managing device e according to present embodiment, can be by the suction of alkaline-based developer Receive gas concentration lwevel and manage into below given management value or management value.
(the 4th embodiment)
Fig. 6 is the density value based on the developer solution being determined by densimeter, the density according to developer solution with Corresponding relation between gas concentration lwevel, calculates gas concentration lwevel, and based on the development calculating The gas concentration lwevel of liquid to feed replenisher to developer solution, thus the gas concentration lwevel to developer solution The schematic diagram of the developer solution managing device being managed.For convenience of description, developer solution managing device e In the way of being connected with developing procedure equipment b, and developing procedure equipment b, replenisher storage portion c, Circulation stirring mechanism d is illustrated together.
The developer solution managing device of present embodiment is to be separately constructed the survey of the density according to developer solution The control of the gas concentration lwevel of the arithmetic element of fixed value calculation gas concentration lwevel and control developer solution The developer solution managing device of unit processed.
Developer solution managing device e of present embodiment possesses determination part 1, operational part 2 and control unit 3. Determination part 1 possesses densimeter 11 and other determination units 12,13.Operational part 2 possesses computing module 21, this computing module 21 is according to the measured value of density, corresponding with gas concentration lwevel based on density Relation (for example, the linear relationship of Fig. 1), calculates the gas concentration lwevel of developer solution.Control unit 3 has Standby control module 31, this control module 31, based on the gas concentration lwevel calculating, is mended to developer solution The gas concentration lwevel to be controlled such that developer solution to replenisher becomes given management value or pipe Below reason value.
The density value of sampled developer solution in determination part 1, is measured by densimeter 11.Surveyed Fixed density value is sent to operational part 2 by holding wire.In addition, the detailed feelings of determination part 1 Condition is identical with second embodiment, therefore omits the description.
The operational part 2 having accepted the measured value of the density of developer solution utilizes computing module 21, based on aobvious Corresponding relation (for example, the linear relationship of Fig. 1) between the density of shadow liquid and gas concentration lwevel, root Calculate the gas concentration lwevel of corresponding developer solution according to the measured value of density.The carbon dioxide being calculated Concentration is sent to control unit 3 as the measured value of the gas concentration lwevel of developer solution.
Operational part 2 can also possess for example for calculating the alkaline components of developer solution as calculation function Concentration and the computing module of dissolving photoresist agent concentration.
Control unit 3, based on the gas concentration lwevel being measured, sends to control valve 41～43 and controls letter Number the gas concentration lwevel of developer solution is made to become below given management value or management value.Developer solution meeting Absorbing carbon dioxide, therefore gas concentration lwevel can increase, so controlling is to have by supply to make two The replenisher of the oxidation thinning effect of concentration of carbon is carrying out.The details controlling and the second embodiment party Explanation in formula is identical, therefore omits the description.
Control unit 3 can also possess for example for controlling the alkaline components of developer solution as control function Concentration and the control module of dissolving photoresist agent concentration.
As described above, according to developer solution managing device e of present embodiment, can be by alkaline-based developer Absorbing carbon dioxide concentration management become below given management value or management value.
Then, the variation of developer solution managing device e of present embodiment is described.
In Fig. 4～6, depict determination part 1 and operational part 2, the control of developer solution managing device The developer solution managing device that portion 3 is integrally formed, but developer solution managing device e of present embodiment is not It is limited to this.Determination part 1 can also be separately formed.
Each determination unit 11～13 including densimeter is due to the measuring principle being respectively adopted Difference and each there is optimal method to set up, therefore for example can also be by determination part 1 and developer solution Pipeline 80 on-line joining process, or be arranged to be immersed in measuring probe in developer solution storage tank 61.? Each determination unit 11～13 can be individually set.Developer solution management dress for present embodiment For putting the realization of e, as long as each determination unit 11～13 mutually may be used with operational part 2 and control unit 3 Get in touch with into and can exchange determination data.
Equally, in Fig. 4～6, densimeter and other determination units 11～13 are depicted by series connection even Developer solution managing device e connecing, but the developer solution managing device e not limited to this of present embodiment.Respectively Determination unit 11～13 both can be connected in parallel it is also possible to be configured independently respectively.If according to Measuring principle that each determination unit is adopted and need to add reagent, then each determination unit can also possess For realizing the pipe arrangement of this function, if desired waste liquid, then each determination unit can also possess for realizing The pipeline of this function.Even if not being connected in series the development that each determination unit is also capable of present embodiment Liquid managing device e.
The operational part 2 of developer solution managing device e of present embodiment is except possessing the density from developer solution It is based on developer solution in corresponding relation (linear relationship as such as Fig. 1) and gas concentration lwevel between Density measured value to calculate the calculation function of gas concentration lwevel beyond, can also possess other Calculation function.For example, it is also possible to possessing the alkaline components concentration for calculating developer solution and dissolving photic The calculation function of the other compositions concentration such as agent concentration against corrosion.
The control unit 3 of developer solution managing device e of present embodiment is except possessing for mending to developer solution To control into replenisher developer solution gas concentration lwevel become given management value or management value with Under control function beyond, can also possess other control functions.For example, it is also possible to possess for inciting somebody to action The other compositions concentration such as the alkaline components concentration of developer solution and dissolving photoresist agent concentration controls into For given management value, become below given management value or enter the control in given range of management Function processed.For realize the control of this function except by developer solution feed replenisher realize with Outward, can also be addition of the control suitably developer solution abolished and to realize control, addition of and make to lead to The control that the regeneration developer solution of regeneration after crossing the impurity screenings such as filter returns is each come the control to realize etc. Plant and control.
In Fig. 4～6, depict developer solution managing device e and replenisher pipeline 81,82 and pure Water pipeline 83 is connected to be fed to the control of setting on the stream of the replenisher in developer solution in conveying Valve 41～43 processed is the situation of the internal part of developer solution managing device e, but present embodiment is aobvious Shadow liquid managing device e not limited to this.Control valve 41～43 can not also be set by developer solution managing device It is set to internal part it is also possible to not be connected with the pipeline 81～83 feeding replenisher to developer solution.
Control unit 3 in developer solution managing device e of present embodiment and being arranged on for feeding supplement As long as the control valve 41～43 on the pipeline of liquid is in and mutually can carry out contact and make control valve 41～43 Accept the state of the control signal sending from the control unit 3 of developer solution managing device e.Even if Control valve is not the internal part of developer solution managing device e it is also possible to realize the aobvious of present embodiment Shadow liquid managing device e.
The control unit 3 of developer solution managing device e can not also with determination part 1 and operational part 2 integratedly Constitute, control unit 3 can be separately formed.Determination part 1, operational part 2 and control unit 3 can also be by It is arranged to device independent of each other.As long as contact can be carried out to be made it possible to by holding wire etc. mutually hand over Change determination data, operation result, control signal etc. it becomes possible to realize the development liquid pipe of present embodiment Reason device e.
The function of control gas concentration lwevel of control unit 3 and control alkaline components concentration and dissolving The function of the other compositions such as photoresist agent concentration is preferably realized by same control unit, but also may be used To be realized by different control units.Replenisher and the pipe conveying this replenisher used in control Road and control valve etc., can prepare according to the object component of in check developer solution, respectively if but energy Enough it is used in conjunction with, then be preferably used in conjunction with.
The developer solution managing device of the present invention allows above-mentioned various modifications example, and it possesses densimeter, uses Corresponding relation between the density of developer solution and gas concentration lwevel is (for example, as shown in Figure 1 linear Relation), the density value based on the developer solution being determined by densimeter or based on according to densimeter measure The carbon dioxide concentration value of the developer solution to calculate for the density value of the developer solution going out, to developer solution supply Replenisher becomes below given management value or management value come the gas concentration lwevel to control into developer solution.
As described above, according to the developer solution managing device of the present invention, can be by the absorption of alkaline-based developer Gas concentration lwevel manages into below given management value or management value.Therefore, by present embodiment Developer solution managing device, alkaline-based developer can be made to maintain the titanium dioxide playing optimal developing performance In the state of concentration of carbon, it is capable of desired live width and residual film thickness.
The present invention developer solution managing device can also to the alkaline components concentration of alkaline-based developer and In the case that dissolving photoresist agent concentration is managed, each constituent concentration of alkaline-based developer is managed Become given state.Therefore, compared with the existing developer solution management that cannot manage gas concentration lwevel, According to the developer solution managing device of the present invention, can more precisely carry out maintaining management to make alkalescence aobvious The developing performance of shadow liquid is constant.Permanent therefore, it is possible to expect developing powder when making development of photoresist Determine and realize stabilisation, the live width based on development treatment and residual film thickness are constant, and product quality is carried Height, contributes to realizing further miniaturization and highly integrated.
In addition, according to the developer solution managing device of the present invention, because developer solution is automatically maintained all the time Optimal developing performance, therefore, it is possible to expect to improve production rate, and does not need developer solution more Change operation, contribute to reducing operating cost and waste liquid cost.

Claims (7)

1. a kind of component concentration measuring device of developer solution, possesses:
Densimeter；And
Arithmetic element, based on the density value in alkaline developer solution being determined by above-mentioned densimeter, Corresponding relation between density value according to above-mentioned developer solution and carbon dioxide concentration value, calculates above-mentioned aobvious The gas concentration lwevel of shadow liquid.
2. a kind of component concentration measuring method of developer solution, comprising:
The step measuring the density of developer solution in alkalescence；And
Based on the density of the above-mentioned developer solution being measured, the density according to above-mentioned developer solution and carbon dioxide Corresponding relation between concentration, the step calculating the gas concentration lwevel of above-mentioned developer solution.
3. a kind of developer solution managing device, possesses:
Densimeter；And
Control unit, based on the density value in alkaline developer solution being determined by above-mentioned densimeter, Using the corresponding relation between the density value of above-mentioned developer solution and carbon dioxide concentration value, defeated to being arranged on Send control valve on the stream of the replenisher being fed in above-mentioned developer solution to send control signal so that on The gas concentration lwevel stating developer solution becomes below given management value or given management value.
4. a kind of developer solution management method, comprising:
The step measuring the density of developer solution in alkalescence；And
Based on the density of the above-mentioned developer solution being measured, using density and the carbon dioxide of above-mentioned developer solution Corresponding relation between concentration, feeds, to above-mentioned developer solution, the titanium dioxide that replenisher makes above-mentioned developer solution Concentration of carbon becomes given management value or given management value below step.
5. a kind of developer solution managing device, possesses:
Densimeter；And Operations Analysis,
This Operations Analysis possesses:
Operational part, based on the density value in alkaline developer solution being determined by above-mentioned densimeter, root According to the corresponding relation between the density value of above-mentioned developer solution and carbon dioxide concentration value, calculate above-mentioned development The gas concentration lwevel of liquid；And control unit, based on the above-mentioned development being calculated by above-mentioned operational part The gas concentration lwevel of liquid, is fed on the stream of the replenisher in above-mentioned developer solution to being arranged on conveying Control valve send control signal so that the gas concentration lwevel of above-mentioned developer solution becomes given management Below value or given management value.
6. a kind of developer solution managing device, possesses:
Densimeter；
Arithmetic element, based on the density value in alkaline developer solution being determined by above-mentioned densimeter, Corresponding relation between density value according to above-mentioned developer solution and carbon dioxide concentration value, calculates above-mentioned aobvious The gas concentration lwevel of shadow liquid；And
Control unit, the dense carbon dioxide based on the above-mentioned developer solution being calculated by above-mentioned arithmetic element Degree, is fed to the control valve transmission control on the stream of the replenisher in above-mentioned developer solution to being arranged on conveying Signal processed is so that the gas concentration lwevel of above-mentioned developer solution becomes given management value or given management Value is following.
7. a kind of developer solution management method, comprising:
The step measuring the density of developer solution in alkalescence；
Based on the density of the above-mentioned developer solution being measured, the density according to above-mentioned developer solution and carbon dioxide Corresponding relation between concentration, the step calculating the gas concentration lwevel of above-mentioned developer solution；And
Feed the gas concentration lwevel of the above-mentioned developer solution that replenisher makes to be calculated to above-mentioned developer solution Become given management value or given management value below step.
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