CN106371295A - Developing solution managing method and apparatus - Google Patents

Abstract

A developing solution managing method and apparatus are provided and can achieve developing treatment with maintainable expected developing performance, maintainable expected line width and maintainable expected residual film thickness. The developing solution managing apparatus (D) is provided with a control unit (21). The control unit is provided with a data memory part (23) memorizing electric conductivity data provided with electric conductivity values of a developing solution each concentration zone of which adopting as indexes the concentration of a dissolved photoresist and the concentration of absorbed carbon dioxide of an alkaline and repeatedly used developing solution is confirmed in advance to achieve preset developing performance, and a control part (31) setting an electric conductivity value, memorized in the data memory part (23), of a concentration zone having a determined concentration of absorbed carbon dioxide and a determined concentration of the dissolved photoresist in the developing solution as a control target value, and sending a control signal to control valves (41-43) on a flow path conveying a supplement liquid to the developing solution so that the electric conductivity value of the developing solution is the target control value.

Description

The management method of developer solution and device

Technical field

The present invention relates to a kind of management method of developer solution and device, especially relate in quasiconductor or liquid crystal panel In order that photoresist film development and the management in alkaline developer solution of Reusability in developing procedure of circuit substrate etc. Method and device.

Background technology

In the developing procedure of photoetching of fine pitch wirings processing in realizing quasiconductor or liquid crystal panel etc., as making in base The medicinal liquid of the photoresist dissolving of film forming on plate, using in alkaline developer solution (hereinafter referred to as " alkaline-based developer ").

In the manufacturing process of quasiconductor or base plate of liquid crystal panel, in recent years, the maximization of chip or glass substrate and cloth The miniaturization of line processing and highly integrated be developed.In this condition, in order to realize large substrate wiring processing Miniaturization and highly integrated, needs the concentration more precisely measuring the main component of alkaline-based developer developer solution is tieed up Hold management.

The mensure of the constituent concentration of existing alkaline-based developer make use of can be in the concentration of the alkaline components of alkaline-based developer (hereinafter referred to as " alkaline components concentration ") obtains good linear relationship this point (for example, patent documentation and conductivity between 1).

However, in recent years, alkaline-based developer and the chance of air contact is led to increase because of development treatment, alkaline-based developer Carbon dioxide in meeting absorption air, the therefore absorbtivity of the carbon dioxide of alkaline-based developer increase.If the titanium dioxide being absorbed Concentration of carbon raises, then can produce and be unable to maintain that, by the developer solution management of existing method, the problems such as given live width is processed.

The cause of this problem is, produces in the reaction of carbonate in the absorption because of carbon dioxide, in alkaline-based developer The alkaline components with developing activity are consumed.Additionally, cause also resides in, produce photic anti-in the dissolving because of photoresist In the reaction of erosion agent salt, the alkaline components in alkaline-based developer with developing activity are consumed.

For this problem, attempt the developer solution management of the alkaline components that various supplements decrease because being consumed.This In a little trials, by measuring carbonate concentration, feed the alkali being consumed in producing the reaction of carbonate using replenisher Property composition, so that have the constant concentration of the alkaline components of developing activity.Dissolving because of photoresist is consumed The alkaline components falling similarly are processed.The alkaline components that these are all based on becoming carbonate or photoresist salt lose aobvious Shadow activity and this viewpoint that lost efficacy (for example, patent documentation 2).

Patent documentation 1: No. 2561578 publications of Japanese Patent No.

Patent documentation 2: Japanese Unexamined Patent Publication 2008-283162 publication

However, gratifying developer solution management is still difficult to by the trial that this various developer solutions manage.

The result that the present inventor carries out research with keen determination to developer solution management has obtained following opinion: carbonate or anti- In developer solution, some free and contributes to development effect erosion agent salt occurs；By line pipe is entered to the conductivity values of developer solution Reason, is capable of considering in the lump and thinks that these compositions of inefficacy manage to the developer solution of the contribution that development acts in the past；And The management value of this conductivity is different with the difference of absorbing carbon dioxide concentration and dissolving photoresist agent concentration.

Think that these are to be based on: become carbonate or the alkaline components of photoresist salt do not have inefficacy, but have one Part occurs free and contributes to development effect；And, from alkaline components, carbonate and the trip of resist salt with developing activity From after contribute to development effect composition all act on conductivity.That is, inventor be found that conductivity values according to developer solution Lai The composition that management has development effect is overall, can most preferably manage the composition entirety with development effect, complete on this basis Become the present invention.

Content of the invention

The present invention be in view of above-mentioned problem and complete, it is intended that provide one kind can reach for photoresist To the given management method of the developer solution of developing performance and device.

To achieve these goals, the management method of the developer solution of the present invention, measure Reusability in alkaline development The conductivity of liquid, dissolving photoresist agent concentration and absorbing carbon dioxide concentration, will have in the dissolving determining above-mentioned developer solution Photoresist agent concentration and absorbing carbon dioxide concentration as index each concentration range be previously validated can reach given The conductivity data of the conductivity values of above-mentioned developer solution of developing performance among, dense by the dissolving photoresist being measured Degree and the above-mentioned conductivity values of the concentration range of absorbing carbon dioxide concentration determination being measured, are set as leading of above-mentioned developer solution The control targe value of electric rate, makes the conductivity of above-mentioned developer solution become above-mentioned control targe to above-mentioned developer solution supply replenisher Value.

The management method of the developer solution according to the present invention, no matter developer solution become what kind of dissolving photoresist agent concentration and Absorbing carbon dioxide concentration, in developer solution, to development effect, activated composition remains constant, therefore, it is possible to realize maintaining the phase Hope developing performance and desired live width and the development treatment of residual film thickness can be maintained.

To achieve these goals, the developer solution managing device of the present invention, possesses control unit, and this control unit possesses: Data store, preserves conductivity data, and this conductivity data has molten in alkaline developer solution in determination Reusability Solution photoresist agent concentration and absorbing carbon dioxide concentration as index each concentration range be previously validated can reach to The conductivity values of the above-mentioned developer solution of fixed developing performance；And control unit, by the dissolving photoresist by above-mentioned developer solution Being saved in above-mentioned data store of the concentration range that the measured value of the measured value of concentration and absorbing carbon dioxide concentration determines Above-mentioned conductivity values be set to control targe value, to be arranged on conveying be fed on the stream of the replenisher in above-mentioned developer solution Control valve sends control signal so that the conductivity of above-mentioned developer solution becomes above-mentioned control targe value.

According to the developer solution managing device of the present invention, no matter developer solution becomes what kind of dissolving photoresist agent concentration and suction Receive gas concentration lwevel, in developer solution, activated composition remains constant to development effect, therefore, it is possible to realize maintaining expectation Developing performance and desired live width and the development treatment of residual film thickness can be maintained.

The preferred version of the developer solution managing device according to the present invention, developer solution managing device is also equipped with: multiple mensure fills Put, to include with above-mentioned developer solution dissolving the concentration dependent above-mentioned developer solution of photoresist characteristic value and with above-mentioned The characteristic value of the concentration dependent above-mentioned developer solution of absorbing carbon dioxide of developer solution is in multiple characteristic values of interior above-mentioned developer solution It is measured；Above-mentioned control unit is also equipped with: operational part, according to the above-mentioned developer solution being determined by multiple said determination devices Multiple characteristic values, calculate the measured value of dissolving photoresist agent concentration and the suction of above-mentioned developer solution by multivariate method Receive the measured value of gas concentration lwevel.

The preferred version of the developer solution managing device according to the present invention, developer solution managing device is also equipped with: multiple mensure fills Put, to include with above-mentioned developer solution dissolving the concentration dependent above-mentioned developer solution of photoresist characteristic value and with above-mentioned The characteristic value of the concentration dependent above-mentioned developer solution of absorbing carbon dioxide of developer solution is in multiple characteristic values of interior above-mentioned developer solution It is measured；And arithmetic element, according to multiple characteristic values of the above-mentioned developer solution being determined by multiple said determination devices, profit The measured value of dissolving photoresist agent concentration and the absorbing carbon dioxide that calculate above-mentioned developer solution with multivariate method are dense The measured value of degree.

The preferred version of the developer solution managing device according to the present invention, developer solution managing device is also equipped with densimeter, above-mentioned Control unit is also equipped with: operational part, the corresponding relation between the absorbing carbon dioxide concentration based on above-mentioned developer solution and density, profit The density of the above-mentioned developer solution with being determined by above-mentioned densimeter, calculates the absorbing carbon dioxide concentration of above-mentioned developer solution.

The preferred version of the developer solution managing device according to the present invention, developer solution managing device is also equipped with: densimeter；And Arithmetic element, the corresponding relation between the absorbing carbon dioxide concentration based on above-mentioned developer solution and density, using by above-mentioned density Measure the density of the above-mentioned developer solution made, calculate the absorbing carbon dioxide concentration of above-mentioned developer solution.

According to the developer solution management method of the present invention, measured based on the conductivity in alkaline developer solution for the Reusability Alkali concn, measures and the photoresist agent concentration that dissolves of above-mentioned developer solution has the absorbance of dependency relation, measures above-mentioned developer solution Absorbing carbon dioxide concentration, will have and determine the absorbance of above-mentioned developer solution and absorbing carbon dioxide concentration as index Each concentration range has been previously validated the alkali concn number of the alkali concn value of the above-mentioned developer solution that can reach given developing performance According among, by the absorbance being measured and the above-mentioned alkali of concentration range that determines of the absorbing carbon dioxide concentration that measured is dense Degree, is set as the control targe value of the alkali concn of above-mentioned developer solution, feeds replenisher so that above-mentioned developer solution to above-mentioned developer solution Alkali concn become above-mentioned control targe value.

According to the developer solution managing device of the present invention, possess control unit, this control unit possesses: data store, protect Deposit alkali concn data, this alkali concn data has the dissolving photoresist in alkaline developer solution in determination and Reusability Concentration has each concentration range meeting of being previously validated as index of the absorbance of dependency relation and absorbing carbon dioxide concentration Reach the alkali concn value of the above-mentioned developer solution of given developing performance；And control unit, by by above-mentioned developer solution absorbance and The above-mentioned alkali concn value being saved in above-mentioned data store of the concentration range that the measured value of absorbing carbon dioxide concentration determines It is set to control targe value, be fed to the control valve transmission control on the stream of the replenisher in above-mentioned developer solution to being arranged on conveying Signal is so that the alkali concn of above-mentioned developer solution becomes above-mentioned control targe value.

Invention effect

According to the present invention, no matter developer solution becomes what kind of dissolving photoresist agent concentration and absorbing carbon dioxide concentration, In developer solution, to development effect, activated composition remains constant, therefore, it is possible to realize to maintain desired developing performance and can tieing up Hold desired live width and the development treatment of residual film thickness.

Brief description

Fig. 1 is the schematic diagram of the developing procedure of the developer solution managing device for first embodiment is described.

Fig. 2 is the schematic diagram of the developing procedure of the developer solution managing device for second embodiment is described.

Fig. 3 is the schematic diagram of the developing procedure of the developer solution managing device for the 3rd embodiment is described.

Fig. 4 is the schematic diagram of the developing procedure of the developer solution managing device for the 4th embodiment is described.

Fig. 5 is the chart representing the relation between the gas concentration lwevel of developer solution and density.

Fig. 6 is the schematic diagram of the developing procedure of the developer solution managing device for the 5th embodiment is described.

Symbol description

A... developing procedure equipment；B... replenisher storage portion；C... circulation stirring mechanism；D... developer solution management dress Put；1... determination part；11... conductivity meter；12... the 1st concentration mensuration unit；12a... the 1st characteristic value determination unit； 13... the 2nd concentration mensuration unit；13a... the 2nd characteristic value determination unit；13b... densimeter；14... sampling pump；15... adopt Sample pipe arrangement；16... export side line；21... control unit (such as computer)；23... data store；31... control unit； 32nd, 33... operational part；36th, 37... arithmetic element；41～43... control valve；44th, 45,46,47... valve；61... developer solution Storage tank；62... overflow launder；63... liquid level meter；64... developing room cover；65... roller path；66... substrate；67... Developer solution shower nozzle；71... waste drains pump；72nd, 74... circulating pump；73rd, 75... filter；80... develop liquid pipeline；81、 82... replenisher (development stock solution and/or new liquid) uses pipeline；83... pure water pipeline；84... collaborate pipeline；85... circulate Pipeline；86... nitrogen pipeline；91st, 92... replenisher (development stock solution and/or new liquid) storage tank.

Specific embodiment

Hereinafter, suitably referring to the drawings, describe the preferred embodiment of the present invention in detail.Wherein, institute in these embodiments The shape of the device etc. recorded, size, size ratio, relative configuration etc. in case of no particular description however it is not limited to this Bright illustrated scope.It is merely possible to example is described and schematically illustrate these.

Additionally, in the following description, as the concrete example of developer solution, suitably using in quasiconductor or base plate of liquid crystal panel Primary 2.38% tetramethylammonium hydroxide aqueous solution (below, Tetramethylammonium hydroxide being referred to as tmah) in manufacturing process is entering Row explanation.But, present invention developer solution applicatory is not limited to this.Management method as the developer solution of the present invention and management The example of other developer solutions that device can be suitable for, can enumerate potassium hydroxide, sodium hydroxide, sodium phosphate, sodium silicate etc. no The aqueous solution of the organic compound such as the aqueous solution of machine compound, hydroxide hydroxyethyl ammonium (choline).

In the following description, the composition such as alkaline components concentration, dissolving photoresist agent concentration, absorbing carbon dioxide concentration is dense Degree is the concentration based on weight percent concentration (wt%)." dissolving photoresist agent concentration " refers to, photic anti-by dissolved Come concentration when being converted, " absorbing carbon dioxide concentration " refers to the amount losing agent as photoresist, by absorbed Carbon dioxide as carbon dioxide amount come concentration when being converted.

In development treatment operation, developer solution by the photoresist film after exposure-processed without being partly dissolved, from And developed.The alkaline components of the photoresist and developer solution that are dissolved in developer solution produce photoresist salt.Therefore, if Inappropriate management developer solution, then with the carrying out of development treatment, the alkaline components in developer solution with developing activity be consumed and It is deteriorated, developing performance can run down.Meanwhile, the photoresist being dissolved in developer solution can be used as the light with alkaline components Resist salt is caused down by gradually accumulation.

The photoresist being dissolved in developer solution assumes surface-active action in developer solution.Therefore, it is dissolved in developer solution Photoresist improve to development treatment supply photoresist film with respect to developer solution wellability (wettability) developer solution and the affinity of photoresist film, is made to become good.Therefore, moderately comprising photic resisting In the developer solution of erosion agent, developer solution can also enter in the trickle recess of photoresist film, can implement well to have The development treatment of the photoresist film of fine irregularities.

Additionally, in development treatment in recent years, along with the maximization of substrate, substantial amounts of developer solution obtains profit repeatedly With therefore developer solution is exposed to the chance of air and increases.If however, alkaline-based developer is exposed in the air, in meeting absorption air Carbon dioxide.The carbon dioxide being absorbed produces carbonate with the alkaline components of developer solution.Therefore, if inadequately managing aobvious Shadow liquid, then have the carbon dioxide-depleted that the alkaline components of developing activity can be absorbed, therefore can reduce in developer solution.With When, in developer solution, the carbon dioxide that developed liquid absorbs can be gone down by gradually accumulation as the carbonate with alkaline components.

However, the carbonate in developer solution, due to being in alkalescence in developer solution, therefore has development effect.

So, for the photoresist being dissolved in developer solution or absorbed carbon dioxide, and make at development The such existing understanding of developing activity inefficacy of reason is different, actually contributes to the developing performance of developer solution.Therefore, no The developer solution management being about to dissolve photoresist or absorbing carbon dioxide exclusion completely should be entered, but need a kind of permission aobvious While there is dissolving photoresist or absorbing carbon dioxide in shadow liquid, they are maintained the developer solution managing into optium concentration Management.

Additionally, a part for the photoresist salt producing in developer solution or carbonate is decomposed, thus producing photic Multiple free ion such as resist ion, carbanion, bicarbonate ion.And, these free ions are with various contributions Rate affects the conductivity of developer solution.

With regard to this point, the result that the present inventor carries out research with keen determination to developer solution management has obtained seeing below Solution: carbonate and resist salt also some can occur free and contribute to development effect in developer solution；By to development The conductivity values of liquid are managed, and are capable of considering the tribute in the past thinking that these compositions that can lose efficacy act on to development in the lump The developer solution management offered；And the management value of this conductivity is with absorbing carbon dioxide concentration and dissolving photoresist agent concentration Difference and different.

Therefore, inventor assume that situation about tmah aqueous solution being managed as developer solution, will dissolve photic anti- Erosion agent concentration, absorbing carbon dioxide concentration change into different value, obtained to photoresist desired developing performance with aobvious Relation between the conductivity values of shadow liquid.

Modulate and changed absorbing carbon dioxide concentration between 0.0～1.3 (wt%), in 0.0～0.40 (wt%) (phase When in 0.0～1.3 (abs)) between change dissolving photoresist agent concentration obtained from tmah aqueous solution developer solution sample. The inventor conductivity of developer solution, absorbing carbon dioxide concentration and dissolving photoresist agent concentration to these sample determinations, enter Go to the dependency relation between developing performance, conductivity, absorbing carbon dioxide concentration and dissolving photoresist concentration components The experiment being confirmed.Made by absorbing carbon dioxide concentration be set to a project and vertical or horizontal carry out arranging, will Dissolving photoresist agent concentration is set to another project and the matrix (combination table) laterally or longitudinally being arranged.According to absorption Gas concentration lwevel is combined with dissolving each of photoresist agent concentration, obtains satisfaction desired development to photoresist respectively The conductivity of the developer solution of performance, and be logged in each hurdle, matrix has thus been obtained.

Here, given developing performance refers to, the live width realized and residual film thickness is wanted to be achieved by developing procedure When developer solution developing performance.

Illustrate the mensure knot of the absorbing carbon dioxide concentration, dissolving photoresist agent concentration and conductivity of typical each sample Really.Absorbing carbon dioxide concentration be 0.0 (wt%), dissolving photoresist agent concentration (be equivalent to 0.0 for 0.0 (wt%) (abs), in situation (so-called new liquid)), the conductivity that can play the developer solution of given developing performance is 54.58 (ms/ cm).

It is 0.0 (wt%) in absorbing carbon dioxide concentration, dissolving photoresist agent concentration (is equivalent to for 0.25 (wt%) When 0.8abs), the conductivity that can play the developer solution of given developing performance is 54.55 (ms/cm), in dissolving photoresist When agent concentration is 0.40 (wt%) (being equivalent to 1.3abs), the conductivity of developer solution is 54.53 (ms/cm).

Additionally, being 0.0 (wt%) (being equivalent to 0.0 (abs)) in dissolving photoresist agent concentration, absorbing carbon dioxide concentration During for 0.6 (wt%), the conductivity of developer solution is 54.60 (ms/cm), when absorbing carbon dioxide concentration is 1.3 (wt%), shows The conductivity of shadow liquid is 54.75 (ms/cm).

Additionally, being 0.6 (wt%) in absorbing carbon dioxide concentration, dissolving photoresist agent concentration is 0.22 (wt%) (phase When in 0.7abs) when, the conductivity of developer solution is 54.60 (ms/cm), is 0.40 (wt%) in dissolving photoresist agent concentration When (being equivalent to 1.3abs), the conductivity of developer solution is 54.58 (ms/cm).

Additionally, being 1.3 (wt%) in absorbing carbon dioxide concentration, dissolving photoresist agent concentration is 0.22 (wt%) (phase When in 0.7abs) when, the conductivity of developer solution is 54.75 (ms/cm), is 0.40 (wt%) in dissolving photoresist agent concentration When (being equivalent to 1.3abs), the conductivity of developer solution is 54.75 (ms/cm).

If in addition, increasing in certain concentration range absorbing carbon dioxide concentration it was found that, having above-mentioned, conductivity The trend that also increases of management value, and if there is dissolving photoresist agent concentration increase, what the management value of conductivity reduced becomes Gesture.

In above-mentioned experiment, the conductivity of the developer solution of each sample employs the value determining by conductivity meter.Absorb Gas concentration lwevel employs the value determining by titrimetry.Dissolving photoresist agent concentration employs weight modulation Value.Titration be using hydrochloric acid as titer reagent acid-base titration.As titration appratuss, employ analysis company (three of Mitsubishi Chemical Pedicellus et Pericarpium Trapae chemistry ア Na リ テ ツク society) the automatic titration device gt-200 that manufactures.

In addition, above-mentioned conductivity, absorbing carbon dioxide concentration and dissolving photoresist agent concentration be used for finding conductivity, Relatedness between absorbing carbon dioxide concentration and dissolving photoresist agent concentration and developing performance, is not limited to each numerical value.

As mentioned above it will be appreciated that the conductivity that can play developing performance is photic with absorbing carbon dioxide concentration and dissolving The difference of agent concentration against corrosion and different.So, in the management of developer solution, comprising absorbing carbon dioxide and dissolving photic In the developer solution of resist, by being set to conductivity, management value measures absorbing carbon dioxide concentration further and dissolving is photic Agent concentration against corrosion, makes the management value of conductivity different, thus, it is possible to play given developing performance based on each measurement result.

That is, it is capable of following developer solution management: storage conductivity data (matrix), this conductivity data has and will show The dissolving photoresist agent concentration of shadow liquid and each concentration range of determining as index of absorbing carbon dioxide concentration are pre- First confirmation can reach the conductivity values of the developer solution of given developing performance, and utilizes conductivity data (matrix), can play Given developing performance.

Additionally, the result that inventor carries out research with keen determination to developer solution management has obtained following opinion: carbonate or against corrosion Also in developer solution, some free and contributes to development effect agent salt occurs；By line pipe is entered to the alkali concn value of developer solution Reason, is capable of considering in the lump and thinks that these compositions that can lose efficacy manage to the developer solution of the contribution that development acts in the past；With And the management value of this alkali concn has dependency relation with absorbing carbon dioxide concentration and dissolving photoresist agent concentration The difference of absorbance and different.

Therefore, inventor assume that situation about tmah aqueous solution being managed as developer solution, will be based in alkalescence The conductivity of developer solution and the dissolving photoresist agent concentration of the alkali concn that measures and developer solution has the extinction of dependency relation Degree, the absorbing carbon dioxide concentration of developer solution change into different value, have obtained with respect to the desired developability of photoresist Relation between energy and the alkali concn of developer solution.

Modulate and change absorbing carbon dioxide concentration between 0.0～1.3 (wt%), change between 0.0～1.3 (abs) Become the sample with dissolving photoresist agent concentration with the developer solution of tmah aqueous solution obtained from the absorbance of dependency relation.Send out A person of good sense alkali concn of developer solution, absorbing carbon dioxide concentration and absorbance to these sample determinations, carried out to developing performance, The experiment that dependency relation between alkali concn, absorbing carbon dioxide concentration and absorbance is confirmed.Make and will absorb dioxy Change concentration of carbon to arrange vertical or horizontal arrangement, absorbance as a project and as another project and laterally or longitudinally Matrix (combination table).According to combining of each absorbing carbon dioxide concentration and absorbance, obtain satisfaction respectively to photoresist The alkali concn of the developer solution of desired developing performance, and be logged in each hurdle, matrix has thus been obtained.

Here, given developing performance refers to, the live width realized and residual film thickness is wanted to be achieved by developing procedure When developer solution developing performance.

Illustrate the measurement result of absorbing carbon dioxide concentration, absorbance and the alkali concn of typical each sample.Absorbing two Oxidation concentration of carbon is 0.0 (wt%), absorbance is in the situation (so-called new liquid) of 0.0 (abs), can play given development The alkali concn of the developer solution of performance is 2.380 (wt%).

It is 0.0 (wt%) in absorbing carbon dioxide concentration, in the case that absorbance is 0.8abs, given showing can be played The alkali concn of the developer solution of shadow performance is 2.379 (wt%), and in the case that absorbance is for 1.3abs, the alkali concn of developer solution is 2.378 (wt%).

Additionally, being 0.0 (abs) in absorbance, in the case that absorbing carbon dioxide concentration is 0.6 (wt%), developer solution Alkali concn is 2.381 (wt%), and in the case of absorbing carbon dioxide concentration is 1.3 (wt%), the alkali concn of developer solution is 2.388 (wt%).

Additionally, being 0.6 (wt%) in absorbing carbon dioxide concentration, in the case that absorbance is 0.7abs, the alkali of developer solution Concentration is 2.381 (wt%), and in the case that absorbance is for 1.3abs, the alkali concn of developer solution is 2.380 (wt%).

Additionally, being 1.3 (wt%) in absorbing carbon dioxide concentration, in the case that absorbance is 0.7abs, the alkali of developer solution Concentration is 2.388 (wt%), and in the case that absorbance is for 1.3abs, the alkali concn of developer solution is 2.388 (wt%).

If in addition, increasing in certain concentration range absorbing carbon dioxide concentration it was found that, having above-mentioned, alkali concn The trend that also increases of management value, and if there is absorbance increase, the trend that the management value of alkali concn reduces.

In above-mentioned experiment, the alkali concn of the developer solution of each sample can be by using the method for conductivity meter mensure conductivity To obtain.Specifically, by between the alkali concn of the new liquid (the tmah aqueous solution before development) of tmah aqueous solution and conductivity values Dependency relation (such as linear relationship) make as standard curve in advance.Based on this standard curve, can be according to conductivity Value obtains alkali concn.

Absorbing carbon dioxide concentration employs the value measuring by titrimetry.Titration is as titer reagent using hydrochloric acid Acid-base titration.As titration appratuss, employ Mitsubishi Chemical and analyze the automatic titration device gt-200 that company manufactures.Absorbance Mensure employ extinction photometer.

In addition, above-mentioned alkali concn, absorbing carbon dioxide concentration and absorbance are used for finding alkali concn, absorbing carbon dioxide Relatedness between concentration and absorbance and developing performance, is not limited to each numerical value.

As mentioned above it will be appreciated that the alkali concn of developing performance can be played with absorbing carbon dioxide concentration and absorbance Different and different.So, in the management of developer solution, in the development comprising absorbing carbon dioxide and dissolving photoresist In liquid, by alkali concn being set to the management value of developer solution, measure absorbing carbon dioxide concentration and absorbance further, based on each Item measurement result makes the management value of alkali concn different, thus, it is possible to play given developing performance.

That is, in each concentration range determining the absorbance of developer solution and absorbing carbon dioxide concentration as index, Storage has the alkali concn data (square confirming the alkali concn value reaching the given developer solution of developing performance this point in advance Battle array), using alkali concn data (matrix), given developing performance can be played.

Then, it is described with reference to specific embodiment.

(first embodiment)

Fig. 1 is the schematic diagram of the developing procedure of developer solution managing device d for present embodiment is described.The present invention's is aobvious Shadow liquid managing device d is illustrated together with developing procedure equipment a, replenisher storage portion b, circulation stirring mechanism c etc..

First, briefly describe developing procedure equipment a.

Developing procedure equipment a 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 has developer solution.Developer solution is to be entered by supplementing replenisher Row composition management.Developer solution storage tank 61 possesses liquid level meter 63 and overflow launder 62, the liquid measure that supply replenisher is caused Increase is managed.Developer solution storage tank 61 and developer solution shower nozzle 67 are connected by development liquid pipeline 80.Developer solution The circulating pump 72 that the developer solution stored in storage tank 61 passes through to be arranged on development liquid pipeline 80 is sent via after filter 73 To developer solution shower nozzle 67.Roller path 65 is arranged on the top of developer solution storage tank 61, and transmission is formed with photoresist The substrate 66 of agent film.Developer solution drips from developer solution shower nozzle 67.The substrate 66 being transmitted by roller path 65 is in drippage Developer solution in pass through, thus developed immersion stain.Then, developer solution is recycled to developer solution storage tank 61 and stores again. So, developer solution circulates in developing procedure and is repeatedly used.In addition, sometimes through the development in small-sized glass substrate Interior to prevent the process of the carbon dioxide in absorption air full of nitrogen etc..In addition, the developer solution of deterioration passes through waste drains pump 71 Work form waste liquid (drain, discharge).

Circulation stirring mechanism c is described.Circulation stirring mechanism c is mainly used in the development making to be stored in developer solution storage tank 61 Liquid circulates and is stirred.

The sidepiece of the bottom of developer solution storage tank 61 and developer solution storage tank 61 pass through midway be provided with circulating pump 74 and The circulation line 85 of filter 75 and be connected.If making circulating pump 74 work, the etching stored in developer solution storage tank 61 Liquid circulates via circulation line 85.Developer solution returns to development via after circulation line 85 from the sidepiece of developer solution storage tank 61 Liquid storage tank 61.Thus, stir stored developer solution.

Additionally, in replenisher via interflow pipeline 84 in the case of flowing in circulation line 85, the replenisher of inflow and It is fed in developer solution storage tank 61 while the developer solution of circulation line 85 interior circulation is mixed.

Then, developer solution managing device d of present embodiment is described.Developer solution managing device d of present embodiment be with It may be assumed that using conductivity data, this conductivity data has by alkaline developer solution the developer solution managing device of under type Dissolve in each concentration range that photoresist agent concentration and absorbing carbon dioxide concentration determine as index by true in advance Recognize the conductivity values of the developer solution that can reach given developing performance, by the survey of the dissolving photoresist agent concentration according to developer solution The conductivity of the concentration range that the measured value of definite value and absorbing carbon dioxide concentration determines, as control targe value, is mended to developer solution The conductivity making developer solution to replenisher becomes control targe value.

Developer solution managing device d possesses determination part 1 and control unit 21.Developer solution managing device d passes through pipe arrangement 15 of sampling And export side line 16 and be connected with developer solution storage tank 61.

Determination part 1 possesses sampling pump 14, conductivity meter 11, measures the 1st concentration mensuration list dissolving photoresist agent concentration Unit 12 and the 2nd concentration mensuration unit 13 for measuring absorbing carbon dioxide concentration.Conductivity meter 11, the 1st concentration mensuration list First 12 and the 2nd concentration mensuration unit 13 is connected in series in the rear class of sampling pump 14.Determination part 1 measures essence to improve further Degree, is preferably provided with making the stable thermostat unit (not shown) in given temperature of sampled developer solution.Now, preferably will Thermostat unit is arranged on the positive prime of determination unit.The sampling of the determination part 1 of sampling pipe arrangement 15 and developer solution managing device d Pump 14 connects, and outlet side line 16 is connected with the pipe arrangement of determination unit end.

Additionally, in fig. 1 it is illustrated that conductivity meter 11, the 1st concentration mensuration unit 12 and the 2nd concentration mensuration unit 13 quilt The mode being connected in series, but the connection of conductivity meter 11, the 1st concentration mensuration unit 12 and the 2nd concentration mensuration unit 13 is not limited to This.Both can be connected in parallel it is also possible to separately possess liquor charging path to be measured.Conductivity meter 11, the 1st concentration are surveyed The order of order unit the 12 and the 2nd concentration mensuration unit 13 is also not particularly limited it successively.Can according to the feature of each determination unit, Suitably it is measured by optimal order.

Control unit 21 possesses data store 23 and control unit 31.Data store 23 is preserved and has and will use The conductivity values of developer solution conductivity data, this conductivity values has been identified in advance by the dissolving in alkaline developer solution Can reach given aobvious in each concentration range that photoresist agent concentration and absorbing carbon dioxide concentration determine as index Shadow performance.

Control unit 21 is dense with the conductivity meter 11 of determination part 1, the 1st concentration mensuration unit 12 and the 2nd by holding wire Degree determination unit 13 connects.Conductivity values, dissolving photoresist concentration value and the absorbing carbon dioxide being determined by determination part 1 Concentration value is sent to control unit 21.

The control unit 31 of control unit 21 is conveyed on the stream of replenisher to developer solution with being arranged on by holding wire Control valve 41～43 connects.In FIG, control valve 41～43 is depicted as being the internal part of developer solution managing device d, but control Valve 41～43 processed is not necessarily the part of developer solution managing device d of present embodiment.As long as control unit 31 can be with control valve 41 ～43 are got in touch with to control the action of control valve 41～43 to feed replenisher to developer solution.Control valve 41～43 also may be used To be arranged on the outside of developer solution managing device d.

Then, the action of developer solution managing device d of present embodiment is described.

It is sent in determination part 1 from the developer solution of developer solution storage tank 61 sampling, here carries out temperature adjustment.Then, show Shadow liquid is sent to conductivity meter 11, the 1st concentration mensuration unit 12 and the 2nd concentration mensuration unit 13, and mensure conductivity, dissolving are photic Agent concentration against corrosion and absorbing carbon dioxide concentration.Each determination data is sent to control unit 21.

It is set with the management value of the conductivity corresponding with the conductivity values of conductivity data, this conduction in control unit 31 Rate data has every determine the dissolving photoresist agent concentration of developer solution and absorbing carbon dioxide concentration as index Individual concentration range has been previously validated the conductivity values of the developer solution that can reach given developing performance.Control unit 31 is according to from survey Determine the determination data that portion 1 accepts, be carried out as follows control.

Control unit 31, based on the dissolving photoresist agent concentration accepting from determination part 1 and absorbing carbon dioxide concentration, is obtained In the conductivity data that data store 23 is stored, by the dissolving photoresist agent concentration being measured and the absorption that measured The conductivity values of the concentration range that gas concentration lwevel determines.The conductivity values obtained are set as the control of the conductivity of developer solution Desired value processed.

Control unit 31 enters to the conductivity determining accepting from determination part 1 and the conductivity being set to control targe value Row compares, and is managed as follows according to comparative result.That is, in the conductivity being set to control targe value and the conduction determining In the case of rate identical, substantially do not add replenisher to developer solution.Additionally, it is big in the conductivity being set to control targe value The replenisher of the effect improving conductivity in the case of the conductivity determining, is played to developer solution supply.Additionally, Be set to control targe value conductivity be less than the conductivity that determines in the case of, play to developer solution supply reduce conductive The replenisher of the effect of rate.

Here, as the replenisher feeding to developer solution, for example, there are the stock solution of developer solution, new liquid, pure water etc..

Replenisher is stored in the replenisher storage tank 91,92 of replenisher storage portion c.Replenisher storage tank 91,92 and tool The nitrogen pipeline 86 of standby valve 46,47 connects, pressurized by the nitrogen that supplies via this pipeline.Additionally, replenisher storage tank 91st, 92 are connected with replenisher pipeline 81,82 respectively, convey replenisher via the valve 44,45 being generally in the state opened. Replenisher pipeline 81,82 and pure water pipeline 83 are provided with control valve 41～43, by control unit 31 to control valve 41 ～43 controls being turned on and off.By the action of control valve, the replenisher quilt stored in replenisher storage tank 91,92 Pressurized delivered, and pure water is also conveyed.Then, replenisher is collaborated with circulation stirring mechanism c via interflow pipeline 84, is mended It is given in developer solution storage tank 61, and be stirred wherein.

If lead to the replenisher stored in replenisher storage tank 91,92 to reduce because of supply, drops in it and lead Cause quantity delivered to become unstable, therefore suitably open valve 46,47 according to the minimizing of replenisher and supply nitrogen, maintain replenisher The intrinsic pressure state being maintained of storage tank 91,92.When replenisher storage tank 91,92 is drained, shutoff valve 44,45, change It is filled with the new replenisher storage tank of replenisher, or, the replenisher separately preparing is again filled with the replenisher emptying In storage tank.

The control of control valve 41～43 is for example carried out as follows.If the flow flowing when control valve is opened is adjusted Whole, then pass through the time that management opens control valve, the replenisher of the amount that should feed can be fed.Control unit 31 is based on from determination part 1 conductivity determining accepting and the conductivity being set to control targe value, sending control signal to control valve will control Preset time opened by valve processed, so that the replenisher of the amount that should feed flows into.

The mode controlling can adopt makes controlled quentity controlled variable meet the various control methods used in the control of desired value.Especially It is that preferred proportion controls (p control) (p:proportional), integration control (i control) (i:integral), differential to control (d control) (d:derivative) and the control (pi control etc.) that these control combinations are got up.More preferably pid controls.

Thus, developer solution managing device d according to involved by present embodiment, no matter what kind of dissolving light developer solution becomes Cause agent concentration against corrosion and absorbing carbon dioxide concentration, to manage developer solution by using the conductivity in developer solution, development is made The activated composition of apparatus is maintained, and therefore, it is possible to maintain desired developing performance, can achieve and is able to maintain that desired live width And the development treatment of residual film thickness.

Additionally, developer solution managing device d according to involved by present embodiment, using confirming the aobvious of developing performance in advance The conductivity data of the conductivity values of shadow liquid is as control targe management value, even if thus the dissolving photoresist of developer solution is dense Spend for 0.0～0.40 (wt%) (being equivalent to 0.0～1.3 (abs)) and absorbing carbon dioxide concentration be 0.0～1.3 (wt%), Can also act as the developer solution with desired developing activity.That is, the developer solution managing device according to involved by present embodiment D, even if the dissolving photoresist agent concentration of developer solution is more than 0.25 (wt%) (being equivalent to 0.8 (abs)), and absorbs titanium dioxide Concentration of carbon is more than 0.6 (wt%) it is also possible to not discarding developer solution but being used such that it is able to reduce developer solution Waste liquid amount.

In the above description, illustrate the conductivity using developer solution, absorbing carbon dioxide concentration, dissolve photoresist Concentration and the example of conductivity data.But not limited to this it is also possible to using the alkali concn of developer solution, absorbing carbon dioxide concentration, Absorbance and alkali concn data are managing developer solution.

(second embodiment)

Fig. 2 is the schematic diagram of the developing procedure of developer solution managing device d for present embodiment is described.The present invention's is aobvious Shadow liquid managing device d is illustrated together with developing procedure equipment a, replenisher storage portion b, circulation stirring mechanism c etc..In addition, having When pair with the structure identical structure of first embodiment mark same symbol and omit the description.

The determination part 1 of developer solution managing device d possesses conductivity meter 11, to the dissolving photoresist agent concentration with developer solution The related characteristic value of developer solution and being surveyed with the characteristic value of the concentration dependent developer solution of the absorbing carbon dioxide of developer solution Fixed multiple mensure devices.For example, it is measured as to the characteristic value with the dissolving concentration dependent developer solution of photoresist The 1st characteristic value determination unit 12a, for example possess the extinction photometer of the absorbance under mensure λ=560nm.As to suction Receive the 2nd characteristic value determination unit 13a that the characteristic value of the related developer solution of gas concentration lwevel is measured, possess mensure development The densimeter of the density of liquid.

Here, the characteristic value of the developer solution of " related " refers to, there is relation between this characteristic value and its constituent concentration, exist The relation that characteristic value changes according to the change of its constituent concentration.For example, in the constituent concentration of developer solution at least with constituent concentration a The characteristic value a of related developer solution refers to, when characteristic value a is obtained according to the function with constituent concentration as variable, one of variable At least include constituent concentration a.Characteristic value a can also be only the function of constituent concentration a, but can become except composition under normal circumstances Also can be now (for example polynary using multivariate method with the multi-variable function as variable such as constituent concentration b or c beyond concentration a Regression analyses) meaning big.

Control unit 21 possesses data store 23, control unit 31 and operational part 32.Operational part 32 is surveyed according to by determination part 1 Multiple characteristic values of the developer solution made, calculate the mensure of the dissolving photoresist agent concentration of developer solution by multivariate analyses Value and the measured value of absorbing carbon dioxide concentration.

In the present embodiment, it is sent in determination part 1 from the developer solution of developer solution storage tank 61 sampling and enter trip temperature tune Section.Then, developer solution is sent to conductivity meter 11, the 1st characteristic value determination unit 12a and the 2nd characteristic value determination unit 13a, surveys Determine conductivity, absorbance and density.Each determination data is sent to control unit 21.

Operational part 32, according to the absorbance being determined by determination part 1 and density, calculates developer solution by multivariate analyses The dissolving measured value of the photoresist agent concentration and measured value of absorbing carbon dioxide concentration.Now, can also according to conductivity, Absorbance and density, calculate measured value and the absorbing carbon dioxide concentration of dissolving photoresist agent concentration by multivariate analyses Measured value.

Control unit 31, based on the dissolving photoresist agent concentration being calculated by operational part 32 and absorbing carbon dioxide concentration, is asked Go out in the conductivity data that data store 23 is stored, by the dissolving photoresist agent concentration being measured and the suction being measured Receive the conductivity values of the concentration range that gas concentration lwevel determines.The conductivity values obtained are set as the conductivity of developer solution Control targe value.

Other structures, action etc. are identical with first embodiment, therefore omit the description.

Then, the multiple characteristic values according to developer solution are described, calculate dissolving photoresist by multivariate analyses dense The measured value of degree and the method for absorbing carbon dioxide concentration.

Inventor is found that, if using multivariate method (for example, multiple regression analysis method) in operation method, then with Situation using existing method is compared, and can accurately calculate the concentration of each composition of developer solution, and can measure with The past absorbing carbon dioxide concentration being difficult to measure.If calculating using by multivariate method (for example, multiple regression analysis method) The constituent concentration (dissolving photoresist agent concentration and absorbing carbon dioxide concentration) of the developer solution going out, then can be easily pre- from having First confirm the conductivity data of dissolving photoresist agent concentration, absorbing carbon dioxide concentration and the conductivity values of developing performance In, obtain target conductivity values.

Assume that the situation of the management carrying out 2.38%tmah aqueous solution, modulating will be photic to alkaline components concentration, dissolving Agent concentration against corrosion, absorbing carbon dioxide concentration change into various tmah aqueous solutions obtained from different value, as simulation developer solution Sample.Inventor has carried out various characteristic values according to obtained from these simulation developer solution samples are measured, by polynary Regression analyses try to achieve the experiment of its constituent concentration.Hereinafter, the general operation method based on multiple regression analysis method is first described, It is then based on the operation method that the description of test that inventor carries out employs the constituent concentration of developer solution of multiple regression analysis method.

Multiple regression analysis include correcting and predict this two stages.In the multiple regression analysis of n composition system, prepare m Individual calibration standard solution.The concentration of j-th composition present in i-th solution is expressed as c_ij.Here, i=1～m, j=1～ n.M standard solution is measured respectively with p characteristic value (for example, the physics value such as the absorbance under certain wavelength, conductivity) a_ik(k=1 ～p).By concentration data and performance data can in the form of integrating representation is as matrix respectively (c, a).

[mathematical expression 1]

$\begin{array}{cc}c=\left[\begin{array}{cccc}{c}_{11}& c_{12}& \mathrm{...}& c_{1n}\\ c_{21}& c_{22}& \mathrm{...}& c_{2n}\\ \mathrm{...}& \mathrm{...}& \mathrm{...}& \mathrm{...}\\ c_{m1}& c_{m2}& \mathrm{...}& c_{mn}\end{array}\right],& a=\left[\begin{array}{cccc}{a}_{11}& a_{12}& \mathrm{...}& a_{1p}\\ a_{21}& a_{22}& \mathrm{...}& a_{2p}\\ \mathrm{...}& \mathrm{...}& \mathrm{...}& \mathrm{...}\\ a_{m1}& a_{m2}& \mathrm{...}& a_{mp}\end{array}\right]\end{array}$

The matrix that these matrix correlation are got up is referred to as correction matrix, here mark s (s_kj, k=1～p, j=1～n) To represent.

[mathematical expression 2]

C=a s

According to known c and a, (content of a is not limited to the measured value of same nature, can also be mixed with survey of different nature Definite value.For example, conductivity, absorbance, density) calculated by matrix operationss s stage be calibration phase.Now it is necessary to Meet p >=n, and m >=np.Each key element of s is entirely unknown number, therefore preferably m ＞ np, is carried out as follows minimum in this case Two multiplications.

[mathematical expression 3]

S=(a^ta)^-1(a^tc)

Here, subscript t represents transposed matrix, subscript -1 represents inverse matrix.

If the sample liquid unknown to concentration measures p characteristic value, and is set to au (au_k, k=1～p), then thereon After being multiplied by s, the concentration c u (cu that should obtain can be obtained_j, j=1～n).

[mathematical expression 4]

Cu=au s

This is forecast period.

Inventor is photic including alkaline components, dissolving by being regarded as using complete alkaline-based developer (2.38%tmah aqueous solution) The multicomponent system (n=3) of this 3 kinds of compositions of resist, absorbing carbon dioxide, has carried out following experiment: as this developer solution Characteristic value, according to 3 characteristic values (p=3), the i.e. conductivity values of developer solution, the absorbance under specific wavelength and density value, leads to Cross above-mentioned multiple regression analysis method and calculate each constituent concentration.Inventor will be basic as developer solution for 2.38%tmah aqueous solution Composition, has modulated and has changed alkaline components concentration (tmah concentration), dissolving photoresist agent concentration, absorbing carbon dioxide concentration 11 calibration standard solution (m=11 meets p >=n and m ＞ np) obtained from different value.

In an experiment, to 11 calibration standard solution, measure conductivity values, the absorbance under wavelength X=560nm, with And density value is used as the characteristic value of developer solution, (multiple linear regression- is analyzed by linear multiple regression inverse least squares；Mlr-ils) each constituent concentration of computing.

Mensure is that correction standard solution is being adjusted to 25.0 DEG C of temperature and is carried out.Temperature adjustment is in the following manner: Temperature treatment is long-time in 25 DEG C about of thermostatic water bath soak the bottle enclosing calibration standard solution, from wherein carrying out Sampling, was adjusted to 25.0 DEG C by temperature controller further before will being measured once again.Conductivity meter employs this The conductivity meter that company manufactures.It is measured using the conductivity flow cell that the our company implementing platinum black process manufactures.To The cell constant of conductometric vessel of the conductivity flow cell that conductivity meter input is separately confirmed by correction operation.Extinction photometer is also adopted by The extinction photometer that our company manufactures.It is the extinction in the light source portion, photometric measurer and glass flow cell that possess wavelength X=560nm Photometer.Density measurement employs and tries to achieve consolidating of density using according to the natural frequency exciting u word pipe flow cell and measuring There is the densimeter of vibratory drilling method.The conductivity values that measured, absorbance, the unit of density value are respectively ms/cm, abs. (absorbance)、g/cm³.

Computing is carried out based on following methods, i.e. select one of 11 calibration standard solution calibration standard solution Make unknown sample, obtain correction matrix by remaining 10 standard, calculate the unknown sample of supposition concentration and with known Value (concentration value being measured by other accurate analysis methods and weight modulation value) is compared (leaving-one method: leave-one- Out method).

Table 1 represents the result having carried out mlr-ils calculating.

[table 1]

Carry out when mlr-ils calculates it is contemplated that tmah aqueous solution be strong basicity thus easy absorbing carbon dioxide and bad Situation about changing, employs by analyzing alkaline components concentration exactly and absorb two in the concentration matrix that computing is used The titrimetry of oxidation concentration of carbon separately to measure value obtained from calibration standard solution.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 Mitsubishi Chemical's analysis public The automatic titration device gt-200 that department (Mitsubishi Chemical ア Na リ テ ツク society) manufactures.

Hereinafter, table 2 indicated concentration matrix.

[table 2]

Table 3 represents the measurement result of the physics value of calibration standard solution now.Absorbance one hurdle is wavelength X=560nm Under absorbance (optical path length d=10mm).

[table 3]

Table 4 represents correction matrix.

[table 4]

0.040187	-0.002869	0.000171
			-0.130547	-0.061441	0.300422
432.787314	144.654531	2.02483

Table 5 represents the comparison of the concentration measurement of table 2 and the mlr-ils value of calculation of table 1.

[table 5]

As shown in table 5, the tmah concentration obtained by multiple regression analysis method, dissolving photoresist agent concentration, two are absorbed Oxidation concentration of carbon be all with the tmah concentration being measured by titrimetry, absorbing carbon dioxide concentration and by adjustment weight ask Go out dissolves the very approximate value of photoresist agent concentration.

In this way it can be considered that by the absorbance under the conductivity of mensure alkaline-based developer, specific wavelength and density, and make With multivariate method (for example, multiple regression analysis method), alkaline components concentration, the dissolving photoresist of developer solution can be measured Agent concentration and absorbing carbon dioxide concentration.

Multivariate method (for example, multiple regression analysis method) is effective when obtaining the concentration of multiple compositions through computing 's.By measure multiple characteristic value a of developer solution, b, c ..., and according to these measured values, by multivariate method (example As multiple regression analysis method), can obtain constituent concentration a, b, c ....Now, for the constituent concentration that should obtain, need to Measure at least related to this constituent concentration characteristic value less and use it in computing.

Additionally, constituent concentration is the yardstick representing this composition with respect to overall relative quantity.Developer solution as Reusability The constituent concentration of the mixed liquor that composition has increased and decreased through the passage of time like that is not dependent solely on its composition, under normal circumstances It is the function of the concentration of other compositions.Therefore, the characteristic value of developer solution and the relation of constituent concentration are difficult to by plane graph come table Situation about showing is more.In this case, the operation method etc. by using standard curve is cannot be according to the characteristic value of developer solution Calculate constituent concentration.

But, according to multivariate method (for example, multiple regression analysis method), as long as get all the ready one group with want calculate to become Divide the measured value of concentration dependent multiple characteristic values, then they can be used in computing, thus calculating one group of constituent concentration. Even think the constituent concentration being difficult to measure according to conventional viewpoint, by based on multivariate method, (for example, multiple regression divides Analysis method) component concentration measuring it is also possible to obtain can by measure characteristic value measure the such remarkable result of constituent concentration.

As described above, according to the operation method of the present invention, being capable of characteristic value based on developer solution (for example, conductivity, specific Absorbance under wavelength and density) measured value, calculate developer solution alkaline components concentration, dissolving photoresist agent concentration And absorbing carbon dioxide concentration.According to the operation method of the present invention, compared with the existing methods, can accurately calculate each Constituent concentration.

Additionally, in the present invention due to using multivariate method (for example, multiple regression analysis method), therefore aobvious in calculating Additionally it is possible to there is no the developer solution of linear relationship using the specific constituent concentration with developer solution in the computing of the constituent concentration of shadow liquid Characteristic value.

Additionally, it is not necessary according to the invention that indispensable the carrying out to realize high-precision measuring of invention of patent documentation 2 The preparation of extremely many samples and preparation measure.(experimental example as the aforementioned is such, if the developer solution of component number n=3, then conduct Quantity p=3 of characteristic value to be measured, as long as prepare and measure just to meet the sample number p (such as p=11 sample) of m >=np Be enough to.If component number n=2, sample number is less.)

In addition, the present invention is due to using multivariate method (for example, multiple regression analysis method), therefore, it is possible to accurately Calculate the absorbing carbon dioxide concentration of the developer solution that prior art is difficult to measure.

In the present embodiment, as the characteristic value with the dissolving concentration dependent developer solution of photoresist of developer solution, Exemplified with the absorbance under λ=560nm, but not limited to this.Can also be using the absorbance under other specific wavelengths as characteristic value To be used, i.e. the absorbance under the more preferably specific wavelength of the wavelength region of 360～600nm of visible region, more preferably Absorbance under wavelength X=480nm.This is because, the absorbance under the specific wavelength that these wavelength region are comprised and dissolving Agent concentration against corrosion has the good corresponding relation of comparison.

Additionally, as the characteristic value with the concentration dependent developer solution of the absorbing carbon dioxide of developer solution, exemplified with density, but Not limited to this.As the characteristic dissolving photoresist agent concentration, the concentration dependent developer solution of absorbing carbon dioxide with developer solution Value, with the conductivity of developer solution combine mensure the characteristic value that can adopt of characteristic value for example except above-mentioned specific wavelength Under absorbance and density beyond, ultrasonic propagation velocity, refractive index, titration end-point, ph etc. can also be enumerated.

(the 3rd embodiment)

Fig. 3 is the schematic diagram of the developing procedure of developer solution managing device d for present embodiment is described.The present invention's is aobvious Shadow liquid managing device d is illustrated together with developing procedure equipment a, replenisher storage portion b, circulation stirring mechanism c etc..In addition, having When pair with the structure identical structure of first embodiment and second embodiment mark same symbol and omit the description.

Developer solution managing device d of present embodiment possesses determination part 1, control unit 21 and arithmetic element 36.In this reality Apply in mode, different from second embodiment, control unit 21 is made up of independent device with the arithmetic element 36 entering row operation.

Determination part 1 possesses conductivity meter 11, the 1st characteristic value determination unit 12a and the 2nd characteristic value determination unit 13a.Computing Unit 36, according to the absorbance being determined by the 1st characteristic value determination unit 12a and the 2nd characteristic value determination unit 13a and density, leads to Cross multivariate analyses to calculate the dissolving measured value of photoresist agent concentration and the mensure of absorbing carbon dioxide concentration of developer solution Value.Now, dissolving photoresist agent concentration can be calculated according to conductivity, absorbance and density by multivariate analyses Measured value and absorbing carbon dioxide concentration.

Control unit 31, based on the dissolving photoresist agent concentration being calculated by arithmetic element and absorbing carbon dioxide concentration, is asked Go out in the conductivity data that data store 23 is stored, by the dissolving photoresist agent concentration being measured and the suction being measured Receive the conductivity values of the concentration range that gas concentration lwevel determines.The conductivity values obtained are set as the conductivity of developer solution Control targe value.

Other structures, action etc. are identical with second embodiment, therefore omit the description.

(the 4th embodiment)

Fig. 4 is the schematic diagram of the developing procedure of developer solution managing device d for present embodiment is described.The present invention's is aobvious Shadow liquid managing device d is illustrated together with developing procedure equipment a, replenisher storage portion b, circulation stirring mechanism c etc..In addition, having When pair with the structure identical structure of first embodiment, second embodiment and the 3rd embodiment mark same symbol and save Slightly illustrate.

The determination part 1 of present embodiment possesses conductivity meter 11, the 1st concentration mensuration unit 12 and densimeter 13b.Control single Unit 21 possesses control unit 31, data store 23 and operational part 33.The absorbing carbon dioxide concentration based on developer solution for the operational part 33 Corresponding relation and density between, according to the density of the developer solution being determined by densimeter 13b, calculates the absorption dioxy of developer solution Change concentration of carbon.

Control unit 31 is calculated based on the dissolving photoresist agent concentration being determined by determination part 1 and by operational part 33 Absorbing carbon dioxide concentration, obtain in the conductivity data that data store 23 is stored, photic by the dissolving being measured Agent concentration against corrosion and the conductivity values of the concentration range of absorbing carbon dioxide concentration determination being measured.By the conductivity values obtained It is set as the control targe value of the conductivity of developer solution.

Other structures, action etc. are identical with first embodiment, therefore omit the description.

Relation between the density value of developer solution and absorbing carbon dioxide concentration value is described.Inventor is persistently ground with keen determination The result studied carefully has obtained following opinion.I.e., with the alkaline components concentration of developer solution and dissolving photoresist agent concentration independently, exist Can obtain between the density value of developer solution and absorbing carbon dioxide concentration value comparing good corresponding relation (linear relationship).This Outward, if using this corresponding relation (linear relationship), measuring the density of developer solution by using densimeter, can measure in the past It is difficult to the absorbing carbon dioxide concentration measuring.

Inventor is by 11 schools used in the computing of the constituent concentration of the developer solution being carried out using multivariate method , as simulation developer solution sample, to these sample determinations, alkaline components concentration (tmah concentration), dissolving are photic for positive standard solution Agent concentration against corrosion, absorbing carbon dioxide concentration and density, have carried out confirming the reality of the dependency relation between constituent concentration and density Test.

Table 6 below represents the constituent concentration of each sample and the measurement result of density.Table 6 is the concentration measurement to table 5 (wt%) and table 3 density (g/cm³) table that contrasted.

[table 6]

Fig. 5 represents the absorbing carbon dioxide concentration of each sample shown in table 6 and the chart of density.This chart is by titanium dioxide Concentration of carbon (wt%) is set to transverse axis, by density (g/cm³) it is set to the longitudinal axis, and figure obtained from the value of each sample is described Table.According to each point described, regression straight line is tried to achieve by method of least square.

According to Fig. 5 it is appreciated that with alkaline components concentration, dissolving photoresist agent concentration different independently, development There is good linear relationship between the absorbing carbon dioxide concentration of liquid and the density of developer solution.By this experimental result, invent If people knows the corresponding relation (linear relationship) between the gas concentration lwevel using this developer solution and density, by measuring The density of developer solution is it becomes possible to calculate the absorbing carbon dioxide concentration of developer solution.

Therefore, with alkaline components concentration (tmah concentration), dissolving agent concentration against corrosion independently, this corresponding relation can be passed through (linear relationship), measures the absorbing carbon dioxide concentration of developer solution using densimeter.

The density by using developer solution for the operational part 33 and the relation of absorbing carbon dioxide concentration, can easily measure development The absorbing carbon dioxide concentration of liquid.

(the 5th embodiment)

Fig. 6 is the schematic diagram of the developing procedure of developer solution managing device d for present embodiment is described.The present invention's is aobvious Shadow liquid managing device d is illustrated together with developing procedure equipment a, replenisher storage portion b, circulation stirring mechanism c etc..In addition, having When pair constitute mark same symbol with the structure identical of first embodiment and second embodiment and omit the description.

Developer solution managing device d of present embodiment possesses determination part 1, control unit 21 and arithmetic element 37.In this reality Apply in mode, different from the 4th embodiment, control unit 21 is made up of independent device with the arithmetic element 37 entering row operation. The determination part 1 of present embodiment possesses conductivity meter 11, the 1st concentration mensuration unit 12 and densimeter 13b.Arithmetic element 37 is based on Corresponding relation between the absorbing carbon dioxide concentration of developer solution and density, according to the developer solution being determined by densimeter 13b Density, calculates the absorbing carbon dioxide concentration of developer solution.

Control unit 31 is calculated based on the dissolving photoresist agent concentration being determined by determination part 1 and by arithmetic element 37 Absorbing carbon dioxide concentration, obtain in the conductivity data that data store 23 is stored, photic by the dissolving being measured Agent concentration against corrosion and the conductivity values of the concentration range of absorbing carbon dioxide concentration determination being measured.By the conductivity values obtained It is set as the control targe value of the conductivity of developer solution.

Other structures, action etc. are identical with the 4th embodiment, therefore omit the description.

As described above, according to developer solution managing device d of present embodiment, it is photic no matter what kind of dissolving developer solution becomes Agent concentration against corrosion and gas concentration lwevel, because active to development effect composition in developer solution keeps constant, therefore can Enough maintain desired developing performance, can achieve and be able to maintain that desired live width and the development treatment of residual film thickness.

Then, the variation of developer solution managing device d of present embodiment is described.

In Fig. 1～4,6, depict determination part 1 and control unit 21, the arithmetic element 36,37 of developer solution managing device d Developer solution managing device d being integrally formed, but the developer solution managing device d not limited to this of present embodiment.Can also will measure Portion 1 is separately formed.

In determination part 1, with the difference of the measuring principle being respectively adopted, there are different optimal methods to set up, because This for example can also by determination part 1 and development liquid pipeline 80 on-line joining process, or be arranged to be immersed in developer solution by measuring probe In storage tank 61.Conductivity meter 11, the 1st concentration mensuration unit 12, the 1st characteristic value determination unit can also be individually set 12a, the 2nd concentration mensuration unit 13, each determination unit of the 2nd characteristic value determination unit 13a and densimeter 13b.As long as each survey Order unit can mutually be got in touch with the exchange so as to realize the determination data with control unit 21 and arithmetic element 36,37, Get final product developer solution managing device d of present embodiment.

If the measuring principle being adopted according to each determination unit and need to add reagent, 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 the pipeline for realizing this function.Respectively Even if determination unit is not connected in series is capable of developer solution managing device d of present embodiment yet.

In Fig. 1～4,6, depict developer solution managing device d and connect with replenisher pipeline 81,82 and pure water pipeline 83 The control valve 41～43 being connected into setting on the stream of the replenisher that conveying is fed in developer solution becomes developer solution managing device d Internal part situation, but developer solution managing device d not limited to this of present embodiment.Developer solution managing device can not also Control valve 41～43 is arranged to internal part it is also possible to not connect with the pipeline 81～83 being used for feeding replenisher to developer solution Connect.

Control unit 21 in developer solution managing device d of present embodiment and the pipeline being arranged on for feeding replenisher As long as on control valve 41～43 can mutually be got in touch with thus controlled control valve 41～43 receive by developer solution managing device d The control signal that sends of control unit 21.Even if control valve be not developer solution managing device d internal part it is also possible to Realize developer solution managing device d of present embodiment.

The developer solution managing device of the present invention, in above-mentioned various modifications example, will developed it is also possible that possessing and having The dissolving photoresist agent concentration of liquid and each concentration range of determining as index of gas concentration lwevel are previously validated The conductivity data of the conductivity values of the developer solution of given developing performance can be reached, by the dissolving photoresist by developer solution The conductivity values of the conductivity data of concentration range that the measured value of the measured value of concentration and absorbing carbon dioxide concentration determines are made For control targe value, convey the replenisher being fed in developer solution so that the conductivity of developer solution becomes control targe value.

As described above, according to the management method of the developer solution of the present invention and developer solution managing device, no matter developer solution becomes What kind of dissolving photoresist agent concentration and gas concentration lwevel, due to active to development effect composition quilt in developer solution Maintain constant, therefore, it is possible to maintain desired developing performance, can achieve and be able to maintain that desired live width and the development of residual film thickness Process.

As the optimal way of developer solution managing device, calculate dissolving photoresist by multivariate method dense Degree and absorbing carbon dioxide concentration, dense therefore, it is possible to accurately obtain dissolving photoresist agent concentration and absorbing carbon dioxide Degree.Based on these dissolving photoresist agent concentrations and absorbing carbon dioxide concentration, can obtain from conductivity data becomes mesh Target conductivity values.

In addition, as the optimal way of developer solution managing device, the absorbing carbon dioxide concentration based on developer solution and density Between corresponding relation, according to the density of the developer solution being determined by densimeter, the absorbing carbon dioxide calculating developer solution is dense Degree.Thereby, it is possible to the easier absorbing carbon dioxide concentration that must obtain developer solution.Based on this absorbing carbon dioxide concentration and separately The dissolving photoresist agent concentration obtained, can obtain target conductivity values from conductivity data.

Claims (8)

1. a kind of management method of developer solution,

The conductivity in alkaline developer solution, dissolving photoresist agent concentration and the absorbing carbon dioxide that measure Reusability are dense Degree,

Every as index in the dissolving photoresist agent concentration of the above-mentioned developer solution of determination and absorbing carbon dioxide concentration using having Individual concentration range has been previously validated the conductivity data of the conductivity values of above-mentioned developer solution that can reach given developing performance Among, the concentration range that determined by the dissolving photoresist agent concentration being measured and the absorbing carbon dioxide concentration that measured Above-mentioned conductivity values, are set as the control targe value of the conductivity of above-mentioned developer solution,

The conductivity of above-mentioned developer solution is made to become above-mentioned control targe value to above-mentioned developer solution supply replenisher.

2. a kind of developer solution managing device, possesses control unit, and this control unit possesses:

Data store, preserves conductivity data, and this conductivity data has in determination Reusability in alkaline developer solution Dissolving photoresist agent concentration and absorbing carbon dioxide concentration be previously validated and can reach as each concentration range of index Conductivity values to the given above-mentioned developer solution of developing performance；And

Control unit, by the dissolving measured value of the photoresist agent concentration and mensure of absorbing carbon dioxide concentration by above-mentioned developer solution The above-mentioned conductivity values being saved in above-mentioned data store of concentration range that value determines are set to control targe value, to being arranged on Convey the control valve on the stream of replenisher that is fed in above-mentioned developer solution and send control signal so that the leading of above-mentioned developer solution Electric rate becomes above-mentioned control targe value.

3. developer solution managing device according to claim 2, wherein,

Above-mentioned developer solution managing device is also equipped with: multiple mensure devices, to the dissolving photoresist including with above-mentioned developer solution The characteristic value of concentration dependent above-mentioned developer solution and above-mentioned development concentration dependent with the absorbing carbon dioxide of above-mentioned developer solution The characteristic value of liquid is measured in multiple characteristic values of interior above-mentioned developer solution,

Above-mentioned control unit is also equipped with operational part, and this operational part is according to the above-mentioned developer solution being determined by multiple said determination devices Multiple characteristic values, calculate the dissolving measured value of photoresist agent concentration and the absorption of above-mentioned developer solution by multivariate analyses The measured value of gas concentration lwevel.

4. developer solution managing device according to claim 2, wherein,

Above-mentioned developer solution managing device is also equipped with: multiple mensure devices, to the dissolving photoresist including with above-mentioned developer solution The characteristic value of concentration dependent above-mentioned developer solution and above-mentioned development concentration dependent with the absorbing carbon dioxide of above-mentioned developer solution The characteristic value of liquid is measured in multiple characteristic values of interior above-mentioned developer solution；And

Arithmetic element, according to multiple characteristic values of the above-mentioned developer solution being determined by multiple said determination devices, using multivariate Analytic process is calculating the dissolving measured value of the photoresist agent concentration and measured value of absorbing carbon dioxide concentration of above-mentioned developer solution.

5. developer solution managing device according to claim 2, wherein,

Above-mentioned developer solution managing device possesses densimeter,

Above-mentioned control unit is also equipped with operational part, the absorbing carbon dioxide concentration based on above-mentioned developer solution for this operational part and density it Between corresponding relation, the density of the above-mentioned developer solution being determined using above-mentioned densimeter calculates the absorption dioxy of above-mentioned developer solution Change concentration of carbon.

6. developer solution managing device according to claim 2, wherein, is also equipped with:

Densimeter；And

Arithmetic element, the corresponding relation between the absorbing carbon dioxide concentration based on above-mentioned developer solution and density, using above-mentioned close The density of the above-mentioned developer solution that degree measurement is made calculates the absorbing carbon dioxide concentration of above-mentioned developer solution.

7. a kind of management method of developer solution,

Alkali concn is measured based on the conductivity in alkaline developer solution for the Reusability, measures the dissolving light with above-mentioned developer solution Cause agent concentration against corrosion to have the absorbance of dependency relation, measure the absorbing carbon dioxide concentration of above-mentioned developer solution,

Using have determine the absorbance of above-mentioned developer solution and absorbing carbon dioxide concentration as index each concentration range Among the alkali concn data of the alkali concn value being previously validated the above-mentioned developer solution that can reach given developing performance, by being surveyed Fixed absorbance and the above-mentioned alkali concn value of the concentration range of absorbing carbon dioxide concentration determination being measured, are set as above-mentioned aobvious The control targe value of the alkali concn of shadow liquid,

To above-mentioned developer solution supply replenisher so that the alkali concn of above-mentioned developer solution becomes above-mentioned control targe value.

8. a kind of developer solution managing device, possesses control unit, and this control unit possesses:

Data store, preserves alkali concn data, and this alkali concn data has in determination with Reusability in alkaline development The dissolving photoresist agent concentration of liquid has the absorbance of dependency relation and absorbing carbon dioxide concentration each concentration as index Region has been previously validated the alkali concn value of the above-mentioned developer solution that can reach given developing performance；And

Control unit, by the guarantor of the concentration range being determined by the absorbance of above-mentioned developer solution and the measured value of absorbing carbon dioxide concentration The above-mentioned alkali concn value existing in above-mentioned data store is set to control targe value, is fed to above-mentioned developer solution to being arranged on conveying In the stream of replenisher on control valve send control signal so that the alkali concn of above-mentioned developer solution becomes above-mentioned control targe Value.