CN1108541C - Corrosion inhibitor stripping liquid control device - Google Patents
Corrosion inhibitor stripping liquid control device Download PDFInfo
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- CN1108541C CN1108541C CN98108312A CN98108312A CN1108541C CN 1108541 C CN1108541 C CN 1108541C CN 98108312 A CN98108312 A CN 98108312A CN 98108312 A CN98108312 A CN 98108312A CN 1108541 C CN1108541 C CN 1108541C
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/42—Stripping or agents therefor
- G03F7/422—Stripping or agents therefor using liquids only
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Abstract
A controlling device for a resist stripper used to strip a resist in the production processes of semiconductors and liquid crystal substrates in which the quality of the resist stripper is controlled to a constant level and the use amount of the liquid, shutdown time of operation and cost can be decreased. This device is equipped with a resist concentration detecting and liquid replenishing means and a hydroxyl amine concentration detecting and liquid replenishing means. By the resist concentration detecting and liquid replenishing means, the concentration of the dissolved resist in the resist stripper is detected by an absorptiometer 16 and at least one of the resist stripping solution, hydroxylamine solution, pure water and preliminarily prepared new resist stripper is replenished. By the hydroxylamine concentration detecting and liquid replenishing means, the hydroxyl amine concentration in the resist stripper is detected by an absorptiometer 15 and at least one of the resist stripping solution, hydroxylamine solution and pure water is replenished.
Description
The present invention relates to a kind of control device that in semiconductor fabrication process or crystal liquid substrate manufacturing process, is used to peel off the anticorrosive additive stripping liquid controlling of resist, more particularly, the corrosion inhibitor stripping liquid control device that the present invention relates to has the resist concentration adjusting device of continuous automatically supplying apparatus, azanol concentration adjusting device, moisture concentration regulating device, liquid level regulation device or overflow mechanism that uses and the dissolving of using when peeling off the resist enrichment that dissolves owing to resist when recycling anticorrosive additive stripping liquid controlling.
In the manufacturing process of semiconductor or crystal liquid substrate, can be used for xeroxing the anticorrosive additive material in the operation, be included in the liquefiable positive plate-shaped material in exposure back and after exposure thawless negative-type material, but majority is to use positive plate-shaped material.
As the typical example of positive type resist, can enumerate with naphthoquinone two azide class emulsion and alkali soluble resins (novolac resin) is the resist of major component.
Xeroxing the terminal stage of operation, an operation that resist is peeled off from the substrate fully must arranged.
In the resist stripping technology of semiconductor or crystal liquid substrate, can and use the wet type stripping process of anticorrosive additive stripping liquid controlling to merge use the dry-type ashing process that uses oxygen plasma.
This is because the substrate through the dry-type ashing process that uses oxygen plasma is handled has generated Si oxide and aluminum oxide on its surface, use the wet type stripping process then, not only can peel off resist, and can remove these metal oxides fully, so these measures are necessary.
Open in the flat 7-235487 communique the spy and to have put down in writing a kind of corrosion inhibitor stripping liquid control device, this control device has one and is used for measuring the concentration of the resist that anticorrosive additive stripping liquid controlling dissolves and the anticorrosive additive stripping liquid controlling discharger that anticorrosive additive stripping liquid controlling is discharged by extinction photometer; One is used for measuring the liquid level of anticorrosive additive stripping liquid controlling and supply organic solvent and alkanolamine or peeled off first device for supplying of new liquid by organic solvent and the deployed in advance resist of alkanolamine in view of the above by liquid level gauge; One is used for measuring the concentration of resist alkanolamine and the second at least a device for supplying in supply organic solvent and the alkanolamine in view of the above by extinction photometer.
In addition, the applicant has also developed a kind of corrosion inhibitor stripping liquid control device, and this control device has: one is used for measuring the concentration of the resist that anticorrosive additive stripping liquid controlling dissolves and the anticorrosive additive stripping liquid controlling discharger that anticorrosive additive stripping liquid controlling is discharged by extinction photometer; One be used for by liquid level gauge measure the liquid level of anticorrosive additive stripping liquid controlling and in view of the above the supply resist peel off stoste and pure water or peel off first device for supplying that stoste and the deployed in advance resist of pure water are peeled off new liquid by resist; One be used for by extinction photometer measure the moisture concentration of anticorrosive additive stripping liquid controlling and in view of the above the supply resist peel off the second at least a device for supplying of stoste and pure water.And with this control device application patent (special be willing to flat 8-193005 number).
In the resist stripping technology of semiconductor or crystal liquid substrate, as mentioned above, as anticorrosive additive stripping liquid controlling, mainly be to use the solution that combines by organic base and organic solvent, in addition, the solution that is added with suitable quantity of water also can use, but finds out that the solution that is added with an amount of azanol has better effect.
That is to say, the effect that anticorrosive additive stripping liquid controlling had that contains an amount of azanol is, can be reduced to about 65 ℃ below from required about 80 ℃ of past the treatment temperature of substrate, for example about 40 ℃, so just can when forming substrate or semiconductor circuits, reduce infringement, can remove Si oxide and aluminum oxide simultaneously underlying metal.
For example, the solution of can use the solution formed by dimethyl sulfoxide class and azanol by spray pattern, box-packed mode or impregnation method etc., forming by N-Methyl pyrrolidone class and azanol, the solution of forming by alkanolamine and azanol, the solution of forming by alkanolamine and glycol ether and azanol, or in these solution adding pure water or various adjuvant and the solution that forms etc.
Adopt the mode of batch operation in the past, just the resist that adds a certain amount of normal concentration when beginning in resist lift-off processing groove is peeled off new liquid, then rule of thumb, with the substrate number handled etc. as index, reduce gradually along with anticorrosive additive stripping liquid controlling and when making its deterioration concentration range that reaches regulation, all be replaced by preprepared new liquid once.The replacing time of this stripper is different and different with conditions such as the kind of the capacity of treatment trough and substrate, processing substrate number, changes once but general replacing number of times is about per 4 days.
When anticorrosive additive stripping liquid controlling generation deterioration, can not reach certain peeling rate, and produce and to peel off residue and metal oxide residue, thereby cause the reduction of qualification rate.
In resist stripping process,, will cause big loss if produce inferior goods as the final stage of xeroxing operation.
The anticorrosive additive stripping liquid controlling that contains azanol uses under 30～65 ℃ temperature usually.
The boiling point that is used for the various compositions of anticorrosive additive stripping liquid controlling, organic base or organic solvent are about 160～250 ℃, and azanol is about 160 ℃, and water is 100 ℃.
When using anticorrosive additive stripping liquid controlling, for resist peel groove and atmosphere being separated and using nitrogen purge, meanwhile, lower boiling moisture preferential evaporation makes moisture concentration decline, thereby causes concentration to change.Therefore, the resist stripping performance reduces gradually, and still the past is not carried out The real time measure to moisture, and moisture is not controlled at consistently the concentration of regulation yet.
When moisture concentration further reduces, the danger of blasting is arranged owing to stripper has flash-point.
In addition, when using anticorrosive additive stripping liquid controlling, for resist peel groove and atmosphere being separated and using nitrogen purge, meanwhile, the low boiling azanol that is only second to water evaporates, and makes the density loss of azanol, thereby causes concentration to change.Therefore, the resist stripping performance reduces gradually, and still the past is not carried out The real time measure to azanol concentration, and moisture is not controlled at consistently the concentration of regulation yet.
In addition, when resist is carried out lift-off processing, the resist that is dissolved in the anticorrosive additive stripping liquid controlling concentrates gradually, this is to cause peeling rate to reduce and produce to peel off one of reason of resist stripping performance deteriorations such as residue, but the past is not carried out The real time measure to the resist concentration of dissolving, and resist is not controlled at consistently the concentration of regulation yet.
Therefore, the resist concentration of moisture concentration at this moment, azanol concentration and dissolving changed along with the time, can not keep certain, what cause producing resist peels off residue or metal oxide residue, thereby be difficult to crystal liquid substrate is carried out the precision control of high precision size, make the Products Quality instability and qualification rate is reduced.
In addition, need shut-down operation (stop time) during owing to replacing solution, thereby cause real moving rate to reduce significantly, and be accompanied by the replacing operation of anticorrosive additive stripping liquid controlling, must spend more operating cost of expense.
In view of above-mentioned variety of problems, the objective of the invention is to solve the problem that above-mentioned prior art exists, can in the crystal liquid substrate manufacturing process, be suitable for a large amount of productions, the advantage of carrying out online mode of movement according to easy prior art can be brought into play, and the advantage of the box-packed processing mode of silicon wafer can be in semi-conductive manufacturing process, brought into play again.
That is to say, the objective of the invention is, as long as be ready to have the stoste of predetermined component ratio, the resist concentration of moisture concentration, azanol concentration and dissolving that just can be is according to the rules automatically controlled anticorrosive additive stripping liquid controlling, and can carry out suitable control to the solution supply of resist lift-off processing groove, and the resist stripping performance can be kept constant for a long time, cut down the use amount of stoste, guarantee safety, shorten the stand-by time of operation significantly, can reduce comprehensive production cost.
The present invention confirms by experiment, the resist concentration of dissolving in the anticorrosive additive stripping liquid controlling of resist lift-off processing groove, as shown in figure 11, with solution absorbency confidential relation (linear relationship of height) is arranged, therefore the resist concentration of dissolving can be adjusted and control by the method for measuring absorbance.In addition, confirm by experiment that the moisture concentration in the anticorrosive additive stripping liquid controlling as shown in Figure 7, and also has confidential relation (linear relationship of height) between the solution absorbency, therefore, moisture concentration also can be adjusted and control by the method for measuring absorbance.And then, the present invention also confirms by experiment, the concentration of azanol in the anticorrosive additive stripping liquid controlling as shown in Figure 8, also has confidential relation (linear relationship of height) with solution absorbency, therefore, the concentration of azanol also can be adjusted and control by the method for measuring absorbance, therefore, and in the concentration of moisture concentration, azanol concentration and these 3 kinds of compositions of resist concentration, at least a kind of control individually wherein perhaps side by side can be controlled the concentration of these several compositions.
That is to say, in order to achieve the above object, corrosion inhibitor stripping liquid control device of the present invention is characterised in that, this control device has one and is used for that resist is peeled off stoste, hydroxylamine solution, pure water and deployed in advance resist and peels off at least a of new liquid, supply in the resist lift-off processing groove by the liquid level governor motion, thereby keep the liquid level of constant level to regulate the liquid device for supplying; And one be used for measuring the azanol concentration of anticorrosive additive stripping liquid controlling in this resist lift-off processing groove and in view of the above resist being peeled off the mensuration azanol concentration liquid device for supplying (hereinafter referred to as second device for supplying) (with reference to figure 1) of at least a supply in the resist lift-off processing groove in stoste, hydroxylamine solution and the pure water by extinction photometer.
In addition, corrosion inhibitor stripping liquid control device of the present invention is characterised in that, this control device has one and is used for measuring the resist concentration that anticorrosive additive stripping liquid controlling dissolves in the resist lift-off processing groove by extinction photometer, and in view of the above resist is peeled off stoste, hydroxylamine solution, pure water and deployed in advance resist and peeled off the mensuration resist concentration liquid device for supplying (hereinafter referred to as first device for supplying) of at least a supply in the resist lift-off processing groove in the new liquid; And an azanol concentration that is used for measuring anticorrosive additive stripping liquid controlling in the resist lift-off processing groove, and in view of the above resist is peeled off second device for supplying (referring to Fig. 2) of at least a supply in the resist lift-off processing groove in stoste, hydroxylamine solution and the pure water by extinction photometer.
In addition, corrosion inhibitor stripping liquid control device of the present invention is characterised in that, this control device has one and is used for measuring the resist concentration that anticorrosive additive stripping liquid controlling dissolves in the resist lift-off processing groove and in view of the above resist being peeled off stoste, hydroxylamine solution, pure water and deployed in advance resist and peeled off first device for supplying of at least a supply in the resist lift-off processing groove in the new liquid by extinction photometer; And one be used for measuring the moisture concentration of anticorrosive additive stripping liquid controlling in the resist lift-off processing groove and in view of the above resist being peeled off the mensuration moisture concentration liquid device for supplying (hereinafter referred to as three device for supplying) of at least a supply in the resist lift-off processing groove in stoste, hydroxylamine solution and the pure water by extinction photometer.(referring to Fig. 3).
In addition, corrosion inhibitor stripping liquid control device of the present invention is characterised in that, this control device has one and is used for measuring the azanol concentration of anticorrosive additive stripping liquid controlling in the resist lift-off processing groove and in view of the above resist being peeled off second device for supplying of at least a supply in the resist lift-off processing groove in stoste, hydroxylamine solution and the pure water by extinction photometer; And one be used for measuring the moisture concentration of anticorrosive additive stripping liquid controlling in the resist lift-off processing groove and in view of the above resist being peeled off three device for supplying (referring to Fig. 4 and Fig. 6) of at least a supply in the resist lift-off processing groove in stoste, hydroxylamine solution and the pure water by extinction photometer.
In addition, corrosion inhibitor stripping liquid control device of the present invention is characterised in that, this control device has one and is used for measuring the resist concentration that anticorrosive additive stripping liquid controlling dissolves in the resist lift-off processing groove and in view of the above resist being peeled off stoste, hydroxylamine solution, pure water and deployed in advance resist and peeled off first device for supplying of at least a supply in the resist lift-off processing groove in the new liquid by extinction photometer; One is used for measuring the azanol concentration of anticorrosive additive stripping liquid controlling in the resist lift-off processing groove and in view of the above resist being peeled off second device for supplying of at least a supply in the resist lift-off processing groove in stoste, hydroxylamine solution and the pure water by extinction photometer; And one be used for measuring the moisture concentration of anticorrosive additive stripping liquid controlling in the resist lift-off processing groove and in view of the above resist being peeled off three device for supplying (referring to Fig. 5) of at least a supply in the resist lift-off processing groove in stoste, hydroxylamine solution and the pure water by extinction photometer.
Peel off stoste as resist, for example can use the mixing stoste of dimethyl sulfoxide class stoste, N-Methyl pyrrolidone class stoste, diglycol class stoste, alkanolamine and glycol ethers solvent, perhaps in these stostes, add the stoste that forms behind pure water or the various adjuvant etc.
As alkanolamine, can enumerate: monoethanolamine, diethanolamine, triethanolamine, N, N-dimethylethanolamine, N, N-diethyl ethanolamine, aminoethyl ethanolamine, N-methyl-N, N-diethanolamine, N, N-dibutyl monoethanolamine, N-methylethanolamine, 3-amino-1-propyl alcohol etc.
As glycol ethers solvent, can enumerate: butyldiglycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diglycol monotertiary propyl ether etc.
As various adjuvants, can enumerate: catechol, reductive agent, corrosion inhibitor for metal, sequestrant etc.
Explain preferable embodiment of the present invention with reference to the accompanying drawings.But, the shape of Ji Zai constitution equipment in these embodiments, their relative configuration etc. is not limited to the situation of these specific records, and these embodiments can not be as limiting the scope of the invention, and they are some illustrative examples only.
Fig. 1 is the system diagram of the corrosion inhibitor stripping liquid control device of expression the present invention the 1st embodiment.Ref. No. 1～13rd among the figure constitutes the equipment of known before resist lift-off processing device.That is to say, resist lift-off processing device before is made of following equipment, comprising: the resist lift-off processing groove 1 that is used to store anticorrosive additive stripping liquid controlling, overflow groove 2, liquid level gauge 3, resist stripping cell cover 4, anticorrosive additive stripping liquid controlling sprayer 7, be used for liquid-feeding pump 8 to anticorrosive additive stripping liquid controlling shower nozzle feed flow, be used for removing the filtrator 9 of solids such as anticorrosive additive stripping liquid controlling fine particle, be used for the mounting substrate and it moved continuously so that the roller conveyor 5 that resist is peeled off, substrate 6, the ebullator 11 that is used to make peace and quietization of anticorrosive additive stripping liquid controlling and stirs, be used to remove the filtrator 13 of fine particle, and N
2The conveying pipe arrangement class of gas, pure water etc. etc.
According to the present invention, the equipment that is provided with in above-mentioned resist lift-off processing device has: the extinction photometer 15 that is used to measure azanol concentration, positive displacement pump 19, resist is peeled off stoste charging-tank 20, be used to supply the flow control valve 24 that resist is peeled off stoste, hydroxylamine solution charging-tank 21, be used to supply the flow control valve 25 of hydroxylamine solution, resist is peeled off new liquid charging-tank 22, be used to supply the flow control valve 26 that resist is peeled off new liquid, be used to supply the flow control valve 27 of pure water, and the pipe arrangement class and electric meter class or the air measuring instrument class etc. that are used to connect each equipment.
As having of bulking liquor: resist is peeled off stoste, hydroxylamine solution, resist and is peeled off new liquid and pure water, but these bulking liquors may not need all, can wait according to the acquisition condition of the degree of the composition of anticorrosive additive stripping liquid controlling, concentration change, appointed condition, traffic condition, bulking liquor and select optimal bulking liquor and feedway.In addition, the Ref. No. of following relevant Fig. 2～6 is same as described above.
As hydroxylamine solution, can use the aqueous solution (for example 50% aqueous solution) of azanol, but mixed liquor of azanol and other solvents, 100% azanol liquid etc. can use also.
Be stored in amount of liquid in the resist lift-off processing groove 1 and should enough supply with the required quantity of anticorrosive additive stripping liquid controlling sprayer 7, consider that from the stability of CONTROL PROCESS this condition is necessary.As shown in Figure 1, under normal conditions, the liquid level of resist lift-off processing groove 1 should near position running less than the liquid level gauge of overflow.
For example, be used for storing by monoethanolamine (being designated hereinafter simply as MEA) and basic diglycol (being designated hereinafter simply as BDG) in accordance with regulations the resist of the mixed liquor that forms of concentration peel off stoste charging-tank 20, acceptance is from the N of pipe arrangement 23
2Gas and be pressurized to 1～2kgf/cm
2Pressure, peel off stock solution flow variable valve 24 and resist can be peeled off the stoste force feed and come out as long as at this moment open resist.
The hydroxylamine solution charging-tank 21 that is used to store hydroxylamine solution is accepted to be pressurized to 1～2kgf/cm from the nitrogen of pipe arrangement 23
2Pressure, be about to the hydroxylamine solution force feed and come out as long as at this moment open hydroxylamine solution flow control valve 25.
Being used to store resist peels off the resist of new liquid and peels off new liquid charging-tank 22 and accept to be pressurized to 1～2kgf/cm from the nitrogen of pipe arrangement 23
2Pressure, peel off new flow quantity variable valve 26 and resist can be peeled off new hydraulic pressure and send out as long as at this moment open resist.
Pure water is sent by the arm that is on the pipe arrangement when opening pure water flow control valve 27.
These bulking liquors automatically adjust and liquor charging by variable valve separately, then in pipeline 28 interflow and then flow into pipeline 12, these bulking liquors are circulating middle mixing, flow into then in the resist lift-off processing groove 1.
In addition, these bulking liquors also can not collaborate but be connected with pipeline 12 or resist lift-off processing groove 1 separately.
In addition, be imported in the extinction photometer 15 that the anticorrosive additive stripping liquid controlling spraying is provided with on pipeline 10 lines and its absorbance of METHOD FOR CONTINUOUS DETERMINATION from the sample liquid of pipeline 14, through the feed liquid of mensuration via pipeline 18 in the return pipeline 10.
Fig. 2 is the plant system drawing of expression the present invention the 2nd embodiment.According to the present embodiment, the extinction photometer 16 that is imported into the extinction photometer 15 of measuring azanol concentration in anticorrosive additive stripping liquid controlling spraying being used to of being provided with on pipeline 10 lines and the resist concentration that is used to measure dissolving from the sample liquid of pipeline 14 (for example, two devices constitute one) in, the absorbance of this sample liquid of METHOD FOR CONTINUOUS DETERMINATION respectively, the sample liquid that determines are via pipeline 18 in the return pipeline 10.
In addition, also extinction photometer 15 and extinction photometer 16 can be provided with dividually, and use a kind of ebullator of measuring usefulness that feed liquid is imported in extinction photometer 15 and the extinction photometer 16.
In addition, as shown in Figure 2, under normal conditions, the liquid level of resist lift-off processing groove 1 turns round near the position of overflow weir.Under the situation of the fresh bulking liquor of supply, automatically carry out overflow from the deterioration anticorrosive additive stripping liquid controlling of overflow weir and discharge.In addition, extraction pump 19 is not necessary, a valve can be set replace extraction pump 19.
Other formations etc. are identical with the situation of Fig. 1.
Fig. 3 is the plant system drawing of expression the present invention the 3rd embodiment.According to the present embodiment, from the sample liquid of pipeline 14 be imported into anticorrosive additive stripping liquid controlling spraying being used to of being provided with on pipeline 10 lines measure dissolving resist concentration extinction photometer 16 and the extinction photometer 17 that is used to measure moisture concentration (for example, two devices constitute one) in, the absorbance of this sample liquid of METHOD FOR CONTINUOUS DETERMINATION respectively, the sample liquid of measuring are via pipeline 18 in the return pipeline 10.
In addition, as shown in Figure 3, under normal conditions, the liquid level of resist lift-off processing groove 1 turns round near the position of overflow weir.Other formations etc. are identical with the situation of Fig. 1 and Fig. 2.
Fig. 4 is the plant system drawing of expression the present invention the 4th embodiment.According to the present embodiment, be imported into the extinction photometer 15 of measuring azanol concentration in anticorrosive additive stripping liquid controlling spraying being used to of being provided with on pipeline 10 lines and the extinction photometer 17 that is used to measure moisture concentration from the sample liquid of pipeline 14 (for example, two devices constitute one) in, the absorbance of this sample liquid of METHOD FOR CONTINUOUS DETERMINATION respectively, the sample liquid of measuring by the road 18 and in the return pipeline 10.
In addition, as shown in Figure 4, under normal conditions, the liquid level of resist lift-off processing groove 1 turns round near the position of overflow weir.Other formations etc. are identical with the situation of Fig. 1 and Fig. 2.
Fig. 5 is the plant system drawing of expression the present invention the 5th embodiment.According to the present embodiment, the extinction photometer 17 that is imported into the extinction photometer 16 of the extinction photometer 15 of measuring azanol concentration in anticorrosive additive stripping liquid controlling spraying being used to of being provided with on pipeline 10 lines and the resist concentration that is used to measure dissolving from the sample liquid of pipeline 14 and is used to measure moisture concentration (for example, 3 devices constitute one) in, the absorbance of this sample liquid of METHOD FOR CONTINUOUS DETERMINATION respectively, the sample liquid of measuring are via pipeline 18 in the return pipeline 10.
In addition, as shown in Figure 5, under normal conditions, the liquid level of resist lift-off processing groove 1 turns round near the position of overflow weir.Other formations etc. are identical with the situation of Fig. 1 and Fig. 2.
Fig. 6 is the plant system drawing of expression the present invention the 6th embodiment.The present embodiment is a kind of box-packed processing mode, wherein, use a kind ofly to be used for replacing the shovel loader of Fig. 4 roller conveyor 5 to carry out moving into and taking out of of box 33, in box 33, arranging substrate 34 (for example, arranging be used to make 20 of semi-conductive silicon wafers).
According to the present embodiment, be imported into the extinction photometer 15 of measuring azanol concentration in anticorrosive additive stripping liquid controlling spraying being used to of being provided with on pipeline 10 lines and the extinction photometer 17 that is used to measure moisture concentration from the feed liquid of pipeline 14 (for example, two devices constitute one) in, the absorbance of this feed liquid of METHOD FOR CONTINUOUS DETERMINATION respectively, the feed liquid of measuring are via pipeline 18 in the return pipeline 10.
In addition, as shown in Figure 6, under normal conditions, the liquid level of resist lift-off processing groove 1 turns round near the position of overflow weir.Other formations etc. are identical with the situation of Fig. 4.
Control system to the device of embodiment shown in Fig. 1～6 describes below.
Moisture concentration in the resist concentration of dissolving in the azanol concentration of the liquid level of liquid level gauge 3 and resist lift-off processing groove 1, extinction photometer 15 and anticorrosive additive stripping liquid controlling, extinction photometer 16 and the anticorrosive additive stripping liquid controlling, extinction photometer 17 and the anticorrosive additive stripping liquid controlling; Basically work with their standalone features separately, but the invention is characterized in, replenish mutually and realize function of the present invention by functions two or more in these functions.
In addition, must the concentrated ultimate value of the resist concentration of the desired value of moisture concentration in the desired value of azanol concentration in the necessary anticorrosive additive stripping liquid controlling in the quality control of goods substrate, the anticorrosive additive stripping liquid controlling, dissolving etc. be set in advance in each controller according to the actual conditions or the calculated value of operation.
Below explain to use the embodiment of a kind of mixed solution that forms by MEA, BDG, azanol and pure water as anticorrosive additive stripping liquid controlling.
Usually, mainly due to the water evaporates of following nitrogen blowing to cause and along with the increase of processing substrate number, make the moisture concentration that is maintained at about 65 ℃ of anticorrosive additive stripping liquid controllings under the constant liquid temperature reduce gradually, therefore cause the resist stripping performance deterioration of anticorrosive additive stripping liquid controlling.
Therefore, moisture concentration must be controlled at the desired value of regulation, for example in 24.0 ± 1.0% scope.Past all is to wait the degree of judging the anticorrosive additive stripping liquid controlling deterioration according to that learn by experience with relation or chemical analysis processing substrate sheet number, but is difficult to like this hold rapidly and correctly.
The inventor studies moisture concentration in the anticorrosive additive stripping liquid controlling and the relation between the absorbance by experiment, and the scope of 950nm～1010nm that the mensuration wavelength of absorbance suits near infrared range particularly has good sensitivity near 976nm.
In addition, when selecting the mensuration wavelength, can select for use respectively according to the kind and the concentration of stripper and resist near infrared range.
As shown in Figure 7, there is the linear relationship of height between absorbance when measuring wavelength X=976nm and the moisture concentration, owing to measured absorbance, thus can correctly measure moisture concentration.
Shown in Fig. 3,4,5,6, (extinction photometer 15 and/or extinction photometer 16 can be by integral types or split type for the extinction photometer 17 that is provided with on pipeline 10 lines, perhaps be provided with individually) have and be used to the various compensate functions and the absorbance controller 32 that make error at measurment become minimum value.The absorbance measurement value input absorbance controller 32 of the sample liquid that imports by pipeline 10, with this numerical value as desired value, then according to output signal and under the condition of automatic control flow variable valve 24,25,27 the supply resist peel off at least a in stoste, hydroxylamine solution and the pure water so that moisture concentration is adjusted to desired value.
In addition, the azanol in the anticorrosive additive stripping liquid controlling has the low boiling that is only second to water, reduces gradually owing to the azeotropic vaporization with moisture makes its concentration, thereby makes the resist stripping performance deterioration of anticorrosive additive stripping liquid controlling.
Therefore, azanol concentration must be controlled at the desired value of regulation, for example in 6.0 ± 1.0% scope.Past all is to wait the degree of judging the anticorrosive additive stripping liquid controlling deterioration according to that learn by experience with relation or chemical analysis processing substrate sheet number, but is difficult to like this hold rapidly and correctly.
The inventor studies the azanol concentration of anticorrosive additive stripping liquid controlling and the relation between the absorbance by experiment, the mensuration wavelength of absorbance is suitable and in the scope of the 1050nm～1090nm of near infrared range, particularly has very good sensitivity near the less 1074nm of other composition influences.
In addition, when selecting the mensuration wavelength, can select for use respectively according to the kind and the concentration of stripper and resist near infrared range.
As shown in Figure 8, there is the linear relationship of height between the absorbance when measuring wavelength X=1074nm and the azanol concentration, owing to having measured absorbance, thereby can correctly measures the concentration of azanol.
Shown in Fig. 1,2,4,5,6, the extinction photometer 15 that is provided with on pipeline 10 lines has and is used to the various compensate functions and the absorbance controller 30 that make error at measurment become minimum value.The absorbance measurement value input absorbance controller 30 of the sample liquid that imports by pipeline 10, with this numerical value as desired value, then according to output signal and under the condition of automatic control flow variable valve 24,25,27 the supply resist peel off at least a in stoste, hydroxylamine solution and the pure water so that azanol concentration is adjusted to desired value.
The deterioration of resist stripping performance is except relevant with azanol concentration with above-mentioned moisture concentration, and is also relevant with the resist concentration of dissolving.The anticorrosive additive stripping liquid controlling that processing substrate is used takes out from resist peel groove 1 by liquid-feeding pump 8, recycles through anticorrosive additive stripping liquid controlling sprayer 7 again, and therefore, dissolved material concentrates in anticorrosive additive stripping liquid controlling gradually.Wherein, main dissolved substance is a resist, and as illustrating as operational example among Fig. 9, the concentration of resist concentrates gradually along with the increase of processing substrate number, and the result is the remarkable deterioration of resist stripping performance.Past is not carried out The real time measure to this concentration change, and the resist stripping performance is not controlled at certain numerical value.The curve that the curve representation of Fig. 9 obtains when using the mixed liquor of being made up of MEA, BDG, azanol and pure water.
That is to say, though can be with the treating number of substrate as the deterioration index, but, because the mode of peeling off of the shape of substrate or the thickness of resist or resist not necessarily, so the amount of the resist that dissolves from every kind of substrate is inequality, be irrational as the principal element of judging therefore with the substrate number of handling.
The inventor mainly is that the relation of agent concentration against corrosion and absorbance is measured for to because the concentrated pollutional condition that causes of the resist in the anticorrosive additive stripping liquid controlling is studied, and by experiment, has obtained result as shown in Figure 10 and Figure 11.As seen from Figure 11, the linear relationship that is height between the resist concentration of dissolving and the absorbance, be not subjected to the influence of moisture concentration etc., therefore can just can not judge the ultimate value of the resist stripping performance that is determined by the resist concentration itself of dissolving according to the number of processing substrate.As the suitable mensuration wavelength of the resist concentration of measuring dissolving, use λ=560nm.In addition, when the 400nm from the visible region selects to measure wavelength to the scope of the 800nm of near infrared region, can select respectively to use according to the kind or the concentration of resist.
Shown in Fig. 2,3,5, the extinction photometer 16 that is provided with on pipeline 10 lines has and is used to the various compensate functions and the absorbance controller 31 that make error at measurment become minimum value.Extinction photometer 16 is measured the resist concentration of dissolving in the anticorrosive additive stripping liquid controlling continuously, and measure whether exceeded the deterioration ultimate value in view of the above, according to the output signal supply resist of absorbance controller 31 peel off stoste, hydroxylamine solution, pure water and deployed in advance resist peel off at least a in the new liquid and by flow control valve 24,25,26,27 automatically the control increments so that the resist concentration of dissolving is adjusted to desired value.The result of the fresh bulking liquor of supply arrives the concentration dilution of the resist of dissolving the ultimate value of deterioration, thereby makes it recover the stripping performance of resist.
As shown in Figure 1, liquid level gauge 3 is connected with fluid level controller 29 (though have only Fig. 1 to show fluid level controller 29, but Fig. 2～6 are equipped with fluid level controller too), its effect be measure owing to anticorrosive additive stripping liquid controlling attached on the substrate and be brought to the caused liquid level reduction of the natural decrement value that causes in the follow-up operation, and peel off stoste according to the output signal supply resist of fluid level controller 29, hydroxylamine solution, pure water and deployed in advance resist are peeled off at least a in the new liquid, simultaneously by flow control valve 24,25,26,27 control various bulking liquors automatically, thereby make liquid level return to original state.
Consequently supply fresh bulking liquor, diluted the concentration of the resist of dissolving, thereby recovered its resist stripping performance.
Relation between the function of the device of the 1st embodiment shown in Fig. 1 and desirable control system is described below.
The present embodiment mainly is applicable to the situation of using the less stripper of a kind of moisture concentration in anticorrosive additive stripping liquid controlling, perhaps, when the resist lift-off processing to the very important situation of the control of azanol concentration etc.
When resist lift-off processing groove 1 is in the dead slot reducing bath, it is empty that liquid level gauge 3 is measured treatment trough, sending into resist according to the output signal of fluid level controller 29 peels off stoste, hydroxylamine solution, pure water and deployed in advance resist and peels off at least a in the new liquid, and control liquor charging respectively automatically, thereby make liquid level reach desired location by flow control valve 24,25,26,27.
Normally send into deployed in advance resist and peel off new liquid according to the output signal of fluid level controller 29.In addition, can regulate the valve opening of flow control valve 24,25,27 according to the output signal of liquid-level controller (LLC) 29, according to suitable flow liquor charging recently, reach with resist and peel off the equal substantially concentration of new liquid so that make resist peel off stoste, hydroxylamine solution and pure water.
Then, the absorbance of anticorrosive additive stripping liquid controlling when extinction photometer 15 is measured reducing bath continuously, output signal according to absorbance controller 30, resist is peeled off at least a in stoste, hydroxylamine solution and the pure water, liquor charging under the condition of the valve opening of at least one variable valve is controlled in view of the above automatically so that make azanol concentration meet desired value in suitable tiny flow quantity and adjusting flow control valve 24,25 and 27.
Then, after beginning to carry out the resist lift-off processing, the decline of decline, the azanol concentration of moisture concentration takes place, because the resist that treating fluid is taken out of the minimizing that causes solution amount and dissolving by substrate is concentrated.
When the density loss of azanol, extinction photometer 15 is measured the absorbance of anticorrosive additive stripping liquid controlling continuously, output signal according to absorbance controller 30, under the condition of suitable tiny flow quantity and the valve opening of regulating flow control valve 25, send into hydroxylamine solution, control automatically in view of the above so that make azanol concentration meet desired value.In addition, when the density loss of azanol, moisture concentration also descends thereupon, therefore, output signal according to absorbance controller 30, under the condition of suitable tiny flow quantity and the valve opening of regulating flow control valve 27, send into pure water, also can add an automatic controls, so that moisture concentration is adjusted in the specialized range.
Taken out of by substrate owing to liquid under the situation that makes the solution amount minimizing, liquid level gauge 3 is measured the liquid level of decline, according to the output signal of fluid level controller 29, sends into deployed in advance resist by flow control valve 26 and peels off new liquid.In addition, can not send into also that resist is peeled off new liquid but according to the output signal of fluid level controller 29, according to suitable throughput ratio with under the condition of the valve opening of regulating flow control valve 24,25,27, send into resist and peel off stoste, hydroxylamine solution and pure water, so that it reaches required concentration.
Relation between the function of the device of the 2nd embodiment shown in Fig. 2 and desirable control system is described below.
The present embodiment mainly be applicable to use a kind of in anticorrosive additive stripping liquid controlling the situation of the less stripper of moisture concentration, perhaps, when the resist lift-off processing to the very important situation of the control of azanol concentration etc.
When resist lift-off processing groove 1 is in the dead slot reducing bath, for example, according to manual operation, resist is peeled off stoste, hydroxylamine solution, pure water and deployed in advance resist peel off at least a in the new liquid, by flow control valve 24,25,26,27 difference liquor chargings, make liquid level reach assigned position.
Usually sending into deployed in advance resist according to manual operation peels off new liquid.In addition, also can under condition, send into resist and peel off stoste, hydroxylamine solution and pure water, peel off the equal substantially concentration of new liquid so that they are reached with resist according to suitable throughput ratio and the valve opening of regulating flow control valve 24,25,27.
Then, the absorbance of anticorrosive additive stripping liquid controlling when extinction photometer 15 is measured reducing bath continuously, output signal according to absorbance controller 30, resist is peeled off at least a in stoste, hydroxylamine solution and the pure water, liquor charging under the condition of the valve opening of at least one variable valve is controlled in view of the above automatically so that make azanol concentration meet desired value in suitable tiny flow quantity and adjusting flow control valve 24,25 and 27.
Along with the carrying out of resist lift-off processing, the decline of decline, the azanol concentration of moisture concentration takes place, because the resist that treating fluid is taken out of the minimizing that causes solution amount and dissolving by substrate is concentrated.
When the density loss of azanol, extinction photometer 15 is measured the absorbance of anticorrosive additive stripping liquid controlling continuously, output signal according to absorbance controller 30, under the condition of suitable tiny flow quantity and the valve opening of regulating flow control valve 25, send into hydroxylamine solution, control automatically in view of the above so that make azanol concentration meet desired value.In addition, when the density loss of azanol, moisture concentration also descends thereupon, therefore, output signal according to absorbance controller 30, under the condition of suitable tiny flow quantity and the valve opening of regulating flow control valve 27, send into pure water, also can add an automatic controls, so that moisture concentration is adjusted in the specialized range.
When the resist of dissolving concentrates and when making its concentration reach the ultimate value of deterioration, extinction photometer 16 is measured the resist concentration of dissolving in the anticorrosive additive stripping liquid controlling continuously, when recording resist concentration, send into deployed in advance resist according to the output signal of absorbance controller 31 by flow control valve 26 and peel off new liquid above the deterioration ultimate value.
In addition, can not send into also that resist is peeled off new liquid but according to the output signal of absorbance controller 31, resist is peeled off stoste, hydroxylamine solution and pure water, according to suitable throughput ratio and under the condition of the valve opening of regulating flow control valve 24,25,27 liquor charging so that make mentioned component reach the concentration of regulation.
Its result and since supply fresh bulking liquor, with the resist concentration dilution of dissolving to the deterioration ultimate value, thereby recovered the resist stripping performance.
Because liquid level is near the position on weir is used in overflow, so when bulking liquor was gone in supply, the anticorrosive additive stripping liquid controlling of deterioration just overflowed with the weir from overflow.
When owing to substrate is taken solution when liquid measure is reduced out of, liquid level is more lower slightly with the position on weir than overflow.
Relation between the function of the device of the 3rd embodiment shown in Fig. 3 and desirable control system is described below.
The present embodiment mainly is applicable to the situation of using a kind of stripper that moisture concentration is bigger in anticorrosive additive stripping liquid controlling, perhaps, when the resist lift-off processing to the very important situation of the control of moisture concentration etc.
When resist lift-off processing groove 1 is in the dead slot reducing bath, for example, according to manual operation, resist is peeled off stoste, hydroxylamine solution, pure water and deployed in advance resist peel off at least a in the new liquid, by flow control valve 24,25,26,27 difference liquor chargings, make liquid level reach assigned position.
Usually sending into deployed in advance resist according to manual operation peels off new liquid.In addition, also can under condition, send into resist and peel off stoste, hydroxylamine solution and pure water, peel off the equal substantially concentration of new liquid so that they are reached with resist according to suitable throughput ratio and the valve opening of regulating flow control valve 24,25,27.
Then, the absorbance of anticorrosive additive stripping liquid controlling when extinction photometer 17 is measured reducing bath continuously, output signal according to absorbance controller 32, resist is peeled off at least a in stoste, hydroxylamine solution and the pure water, at suitable tiny flow quantity with regulate liquor charging under the condition of the valve opening of at least one variable valve in the flow control valve 24,25 and 27, control automatically in view of the above so that make moisture concentration etc. meet desired value.
Along with the carrying out of resist lift-off processing, the decline of decline, the azanol concentration of moisture concentration takes place, because the resist that treating fluid is taken out of the minimizing that causes solution amount and dissolving by substrate is concentrated.
When moisture concentration descends, extinction photometer 17 is measured the absorbance of anticorrosive additive stripping liquid controlling continuously, output signal according to absorbance controller 32, under the condition of suitable tiny flow quantity and the valve opening of regulating flow control valve 27, send into pure water, control automatically in view of the above so that make moisture concentration meet desired value.In addition, when moisture concentration descends, azanol concentration also descends thereupon, therefore, output signal according to absorbance controller 32, at suitable tiny flow quantity with regulate under the condition of valve opening of flow control valve 25 and send into hydroxylamine solution, also can add an automatic controls so that with the azanol concentration adjustment in specialized range.
When the resist of dissolving concentrates and when making its concentration reach the deterioration ultimate value, extinction photometer 16 is measured the concentration of the resist that dissolves in the anticorrosive additive stripping liquid controlling continuously, when recording resist concentration, send into deployed in advance resist according to the output signal of absorbance controller 31 by flow control valve 26 and peel off new liquid above the deterioration ultimate value.
In addition, can not send into also that resist is peeled off new liquid but according to the output signal of absorbance controller 31, resist is peeled off stoste, hydroxylamine solution and pure water, according to suitable throughput ratio and under the condition of the valve opening of regulating flow control valve 24,25,27 liquor charging so that make mentioned component reach the cooperation concentration of regulation.
Its result and since supply fresh bulking liquor, with the resist concentration dilution of dissolving to the deterioration ultimate value, thereby recovered the resist stripping performance.
Because liquid level is in overflow with near the position on weir, so when bulking liquor was gone in supply, the anticorrosive additive stripping liquid controlling of deterioration just overflowed with the weir from overflow.
When owing to substrate is taken solution when liquid measure is reduced out of, liquid level is more lower slightly with the position on weir than overflow.
Relation between the function of the device of the 4th embodiment shown in Fig. 4 and desirable control system is described below.
The present embodiment mainly is applicable to the situation of handling the little substrate of a kind of resist meltage, and perhaps, feasible resist concentration of dissolving does not have the situation of rising etc. in that the supply liquid measure is big.
When resist lift-off processing groove 1 is in the dead slot reducing bath, for example, according to manual operation, resist is peeled off stoste, hydroxylamine solution, pure water and pre-deployed before this resist peel off at least a in the new liquid, by flow control valve 24,25,26,27 difference liquor chargings, make liquid level reach assigned position.
Usually sending into deployed in advance resist according to manual operation peels off new liquid.In addition, also can under condition, send into resist and peel off stoste, hydroxylamine solution and pure water, peel off the equal substantially concentration of new liquid so that they are reached with resist according to suitable throughput ratio and the valve opening of regulating flow control valve 24,25,27.
Then, extinction photometer 15 is measured the absorbance of anticorrosive additive stripping liquid controlling in the reducing bath continuously, output signal according to absorbance controller 30, resist is peeled off at least a in stoste, hydroxylamine solution and the pure water, liquor charging under the condition of the valve opening of at least one variable valve is controlled in view of the above automatically so that make azanol concentration meet desired value in suitable tiny flow quantity and adjusting flow control valve 24,25 and 27.
In addition, extinction photometer 17 is measured the absorbance of anticorrosive additive stripping liquid controlling in the reducing bath continuously, output signal according to absorbance controller 32, resist is peeled off at least a in stoste, hydroxylamine solution and the pure water, liquor charging under the condition of the valve opening of at least one variable valve is controlled in view of the above automatically so that make moisture concentration meet desired value in suitable tiny flow quantity and adjusting flow control valve 24,25 and 27.
Along with the carrying out of resist lift-off processing, the decline of decline, the azanol concentration of moisture concentration takes place, because the resist that treating fluid is taken out of the minimizing that causes solution amount and dissolving by substrate is concentrated.
When moisture concentration descends, extinction photometer 17 is measured the absorbance of anticorrosive additive stripping liquid controlling continuously, output signal according to absorbance controller 32, under the condition of suitable tiny flow quantity and the valve opening of regulating flow control valve 27, send into pure water, control automatically in view of the above so that make moisture concentration meet desired value.
When the density loss of azanol, extinction photometer 15 is measured the absorbance of anticorrosive additive stripping liquid controlling continuously, output signal according to absorbance controller 30, under the condition of suitable tiny flow quantity and the valve opening of regulating flow control valve 25, send into hydroxylamine solution, control automatically in view of the above so that make azanol concentration meet desired value.
Relation between the function of the device of the 5th embodiment shown in Fig. 5 and desirable control system is described below.
The present embodiment is applicable to that mainly each is all important control item purpose situation etc. in the resist concentration of moisture concentration, azanol concentration and dissolving.
When resist lift-off processing groove 1 is in the dead slot reducing bath, for example, according to manual operation, resist is peeled off stoste, hydroxylamine solution, pure water and deployed in advance resist peel off at least a in the new liquid, by flow control valve 24,25,26,27 difference liquor chargings, make liquid level reach assigned position.
Usually sending into deployed in advance resist according to manual operation peels off new liquid.In addition, also can under condition, send into resist and peel off stoste, hydroxylamine solution and pure water, peel off the equal substantially concentration of new liquid so that they are reached with resist according to suitable throughput ratio and the valve opening of regulating flow control valve 24,25,27.
Then, extinction photometer 15 is measured the absorbance of anticorrosive additive stripping liquid controlling in the reducing bath continuously, output signal according to absorbance controller 30, resist is peeled off at least a in stoste, hydroxylamine solution and the pure water, liquor charging under the condition of the valve opening of at least one variable valve is controlled in view of the above automatically so that make azanol concentration meet desired value in suitable tiny flow quantity and adjusting flow control valve 24,25 and 27.
In addition, extinction photometer 17 is measured the absorbance of anticorrosive additive stripping liquid controlling in the reducing bath continuously, output signal according to absorbance controller 32, resist is peeled off at least a in stoste, hydroxylamine solution and the pure water, liquor charging under the condition of the valve opening of at least one variable valve is controlled in view of the above automatically so that make moisture concentration meet desired value in suitable tiny flow quantity and adjusting flow control valve 24,25 and 27.
Along with the carrying out of resist lift-off processing, the decline of decline, the azanol concentration of moisture concentration takes place, because the resist that treating fluid is taken out of the minimizing that causes solution amount and dissolving by substrate is concentrated.
When moisture concentration descends, extinction photometer 17 is measured the absorbance of anticorrosive additive stripping liquid controlling continuously, output signal according to absorbance controller 32, under the condition of suitable tiny flow quantity and the valve opening of regulating flow control valve 27, send into pure water, control automatically in view of the above so that make moisture concentration meet desired value.
When the density loss of azanol, extinction photometer 15 is measured the absorbance of anticorrosive additive stripping liquid controlling continuously, output signal according to absorbance controller 30, under the condition of suitable tiny flow quantity and the valve opening of regulating flow control valve 25, send into hydroxylamine solution, control automatically in view of the above so that make azanol concentration meet desired value.
When the resist of dissolving concentrates and when making its concentration reach the deterioration ultimate value, extinction photometer 16 is measured the concentration of the resist that dissolves in the anticorrosive additive stripping liquid controlling continuously, when recording resist concentration, send into deployed in advance resist according to the output signal of absorbance controller 31 by flow control valve 26 and peel off new liquid above the deterioration ultimate value.
In addition, can not send into also that resist is peeled off new liquid but according to the output signal of absorbance controller 31, resist is peeled off stoste, hydroxylamine solution and pure water, according to suitable throughput ratio and under the condition of the valve opening of regulating flow control valve 24,25,27 liquor charging so that make mentioned component reach the cooperation concentration of regulation.
Its result and since supply fresh bulking liquor, with the resist concentration dilution of dissolving to below the deterioration ultimate value, thereby recovered the resist stripping performance.
Because liquid level is in overflow with near the position on weir, so when bulking liquor was gone in supply, the anticorrosive additive stripping liquid controlling of deterioration just overflowed with the weir from overflow.
When owing to substrate is taken solution when liquid measure is reduced out of, liquid level is more lower slightly with the position on weir than overflow.
The device of the 6th embodiment shown in Fig. 6 is described below.
The present embodiment mainly is applicable to arranges situation of handling the little silicon wafer of a kind of resist meltage etc. in the ordinary course of things by boxlike.
Identical about the situation relevant with the situation shown in Fig. 4 with the function of this control system.
The inventor confirms by experiment, as mentioned above, if use result based on various control function according to the relation of replenishing mutually, promptly can easily realize the resist stripping performance recovery, work continuously and the reduction of anticorrosive additive stripping liquid controlling use amount.
Below, in order to obtain understanding, the effect comparison of the present invention and art methods work pattern has been shown in Figure 12～Figure 17 to notion.According to the method for prior art, as shown in Figure 12, the moisture concentration when beginning for example is 25.0 weight %, and this concentration descends gradually along with the process of time, for example carries out solution and change when being reduced to 10.0 weight % (chemical analysis value).In this case, moisture concentration is indentation over time, just exists to change bigger situation aspect moisture concentration, so the resist stripping performance is non-constant.
But such as shown in Figure 13 if use device of the present invention, even along with the process of time, moisture concentration is also constant in for example 24.0 ± 1.0 weight %, so its resist stripping performance is constant, also needn't carry out solution simultaneously and change operation.
In addition, according to the method for prior art, as shown in Figure 14, the azanol concentration when starting for example is 7.0 weight %, and this concentration descends gradually along with the process of time, for example carries out solution and change when being reduced to 2.0 weight % (chemical analysis value).In this case, azanol concentration is indentation over time, just exists to change bigger situation aspect azanol concentration, so the resist stripping performance is non-constant.
But such as shown in Figure 15 if use device of the present invention, even along with the process of time, azanol concentration is also constant in for example 6.0 ± 1.0 weight %, so its resist stripping performance is stable, also needn't carry out solution simultaneously and change operation.
In addition, according to the method for prior art, as shown in Figure 16, the resist concentration when beginning increases gradually along with the process of time, just need carry out solution and change when this concentration reaches the numerical range that can cause the reduction of resist stripping performance.In this case, as shown in Figure 16, the concentration of the resist of dissolving is indentation over time, and just there is the bigger situation of variation in the concentration of Rong Xie resist, so the resist stripping performance is non-constant.
But such as shown in Figure 17 if use device of the present invention, the resist concentration of dissolving is still keeping constant through after a certain period, and the resist stripping performance is stable, also needn't carry out solution simultaneously and change operation.
In addition, the solution that use MEA, the BDG that the present invention is not limited only to address in the above, azanol and pure water are formed is as the situation of anticorrosive additive stripping liquid controlling, simultaneously, also be applicable to the present invention at the solution that uses the solution formed by organic base and azanol and pure water, the solution of forming by organic solvent and azanol and pure water, the solution of forming by organic base and organic solvent and azanol and pure water, the solution of forming by organic base and organic solvent and azanol and pure water and adjuvant or in these solution, contain pure water hardly under as the situation of anticorrosive additive stripping liquid controlling.
Therefore the aforesaid formation of tool of the present invention has effect as described below.
(1) the present invention is applicable to the resist stripping process of semiconductor or crystal liquid substrate, the resist concentration of the moisture concentration in the watch-keeping anticorrosive additive stripping liquid controlling, azanol concentration and/or dissolving in real time can and accurately be controlled at the concentration range of regulation respectively with these concentration stabilize.
Therefore, the resist stripping performance of substrate also reaches stabilization, thereby has improved the qualification rate of goods significantly.
In addition, anticorrosive additive stripping liquid controlling does not have flash-point under common user mode, has therefore guaranteed security, can work continuously for a long time according to stable liquid level simultaneously.
(2) owing to use cheap anticorrosive additive stripping liquid controlling; and the quality of this stripper can be kept constant and can work continuously; therefore reached and be not used in the stop time of changing solution and useless discarded object; the cost of solution use amount and stripper all reduces significantly; owing to the raising of real moving rate improves throughput rate significantly, owing to the unmanned comprehensive effect of each side such as labour cost reduction that makes.
(3) because azanol concentration is controlled at setting, therefore can positively remove attached to Si oxide on the substrate and aluminum oxide etc.
Therefore, can not produce and peel off residue and metal oxide residue, and can produce inferior goods hardly.
(4) under the situation of using the anticorrosive additive stripping liquid controlling that combines by organic base and organic solvent before, treatment temperature as substrate must reach about 80 ℃, but under the situation of using apparatus of the present invention, owing to contain an amount of azanol, therefore the treatment temperature of substrate can be reduced to about 40 ℃.
Therefore, can alleviate being used to form the infringement that underlying metal caused of substrate or semiconductor circuits.
Simple declaration to accompanying drawing
Fig. 1 is the system diagram of the corrosion inhibitor stripping liquid control device of expression the present invention the 1st embodiment.
Fig. 2 is the system diagram of the corrosion inhibitor stripping liquid control device of expression the present invention the 2nd embodiment.
Fig. 3 is the system diagram of the corrosion inhibitor stripping liquid control device of expression the present invention the 3rd embodiment.
Fig. 4 is the system diagram of the corrosion inhibitor stripping liquid control device of expression the present invention the 4th embodiment.
Fig. 5 is the system diagram of the corrosion inhibitor stripping liquid control device of expression the present invention the 5th embodiment.
Fig. 6 is the system diagram of the corrosion inhibitor stripping liquid control device of expression the present invention the 6th embodiment.
Fig. 7 is expression curve map of the relation of moisture concentration and absorbance in the used stripper among the present invention.
Fig. 8 is the curve map that expression concerns between azanol concentration and the absorbance in the used stripper among the present invention.
Fig. 9 is illustrated in when using anticorrosive additive stripping liquid controlling of the present invention the curve map of the relation between the substrate number of resist lift-off processing and the resist concentration of dissolving.
Figure 10 is that the resist concentration determination of the substrate number of resist lift-off processing and dissolving among expression the present invention is with the curve map that concerns between the absorbance.
Figure 11 is the curve map that concerns between expression resist concentration of dissolving in the anticorrosive additive stripping liquid controlling of the present invention and the absorbance.
Figure 12 is the curve map that is illustrated in the moisture concentration in the art methods and concerns between the activity duration.
Figure 13 is the curve map that is illustrated in moisture concentration and activity duration relation when using device of the present invention.
Figure 14 is illustrated in the azanol concentration in the art methods and the curve map of activity duration relation.
Figure 15 is the curve map that is illustrated in azanol concentration and activity duration relation when using device of the present invention.
Figure 16 is illustrated in the resist concentration of dissolving in the art methods and the curve map of activity duration relation.
Figure 17 is illustrated in the resist concentration of dissolving when using of the present invention device the and the curve map of activity duration relation.
Explanation to symbol
1. resist lift-off processing groove
3. liquid level gauge
5. roller conveyor
6. substrate
7. anticorrosive additive stripping liquid controlling sprayer
8. liquid-feeding pump
11. ebullator
15. extinction photometer
16. extinction photometer
17. extinction photometer
19. extraction pump
20. resist is peeled off the stoste charging-tank
21. hydroxylamine solution charging-tank
22. resist is peeled off new liquid charging-tank
24. stock solution flow variable valve
25. hydroxylamine solution flow control valve
26. new flow quantity variable valve
27. pure water flow control valve
29. fluid level controller
30. absorbance controller
31. absorbance controller
32. absorbance controller
33. box
34. substrate (silicon wafer)
Claims (5)
1. corrosion inhibitor stripping liquid control device, it is characterized in that, this control device has one and is used for that resist is peeled off stoste, hydroxylamine solution, pure water and at least a of new liquid peels off in deployed in advance resist azanol system, supply in the resist lift-off processing groove by the liquid level governor motion, thereby keep the liquid level of constant level to regulate the liquid device for supplying; And one be used for that to measure resist azanol in this resist lift-off processing groove be the azanol concentration of stripper and in view of the above resist is peeled off the azanol concentration determination liquid device for supplying of at least a supply in the resist lift-off processing groove in stoste, hydroxylamine solution and the pure water by extinction photometer.
2. corrosion inhibitor stripping liquid control device, it is characterized in that, this control device has one and is used for measuring by extinction photometer that the resist azanol is the resist concentration that stripper dissolves in the resist lift-off processing groove, and in view of the above resist is peeled off stoste, hydroxylamine solution, pure water and deployed in advance resist azanol system and peeled off the resist concentration determination liquid device for supplying of at least a supply in the resist lift-off processing groove in the new liquid; And one be used for measuring by extinction photometer that the resist azanol is the azanol concentration of stripper in the resist lift-off processing groove, and in view of the above resist is peeled off the azanol concentration determination liquid device for supplying of at least a supply in the resist lift-off processing groove in stoste, hydroxylamine solution and the pure water.
3. corrosion inhibitor stripping liquid control device, it is characterized in that this control device has one and is used for that to measure resist azanol in the resist lift-off processing groove be the stripper resist concentration of dissolving and in view of the above resist is peeled off stoste, hydroxylamine solution, pure water and deployed in advance resist azanol system and peeled off the resist concentration determination liquid device for supplying of at least a supply in the resist lift-off processing groove in the new liquid by extinction photometer; And one be used for measuring by extinction photometer that the resist azanol is that the moisture concentration of stripper and at least a supply of in view of the above resist being peeled off stoste, hydroxylamine solution and pure water are measured the liquid device for supplying to the moisture concentration in the resist lift-off processing groove in the resist lift-off processing groove.
4. corrosion inhibitor stripping liquid control device, it is characterized in that this control device has one and is used for that to measure resist azanol in the resist lift-off processing groove be the azanol concentration of stripper and will be that the resist of stripper constituent is peeled off the azanol concentration determination liquid device for supplying of at least a supply in the resist lift-off processing groove in stoste, hydroxylamine solution and the pure water as the resist azanol in view of the above by extinction photometer; And one be used for measuring by extinction photometer that the resist azanol is that the moisture concentration of stripper and at least a supply of in view of the above resist being peeled off stoste, hydroxylamine solution and pure water are measured the liquid device for supplying to the moisture concentration in the resist lift-off processing groove in the resist lift-off processing groove.
5. corrosion inhibitor stripping liquid control device, it is characterized in that this control device has one and is used for that to measure resist azanol in the resist lift-off processing groove be the stripper resist concentration of dissolving and will be that the resist of stripper constituent is peeled off stoste, hydroxylamine solution, pure water and deployed in advance resist azanol system and peeled off the resist concentration determination liquid device for supplying of at least a supply in the resist lift-off processing groove in the new liquid as the resist azanol in view of the above by extinction photometer; One is used for that to measure resist azanol in the resist lift-off processing groove be the azanol concentration of stripper and in view of the above resist is peeled off the azanol concentration determination liquid device for supplying of at least a supply in the resist lift-off processing groove in stoste, hydroxylamine solution and the pure water by extinction photometer; And one to be used for measuring resist azanol in the resist lift-off processing groove by extinction photometer be that the moisture concentration of stripper and at least a supply of in view of the above resist being peeled off in stoste, hydroxylamine solution and the pure water are measured the liquid device for supplying to the moisture concentration in the resist lift-off processing groove.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP09311403A JP3126690B2 (en) | 1997-10-27 | 1997-10-27 | Resist stripper management system |
| JP311403/1997 | 1997-10-27 | ||
| JP311403/97 | 1997-10-27 |
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| Publication Number | Publication Date |
|---|---|
| CN1215850A CN1215850A (en) | 1999-05-05 |
| CN1108541C true CN1108541C (en) | 2003-05-14 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN98108312A Expired - Fee Related CN1108541C (en) | 1997-10-27 | 1998-05-12 | Corrosion inhibitor stripping liquid control device |
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| Country | Link |
|---|---|
| JP (1) | JP3126690B2 (en) |
| KR (1) | KR100276561B1 (en) |
| CN (1) | CN1108541C (en) |
| TW (1) | TW373237B (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107193189A (en) * | 2016-03-14 | 2017-09-22 | 株式会社平间理化研究所 | The modulating device of the modulating device of water system anticorrosive additive stripping liquid controlling and non-water system anticorrosive additive stripping liquid controlling |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3914721B2 (en) * | 2001-06-25 | 2007-05-16 | 株式会社平間理化研究所 | Non-aqueous resist stripping solution management apparatus and non-aqueous resist stripping solution management method |
| JP3914722B2 (en) * | 2001-06-25 | 2007-05-16 | 株式会社平間理化研究所 | Water-based resist stripping solution management apparatus and water-based resist stripping solution management method |
| KR100481277B1 (en) * | 2002-05-10 | 2005-04-07 | 한국디엔에스 주식회사 | Device and Method for manufacturing semiconductor |
| JP4365404B2 (en) * | 2006-12-28 | 2009-11-18 | 東京エレクトロン株式会社 | Resist solution supply apparatus and substrate processing system |
| CN101685273B (en) * | 2008-09-26 | 2014-06-04 | 安集微电子（上海）有限公司 | Cleanout fluid for removing photoresist layer residue |
| KR101958387B1 (en) * | 2011-07-28 | 2019-03-20 | 주식회사 동진쎄미켐 | Method of controlling copper-film etching process and method of regenerating copper-film etchant composition using near infrared spectrometer |
| JP6098790B2 (en) * | 2012-10-11 | 2017-03-22 | パナソニックＩｐマネジメント株式会社 | Method and apparatus for preparing resist stripping solution |
| CN103913959B (en) * | 2014-03-27 | 2017-09-26 | 京东方科技集团股份有限公司 | The stripping off device and stripping means of a kind of photoresist |
| JP6562789B2 (en) * | 2015-09-10 | 2019-08-21 | キヤノン株式会社 | Removal method of object to be removed |
| CN108645959A (en) * | 2018-06-27 | 2018-10-12 | 深圳市华星光电技术有限公司 | Monitor the method that amine concentration changes in stripper |
| CN116373457A (en) * | 2021-12-30 | 2023-07-04 | 细美事有限公司 | Substrate processing liquid supply device, substrate processing system, and substrate processing method |
-
1997
- 1997-10-27 JP JP09311403A patent/JP3126690B2/en not_active Expired - Fee Related
-
1998
- 1998-03-04 TW TW087103143A patent/TW373237B/en not_active IP Right Cessation
- 1998-05-12 CN CN98108312A patent/CN1108541C/en not_active Expired - Fee Related
- 1998-05-21 KR KR1019980018331A patent/KR100276561B1/en not_active IP Right Cessation
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107193189A (en) * | 2016-03-14 | 2017-09-22 | 株式会社平间理化研究所 | The modulating device of the modulating device of water system anticorrosive additive stripping liquid controlling and non-water system anticorrosive additive stripping liquid controlling |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH11133630A (en) | 1999-05-21 |
| CN1215850A (en) | 1999-05-05 |
| TW373237B (en) | 1999-11-01 |
| KR100276561B1 (en) | 2000-12-15 |
| KR19990036502A (en) | 1999-05-25 |
| JP3126690B2 (en) | 2001-01-22 |
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