CN1196032C - Stripping agent, stripping method, stripping agent circulation equipment and stripping agent controller - Google Patents
Stripping agent, stripping method, stripping agent circulation equipment and stripping agent controller Download PDFInfo
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- CN1196032C CN1196032C CN 99119693 CN99119693A CN1196032C CN 1196032 C CN1196032 C CN 1196032C CN 99119693 CN99119693 CN 99119693 CN 99119693 A CN99119693 A CN 99119693A CN 1196032 C CN1196032 C CN 1196032C
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Abstract
A stripping agent for stripping resist from substrate, stripping method thereof, stripping agent circulation device and stripping agent control device, when making the semiconductor device and the LCD. The stripping agent includes organic amine compound, proton dialcohol ether compound, non-proton multiple polar compound and alkyl pyrrolidone compound, a resist layer experienced chemical and/or physical change can be easily stripped during corrosion process with low temperature in short time, meanwhile hardly corroding metallic thread. In addition, during heating, the stripping agent is vaporized little, so exchanging period of the stripping agent becomes longer. In addition, the stripping agent can be easily regenerated by vaporizing and compositions complementing. The stripping agent recirculation device with structure claimed by the claim 12 can easily regenerate waste stripping agent by vaporizing and compositions complementing. The stripping agent control device with structure claimed by the claim 16 can automatically control compositions of the stripping agent and can automatically provide the stripping agent to the stripping device.
Description
The present invention relates to resist stripping composition (hereinafter being " remover "), use remover to peel off the stripping means of resist, remover recirculation device and stripping agent controller, be particularly related to when making semiconductor devices and liquid crystal display (LCD), peel off the remover of resist from substrate, use remover to peel off the stripping means of resist, remover recirculation device and stripping agent controller.
When making as during the semiconductor devices of integrated electricity (IC), large scale integrated circuit (LSI), VLSI (very large scale integrated circuit) (VLSI) or LCD etc., need repeating a large amount of light etching process.Each light etching process is undertaken by following steps.
At first, resist is spin-coated on and has as on the Semiconductor substrate of the following structure of metal level etc. or form resist layer on the glass substrate.Then, shine on the photoresist layer by mask, on resist layer, form the latent image of figure thus with predetermined pattern as the high energy dynamic rays of ultraviolet ray, electron beam or X ray etc.Subsequently, the development resist layer forms the resist figure identical with above figure.Then, use the resist figure as etching mask wet or dry corrosion Semiconductor substrate or glass substrate, thus with figure transfer on Semiconductor substrate or glass substrate.At last, use remover combination to remove the resist figure.
The aqueous solution of inorganic acid aqueous solution, inorganic base or organic solution have been used as and have peeled off.For example, the open No.Sho 64-42653 of Japanese Patent Laid discloses a kind of remover that contains the potpourri of aromatic hydrocarbon and alkyl benzene sulphonate, the open No.Sho 62-49355 of Japanese Patent Laid discloses a kind of remover that contains ethylene oxide adduct, sulfonated compound and the ethylene glycol monoalkyl ether of alkanolamine, polyalkylene polyamine, and the open No.Sho 64-81950 of Japanese Patent Laid discloses the remover that contains 50% following amino alcohol.
Yet, because above remover is poisonous and corroding metal layer excessively.Therefore, the remover that does not preferably have this problem usually based on organic solvent.This remover is disclosed in the open No.Heisei 4-124668 of Japanese Patent Laid, the open No.Heisei 4-350660 of Japanese Patent Laid, the open No.Heisei 5-273768 of Japanese Patent Laid, and among the open No.Heisei 5-281753 of Japanese Patent Laid.Yet described organic remover has weak stripping ability.
Simultaneously, the useless remover of collecting after the stripping technology contains photoresist (hereinafter being called " resist ") and water.Usually, this useless remover passes through burning disposal.Yet incineration gases is discharged in the air during burning, and has polluted environment thus.In addition, the reusable composition of useless remover is also processed have been fallen, so also uneconomical.Thus, developing remover recirculation device and stripping agent controller will be of great use, and useful thus composition separates with useless remover and is used for reusing.Particularly, along with the quick increase of the sizes of substrate of LCD, the amount of the remover that stripping technology needs also sharply increases.Therefore, the amount that needs along with the increase remover of substrate significantly increases together, is starved of this device.
In addition, according to the batch-type stripping technology of routine, the substrate that the remover of scheduled volume is used to the to peel off scheduled volume wherein amount of substrate rule of thumb determines.Then, fully change used remover.Though the replacement cycle of remover is depended on the type and the size of substrate, in general, about per 12 hours of the replacement cycle of remover once.
In addition, by with the resist composition in the reaction of sour composition, by the vaporization loss that heating and stripping reaction cause, the concentration that is contained in the organic amine compound in the remover reduces, and has reduced stripping ability thus.Thus, As time goes on, the dissolution velocity of resist reduces, and can not remove resist fully, causes the unstable and low yield rate of quality.In addition, necessary shut-down operation is to change remover, and the operating speed of peel-off device reduces thus.In addition, the replacing of remover has increased manufacturing cost.
Overcome the above problems, first purpose of the present invention provides a kind of remover, can: in the following short time of low temperature, peeling off the resist layer that has experienced chemistry and/or physical change during the etching process; Basically do not corrode following metal level; Make composition change minimum by heating and reduce vaporization loss, so that the replacement cycle of remover prolongs; Needn't be with an organic solvent only water just can easily clean; And by the easy recycle use of distillation.
Second purpose of the present invention provides a kind of method of using remover to peel off resist.
The 3rd purpose of the present invention provide a kind of can recycle the remover recirculation device of useless remover.
The 4th purpose of the present invention provides a kind of stripping agent controller; can automatically control the component of remover; and can automatically remover be provided to peel-off device, in predetermined scope, keep stripping ability thus, and the amount of the remover that reduces to use and equipment downtime.
Reach first purpose of the present invention, a kind of remover is provided, comprise organic amine compound, proton glycol ethers compound, non-proton multipolarity compound and alkyl pyrrolidine ketonic compound, wherein the content of organic amine compound is 10～35wt%, the total content of proton glycol ethers compound and non-proton multipolarity compound is 60～85wt%, the content of alkyl pyrrolidine ketonic compound is 0.1～5wt%, and each is all based on the general assembly (TW) of remover.
The content of preferred alkyl pyrrolidone-2 compounds is 0.3～1wt% of remover general assembly (TW).
Preferred organic amine compound is at least one that is selected from following group: Armeen, secondary aliphatic amine, aliphatic tertiary amine, aliphatic cyclic amine, aromatic amine, heterocyclic amine and hydramine.
Preferred proton glycol ethers compound is at least one that is selected from following group: glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, glycol monomethyl phenyl ether, diethylene glycol monoether, diethylene glycol monobutyl ether, diethylene glycol monoethyl ether, dipropylene glycol monomethyl ether, the single ether of dipropylene glycol, the single propyl ether of dipropylene glycol and dipropylene glycol monobutyl ether.
Preferred non-proton multipolarity compound is at least one that is selected from following group: dimethyl sulfoxide (DMSO), dimethyl acetamide, dimethyl formamide, methylimidazole alkane ketone, sulfolane and N-Methyl pyrrolidone.
The preferred alkyl pyrrolidone-2 compounds is at least one that is selected from following group: N-cyclohexyl-2-Pyrrolidone, N-octyl group-2-Pyrrolidone, N-dodecyl-2-Pyrrolidone.
Reach second purpose of the present invention, a kind of method of peeling off resist is provided, wherein according to the present invention, predetermined material layer figure of deposit sequentially contacts with remover with the substrate that forms the material layer figure with the resist figure that is used as etching mask on it.
Preferably before substrate contact remover, use the plasma etching agent on the resist figure, to carry out cineration technics.
The preferred material layer is formed by at least one that is selected from following group: silicon (Si), tantalum (Ta), titanium (Ti), chromium (Cr), molybdenum (Mo), tungsten (W), tin (Sn), nickel (Ni), aluminium (Al), monox (Si
xO
y), silicon nitride (Si
xN
y) and tin indium oxide (ITO).
Reach the 3rd purpose of the present invention, a kind of remover recirculation device is provided, comprising: the first distillation unit, remove from useless remover and anhydrate; The after-fractionating unit receives and removes the useless remover that anhydrates from the first distillation unit, and removes the resist of dissolving from useless remover; Supplementary units is replenished first composition and second composition with the useless remover of regenerating in the useless remover that the after-fractionating unit provides.
The preferred first distillation unit comprises: the distillation column that distills water from useless remover; The retort gas that will contain the water vapor that evaporates in the distillation column is condensed into the condenser of the distillate that contains water; If desired, the distillate that will contain water turns back to the feedback pipe of distillation column; The water recoverer of the water that storage condenser condenses; And the pressure in the reduction distillation column is to reduce the vacuum pump of evaporation of water temperature.
Preferred after-fractionating unit comprises: the distillation column that removes the useless remover that anhydrates that distillation is provided by the first distillation unit; The condenser of the remover that distills in the condensation distillation column; If desired, the remover of the distillation of condenser condenses is turned back to the feedback pipe of distillation column; The remover recover of the remover that storage is condensed by condenser; And vacuum pump, the pressure in the reduction distillation column is to reduce the evaporating temperature of useless stripper.
The preferred addition unit comprises: the analytical equipment of the remover component of the distillation that analysis after-fractionating unit provides; On the basis of the component of analyzing, replenish the supplementary device of first kind of composition and second kind of composition; And with the remover that distills and first kind and second kind of mixing arrangement that composition mixes of replenishing.
Preferred first and second compositions are respectively organic amine compound and non-proton multipolarity compound.
Reach the 4th purpose of the present invention, provide a kind of stripping agent controller to comprise: useless remover memory storage, detect the concentration of the resist that dissolves in the useless remover, the remover that will give up is transported to remover and coagulates supplying apparatus, if the resist concentration of dissolving is equal to or less than predetermined amount, can be used for so reusing and needn't be further processed, if the resist concentration of dissolving surpasses predetermined amount, the remover that will give up so is transported to the remover recirculation device and regenerates; The remover recirculation device removes the resist that anhydrates and dissolve from the useless remover that useless remover memory storage provides, and first kind of composition and second kind of composition in the useless remover of additional gained, with the useless remover of regenerating; The remover memory storage mixes the remover of remover recirculation device regeneration, and stores potpourri with new remover; And the remover generator, the remover that reception and mixing are carried from the remover memory storage, useless remover is directly carried by useless remover memory storage, and first kind of composition provided by external source, and potpourri is provided to peel-off device.
Preferred first kind and second kind of composition are respectively organic amine compound and non-proton multipolarity compound.
To the detailed introduction of preferred embodiment, above purpose of the present invention and advantage will become obviously by with reference to the accompanying drawings, wherein:
Fig. 1 is for showing the structural representation of remover recirculation device according to the present invention;
Fig. 2 is the structural representation of the stripping agent controller according to the present invention;
The calibration curve of Fig. 3 for concerning between the resist concentration of dissolving and the absorbance log of UV spectrometer, measure.
At first introduce according to remover of the present invention.Remover comprises organic amine compound, proton glycol ethers compound, non-proton multipolarity compound and alkyl pyrrolidine ketonic compound, wherein the content of organic amine compound is 10～35wt%, the total content of proton glycol ethers compound and non-proton multipolarity compound is 60～85wt%, the total content of alkyl pyrrolidine ketonic compound is 0.1～5wt%, and each is all based on the general assembly (TW) of remover.
Preferred organic amine compound is at least one that is selected from following group: Armeen, secondary aliphatic amine, aliphatic tertiary amine, aliphatic cyclic amine, aromatic amine, heterocyclic amine and hydramine.The Armeen of preferred especially as monoethanolamine etc., be since its molecular weight very little it can be penetrated in the resist layer well during stripping technology, dissolve easily or the expansion resist layer.
The content of organic amine compound can for 10～35wt%, preferred 15～30%, based on the general assembly (TW) of remover.If the content of organic amine compound is less than 10wt%, remover can not fully be peeled off the resist layer that has experienced chemistry and/or physical change during etching process so.Simultaneously, if the content of organic amine compound has surpassed 35wt%, the corrosion to lower metal layer increases so.
Second kind of composition according to remover of the present invention is proton glycol ethers compound and non-proton multipolarity compound, for mix with organic amine compound good neutral flux.
Proton glycol ethers compound is at least one that is selected from following group: glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, glycol monomethyl phenyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, dipropylene glycol monomethyl ether, the single ether of dipropylene glycol, the single propyl ether of dipropylene glycol and dipropylene glycol monobutyl ether.Preferred especially diethylene glycol monobutyl ether and dipropylene glycol monomethyl ether, they have low surface tension and high-flash.
The example of above-mentioned proton glycol ethers compound can use in independent or two or more mixing.Yet preferred mixture.In addition, when mixing two kind of proton glycol ethers, preferred 5: 95～95: 5 ratio.For example, when the single ether of diethanol and dipropylene glycol monomethyl ether are used as proton glycol ethers compound, preferred 30: 70-70: 30 ratio.
Non-proton multipolarity compound is at least one that is selected from following group: dimethyl sulfoxide (DMSO), dimethyl acetamide, dimethyl formamide, methylimidazole diketone, sulfolane and N-Methyl pyrrolidone.Preferred dimethyl sulfoxide (DMSO) and the N-Methyl pyrrolidone of using, they have the solubleness greater than 10, molecular breakdown or distortion that very strong anti-distillation heating causes, and good mixing character is arranged with water.
Proton glycol ethers compound and non-proton multipolarity compound can be used as neutral flux to be added to according in the remover of the present invention, and it is also very effective not mix use even use separately.Yet, preferably mix these two kinds of compounds to obtain more performance.The total content of neutral flux can be 60～85wt%, preferred 65～80wt%.The preferred content of determining neutral flux makes the reduction minimum of the stripping performance that vaporization loss causes between the long period of heating, and can peel off the resist layer that has experienced chemistry and/or physical change by etching process fully.Thus, can prolong replacement cycle of remover, make the remover of specified rate peel off more substrate quantity as much as possible thus according to remover of the present invention.
According to the third composition of the present invention, the alkyl pyrrolidine ketonic compound can be N-cyclohexyl-2-Pyrrolidone, N-octyl group-2-Pyrrolidone, N-dodecyl-2-Pyrrolidone.The alkyl pyrrolidine ketonic compound is non-ionic surfactant, compares with anionic surface active agent or cationic surfactant and has reduced wetting time.In addition, because the alkyl pyrrolidine ketonic compound has small-sized molecular structure, so compound can be easily mobile in solvent, and reduced surface tension very soon.Particularly N-octyl-2-Pyrrolidone is because its little hydrophilic radical has minimum dynamic surface tension, therefore very effective.
The content of alkyl pyrrolidine ketonic compound is 0.1～5wt%, preferred 0.3-1wt%.If the content of alkyl pyrrolidine ketonic compound is less than 0.1wt%, when peeling off the resist layer that has experienced chemistry and/or physical change by etching process, the effect of surfactant can be ignored so.Simultaneously, if the content of alkyl pyrrolidine ketonic compound surpasses 5wt%, owing to compare its cost height with the capillary effect of its reduction, therefore uneconomical.Can be used alone the alkyl pyrrolidine ketonic compound.Yet,, preferably use the potpourri of two or more alkyl pyrrolidine ketonic compounds owing to Synergistic.
Introduce the method for remover according to the present invention of using now from the substrate desquamation resist.
Use is according to remover of the present invention, and by usual way promptly, the substrate that has resist layer with the remover contact is peeled off resist from substrate.Be sprayed on the described contact of acquisition on the substrate by substrate being immersed in the remover or with remover.Here, can use any contact method, without any restriction.
According to remover of the present invention of great use, can peel off in dry corrosion, wet corrosion and/or ashing or experienced the resist of chemistry and/or physical change on metal level or the insulation course under the serious condition of isolated secondary product.
Here, metal level or insulation course can be by silicon (Si), tantalum (Ta), titanium (Ti), chromium (Cr), molybdenum (Mo), tungsten (W), tin (Sn), nickel (Ni), aluminium (Al), monox, silicon nitride and tin indium oxides.
With reference now to the recirculation device of Fig. 1 introduction according to remover of the present invention.
With reference now to Fig. 1,, is divided into three parts: first distillation unit A, after-fractionating unit B and the supplementary units C according to the recirculation device of remover of the present invention.The first distillation unit A removes from useless remover and anhydrates, and the after-fractionating unit B has been removed the resist of removing dissolving the useless remover that anhydrates from the first distillation unit A.Supplementary units C receives the useless remover that has removed the resist that anhydrates and dissolve from after-fractionating equipment in addition, and add inorganic amine compound and non-proton multipolarity compound to useless remover, so that useless remover has identical or similar component with former remover.
Here, introduce the principle of work be presented among Fig. 1 according to the recirculation device of remover of the present invention below.
Here, reference number 1 expression is stored provisionally from the storage box of the useless remover of peel-off device 30 (see figure 2)s recovery.At first, when detecting the amount that is stored in the useless remover in the storage box 1, first load unit 1 ' surpasses predetermined amount amount, the first controller (not shown) output signal that is connected to first load unit 1 ' is opened first flow control valve 2 ', and operate first transfer pump 2, the remover that will give up thus is sent to distillation water tower 3.Useless remover heats in the distillation water tower, has the water of minimum boiling point by heating evaporation.Here, avoid at high temperature heating decomposition or variation to prevent remover.For this reason, vacuum pump 7 has reduced the pressure in the distillation water tower 3, so that reduce the temperature of water evaporation.The water vapour of evaporation is condensed into water by condenser 4 in distillation water tower 3, is stored in then in the water collection box 6.When second load unit 6 ' detects in the water collection box 6 water yield that reclaims and surpasses predetermined amount, the second controller (not shown) output signal that is connected to second load unit 6 ' is opened second flow control valve 8 ', and operates second transfer pump 8 water that reclaims is discharged into the outside.In addition, when the concentration by the organic amine compound of the distillate of organic amine titrator 4 ' titration surpasses predetermined amount, the 3rd controller 4 " output signal closes the 3rd flow control valve 5 '; open the 4th flow control valve 5 simultaneously ", operate the 3rd transfer pump 5 , distillate is fed back to distillation water tower 3 by feedback pipe 5.Distillation water tower 3 reaches after the stable status, when by the concentration of the organic amine compound of the distillate of organic amine titrator 4 ' titration during less than predetermined amount, the 3rd controller 4 " output signal opens the 3rd flow control valve 5 '; close the 4th flow control valve 5 simultaneously ", and stopping the operation of the 3rd transfer pump 5 , the water with distillation is sent to water collection box 6 thus.As previously mentioned, in the recirculation device of remover of the present invention, determine whether that by organic amine titrator 4 ' distillate feeds back to distillation water tower 3 or distillate is sent to water collection box 6 by the feedback pipe.Yet, can carry out described definite according to imposing a condition of the distillation water tower of making by experience 3.
Then, when the amount of the distillate that flows into organic amine titrator 4 ' is lower than predetermined amount, the 3rd controller 4 " output signal closes vacuum pump 7; open the 5th flow control valve 9 ' simultaneously; and operate the 4th transfer pump 9, will in the first distillation unit A, remove the remover distillation column (being abbreviated as " distillation column ") 11 that the useless remover that anhydrates be sent to the after-fractionating unit B thus.
For the resist composition with dissolving separates from the remover that gives up, distillation column 11 distillation removers, and, arrive the resist composition that accumulates in the dissolving of bottom outside as trash discharge by operating resist emptying pump 18 by resist bleed valve 18a.Here, vacuum pump 15 has reduced the pressure in the distillation column 11.The remover of evaporation condenses by condenser 12 and is stored in the remover collection box 14 in distillation column 11.When the amount that detects the useless remover that reclaims in the useless remover collection box 14 when the 3rd load unit 10 surpasses predetermined amount, the 4th controller (not shown) output signal that is connected to the 3rd load unit 10 is opened the 6th flow control valve 16 ', and operate the 5th transfer pump 16, by gas chromatography (GC) unit 19 of supplementary units C, the remover that distills is sent to blending bin 26 thus.In addition, if desired, close the 7th flow control valve 13 ', open the 8th flow control valve 13 simultaneously ", operate the 6th transfer pump 13 , turn back to distillation column 11 by feedback pipe 13 removers thus with distillation.
The component of the distillation remover that flows in it is analyzed in the GC unit 19 of supplementary units C.The 5th controller 20 is according to the component analysis of GC unit 19, the amount of organic amine compound that calculating lacks and non-proton polarization compound, output signal is opened the 9th flow control valve 22 ' and the tenth flow control valve 23 ', and operate the 7th transfer pump 22 " and the 8th transfer pump 23 ", the organic amine compound and the non-proton polarization compound that provide case 22 and non-proton polarization compound that case 23a is provided from organic amine compound respectively are provided thus are used to the remover of regenerating.When the 4th load unit 21 and the 5th load unit 23 detect the organic amine compound that adds requirement respectively and non-proton polarization compound, the 5th controller 20 output signals are closed the operation of the 9th and the tenth flow control valve 22 ' and 23 ', and stop the 7th and the 8th transfer pump 22 " and 23 " operation, stop to provide organic amine compound and non-proton polarization compound thus.
Then, GC unit 19 takes out a spot of regeneration remover by feedback pipe 24 and feedback pump 25 from blending bin 26, analyzes the component of regeneration remover.If the content that can determine organic amine compound and non-proton polarization compound from the data of analyzing is in predetermined amount, the 5th controller 20 output signals are opened the 11 flow control valve 27 ' so, and operate the 9th transfer pump 27, the remover of will regenerating thus is discharged into the outside.
Next, introduce the stripping agent controller of the remover recirculation device that adopts Fig. 1 of the present invention with reference to figure 2.
With reference to figure 2, by being sprayed on, remover in peel-off device 30, carries out stripping technology on the substrate 35 by nozzle 33.When first load unit 36 detects the amount that is collected in the useless remover 37 in the peel-off device 30 and reaches predetermined amount, the first controller (not shown) output signal that is connected to first load unit 36 is operated first transfer pump 39, is sent to useless remover storage box 43 by first flow control valve 41 remover that will give up thus.Useless remover is stored in that the amount up to useless remover reaches predetermined amount in the useless remover storage box 43.Check the amount that is collected in useless remover in the storage box 43 by second load unit 45.When the amount of the useless remover of collecting reached predetermined amount, the second controller (not shown) output signal that is connected to second load unit 45 stopped the operation of first transfer pump 39 and closes first flow control valve 41.
Then, a spot of useless remover flows in the UV spectrometer 49 from storage box 43 by managing 47, measures the absorbance log of useless remover, detects the concentration of the resist that dissolves in the useless remover thus.
Here, use UV spectrometer 49 to detect before the concentration of the resist that in remover, dissolves, must prepare the calibration graph that concerns between the concentration of the resist that dissolves and the absorbance log, as shown in Figure 3.Here, measure absorbance log at the wavelength (λ) of 353nm.
When the concentration of the resist of the dissolving that detects by UV spectrometer 49 not have to surpass the amount of being scheduled to, the 3rd controller 51 output signals were opened second flow control valve 53, and operate second transfer pump 55.Thus, the remover that will give up is provided to useless remover provides case 57 with the useless remover of recycle, and regeneration does not need extra technology.When second load unit 45 detected useless remover fully from storage box 43 discharges, the 3rd controller 51 output signals were closed second flow control valve 53, and stop the operation of second transfer pump 55.
On the contrary, if UV spectrometer 49 detects in the time of can not re-using remover thus when the concentration of the resist of dissolving surpasses predetermined amount, the 3rd controller 51 output signals are opened the 3rd flow control valve 59 and the 3rd transfer pump 61, and the remover that will give up thus is sent to remover recirculation device 63.Here, remover recirculation device 63 is the identical device of introducing with reference to figure 1.When second load unit 45 detected useless remover fully from storage box 43 discharges, the 3rd controller 51 output signals were closed the 3rd flow control valve 59, and stop the operation of the 3rd transfer pump 61.
Remover recirculation device 63 removes the resist that anhydrates and dissolve from useless remover, and recharges the organic amine compound and the non-proton polarization compound of shortage, and regeneration has remover identical with former remover or similar components.By first flow control valve 65 and the 4th transfer pump 67, the remover of regenerating by remover recirculation device 63 is sent to remover storage box 69.
When the 3rd load unit 70 detected remover storage box 69 and collects the remover of scheduled volume, the 4th controller (not shown) output signal that is connected to the 3rd load unit 70 stopped the operation of the 4th transfer pump 67 and closes the 4th flow control valve 65.In addition, if desired, new remover can add storage box 69 from the outside to.
The 4th load unit 75 detects the amount that remover replenishes remover in the case 57.When the amount of remover is less than scheduled volume in replenishing case 57, the 5th controller (not shown) output signal that is connected to the 4th load unit 75 is operated the 5th transfer pump 73, and open the 5th flow control valve 71, from storage box 69 remover is provided to thus case 57 is provided, the amount of remover reaches predetermined amount in replenishing case 57.When the amount of remover reached predetermined amount in replenishing case 57, the 5th controller output signal stopped the operation of the 5th transfer pump 73, and closes the 5th flow control valve 71.
Organic amine compound is the key factor of appreciable impact remover stripping performance.Owing to react, heat the vapour loss and the stripping reaction that cause by sour composition with the resist component, the concentration that is contained in the organic amine compound in the remover reduces, and contains the small amounts of inorganic amines so directly be provided to the useless remover that replenishes case 57 from storage box 43 by second flow control valve 53.Thus, if desired, add additional case 57, can keep being contained in the stripping performance that replenishes the remover in the case 57 by inorganic amine compound with requirement.
For this reason, a spot of remover flows to amine titrator 79 interior content with organic amine compound in the remover the additional case 57 of titration by pipe 77 from replenishing case 57.When the concentration of the organic amine compound of titration was lower than predetermined amount, the 6th controller 81 output signals were opened the 6th flow control valve 85 and the 6th transfer pump 83, from the additional case 87 of organic amine compound organic amine compound were provided to thus and replenished case 57.Here, be calculated as by the 6th controller 81 and remain on the amount of the organic amine compound that predetermined amount will add replenishing remover concentration in the case 57.The 5th load unit 89 is measured from replenishing the amount of the organic amine compound that case 57 provides, and the result is sent to the 6th controller 81.When the amount of the organic amine compound of measuring by the 5th load unit 89 that provides equaled the requirement of organic amine compound, the 6th controller 81 output signals were closed the operation that the 6th stream send operation valve 85 and stops the 6th transfer pump 83.
Subsequently, the 6th controller 81 output signals are opened the 7th flow control valve 93, and operate the 7th transfer pump 91, by the nozzle 33 spraying removers of peel-off device 30.Here, be provided to before the peel-off device 30, remover passes removes particulate filtration device 95.
Here, at length introduce the present invention with reference to following Example.Yet the present invention is not limited to following Example.In the example below, if there is not special stripping to point out that number percent and blending ratio are based on weight.In below the example and Comparative Examples, the performance of assessment remover.
Test 1: the stripping performance of remover
The preparation of sample
The positive resist composition (DTFR-1011SK of Shi Yonging widely, by Dong-Jin CHEMICAL CO., LTD makes) be deposited on glass substrate (on 1.1mm * 60mm * 70mm) with the aluminium that thickness is 200nm (Al) or chromium (Cr), 110 ℃ were heated 90 seconds down on hot plate, and the dry thus resist layer thickness that forms afterwards is 1.5 μ m.
After the mask that will have a predetermined pattern is placed on the resist layer, irradiation UV ray, use 2.38% tetramethylammonium hydroxide (TMAH) developer solution (DPD-100S, by Dong-Jin CHEMICAL CO., LTD makes) 20 ℃ of development resists 90 seconds, in being set to the baking oven of 120 ℃, 140 ℃, 160 ℃ or 180 ℃, cured firmly 15 minutes then, on Al or Cr metal level, form predetermined resist figure thus.
The sample that obtains is immersed in and contains in the mordant of ceric ammonium nitrate as principal ingredient, and the metal level that corrosion is not covered by the resist figure forms metal layer image thus.Then, use the washed with de-ionized water sample, and at N
2Dry in the atmosphere.
Disbonded test
Sample was immersed in 70 ℃ the remover 5 minutes.From remover, take out after the sample, use the washed with de-ionized water sample, and at N
2Dry in the atmosphere.Whether leave remaining resist between the line of use scanning electron microscope (SEM) inspection metal layer image and on the surface of metal layer image, the stripping performance assessment is as follows.The results are shown in the table 2.
In table 2, the situation that mark zero expression resist residue is fully removed from the space between the line of surface and metal layer image, mark △ represents the situation that the resist residue is partly removed from the space between the line of surface and metal layer image, and mark * expression resist residue is stayed the whole lip-deep situation of metal layer image with the form of film.
Simultaneously, positive photolithographic gelatin composition DTFR-1011SK forms composition, quinonediazide compound by water soluble alkali Novolak resin as film and forms as the composition of photoresists and the organic solvent that can dissolve this composition.
Test 2: the serviceable bife of remover
In order to assess the long stripping technology stripping performance of remover afterwards, the remover of using the simulation remover respectively 2,000 or 4,000 8 inches Semiconductor substrate to be carried out the condition of stripping technology carries out the test 1 of above introduction.That is to say that dissolving resist that the simulation remover contains and liquid water content are identical with the remover of peeling off resist from 2,000 or 4,000 8 inches Semiconductor substrate respectively.Here, as 1 sample introduces in preparing to testing, forming the Cr layer is metal level, cures firmly under 120 ℃, 140 ℃, 160 ℃ or 180 ℃ respectively after the deposit resist layer.Carry out disbonded test in 5 minutes by sample being immersed in 70 ℃ the remover, from remover, take out sample then.With order assessment stripping performance identical in the test 1, the result is presented in the table 3.
Test 3: to the corrosion property of metal level
Obtain 10,20 and 30 samples with test 1 identical method, each all has Al or Cr metal level, is immersed in respectively in 20 liters of removers of 70 ℃ 10 minutes.From remover, take out sample then, by at inductively coupled plasma mass spectrometry instrument (ICP-MS, ELAN6000, PERKIN-ELMER Co., electric evaporator (ETV) measurement is installed USA) is dissolved into the interior Al of remover or the amount of Cr ion, the result is that unit representation is in table 4 with ppb.
Test 4: the loss in weight that evaporation causes
The remover of 100 grams is placed in the glass beaker of 5 cm diameters, and is heated to 70 ℃.Then respectively through 1,2, measure the weight and the change of component of the remover that evaporation causes after 5,10 and 20 hours.The result is presented in table 5 and 6.In table 5, demonstrate the weight of evaporation minimizing, the value meaning of band minus sign is the weight that absorbs the remover of steam increase from air.Using gases stratographic analysis meter (HP-5890SERIES II, Mfg Co.; HEWLETT PACKARD COMPANY) change of component of the remover of listing in the analytical table 6, the result represents with percentage.
Test 5: the content of organic amine compound
This test is whether research amine titrator can be measured exactly in the concentration of peeling off the organic amine compound that takes place during the heating process of resist and reduce.To simulate from 2,000 or 4, the remover of peeling off on 000 8 inches Semiconductor substrate under the condition of resist is heated to 70 ℃, (682Titropcesser, Metrohm AG Co. Switzerland) adopt usual way 1 to use the amine titrator, 2, the remover of sampled analog is measured the content of organic amine compound after 5,10,20 and 40 hours.In addition, the organic amine compound of supplement consumed after 20 and 40 hours, the content of organic amine compound is initial amount thus, promptly 20wt% uses the amine titrator to measure the content of amine after 10 minutes.
The amine content of measuring with percentages show in table 7.In addition, whether accurate in order to study the amine content of measuring by the amine titrator, using gases stratographic analysis meter (HP-5890 SERIES II, Mfg Co.; HEWLETT PACKARD COMPANY) analyze the change of component of remover after 20 and 40 hours, the result with percentages show in table 8.
Test 6: the distillation and the regeneration of useless remover
Whether the long-time useless remover that uses of this experimental study can be by refining regeneration.Use remover recirculation device distillation shown in Figure 1 to contain the resist of dissolving and the useless remover of water, produce and removed the resist of dissolving and the remover of water.Use GC to analyze the component of the remover that obtains.On the basis on the result who analyzes, replenish not enough composition, identical with the original components shown in the table 1, produce the remover of regeneration.Use GC to analyze the component of remover after distillation and the regeneration, the result is presented in the table 9.
Then, the remover of use the remover of initial (newly) respectively, having peeled off the useless remover of simulated conditions of 4,000 8 inches Semiconductor substrate and generation carries out the test 1 of above introduction.The results are shown in the table 10.
Test 7: by surfactant stripping performance and capillary variation
The type of this experimental evidence surfactant and content is the stripping performance and the surface tension of remover relatively.Test the stripping performance introduced in 1 and the change in the dynamic surface tension by changing the type and the content of surfactant, having studied.
Select alkyl pyrrolidine ketone derivatives (Lp-100, make by ISP Co.) and polyoxyethylene alkyl phenyl ether derivant (NOIGEN EA100, make by DKS International Co.) as non-ionic surfactant, (Koremul 290 for the sodium dioctyl sulphosuccinate derivant, make by HanNong CHEMICALSINC.) as anionic surface active agent, poly-ethoxyquin quaternary ammonium salt (ETHOQUAD C/25 is made by LION Co.) is as cationic surfactant.
Use PENANT DROP TENSIONMETET GPDA 10 (making) to measure dynamic surface tension by usual way by KR ü SS GmbH Germany.
According to the type of surfactant, the variation of stripping performance is presented in the table 11.Add the result who obtains table 11 in the remover of dimethyl sulfoxide (DMSO) (DMSO) of the diethylene glycol monoethyl ether (EDG) of the monoethanolamine (MEA) that contains 20wt%, 25wt% and 54.9wt% to by the 0.1wt% that every kind of activating agent of table 11 will be presented at.
Be presented in the table 12 according to the variation in the content dynamic surface tension of surfactant.The remover of DMSO by the surfactant in 0～1.0wt% scope being added to the MEA, the 25wt%EDG that contain 20wt% and 54～55wt% obtains the result of table 12.
＜example 1 to 7 ， ﹠amp; Comparative Examples 1 to 3 〉
On the basis of the component that table 1 is listed, obtain remover (example 1 to 7).Here, in the scope that the present invention requires, change the content of organic amine compound, neutral compound and surfactant.In addition, prepare remover (Comparative Examples 1 to 3) by the content that outside the scope of protection of present invention, changes organic amine compound, neutral compound and surfactant.
The test 1 of carrying out above introduction on the basis of the remover that obtains is to test 7.The results are shown in table 2 in 12.
Reference table 2, the remover of example 1 to 7 can be peeled off the resist layer that has experienced chemistry and/or physical change during etching process well as can be seen, and is irrelevant with lower metal layer and hard stoving temperature.In addition, when curing firmly under 120 ℃, the remover of Comparative Examples 1 to 3 demonstrates good stripping performance.Yet, when the temperature of curing firmly is increased to more than 140 ℃, the stripping performance variation of the remover of Comparative Examples 1 to 3.
Reference table 3, as can be seen when peeling off the resist layer that has cured firmly under 120 ℃, even peeled off after 4,000 8 inches the substrate, the stripping performance of the remover of example 1 to 7 still is equal to the stripping performance of new remover.In addition, when peeling off at 160 ℃ of resist layers that cure firmly, even resist layer has experienced chemistry and/or physical change during the corrosion, the stripping performance of having peeled off the useless remover of 2,000 8 inches substrates still is equal to the stripping performance of new remover.In addition, peeled off 4, even the stripping performance of the useless remover of 000 8 inches substrate is good unlike new remover, but its performance is still good.Thus, can use for a long time according to remover of the present invention as can be seen from the above results.
On the other hand, when peeling off at 140 ℃ of resist layers that cure firmly, even they are not have used new remover, the stripping performance of the remover of Comparative Examples 1 to 3 is very poor.Peeled off after 2,000 8 inches substrates, the further variation of stripping performance has been peeled off after 4,000 8 inches substrates, and remover can not be peeled off resist layer again, and is irrelevant with the temperature of curing firmly.
Table 1 remover is formed
| Organic amine compound | Proton glycol ethers compound | Non-proton multipolarity compound | ||||
| Type | Content wt% | Type | Content wt% | Type | Content wt% | |
| Example 1 | | 20 | | 25 | DMSO | 54.9 |
| Example 2 | | 20 | | 25 | NMP | 54.9 |
| Example 3 | | 20 | | 25 | DMSO | 54.9 |
| Example 4 | MEA | 30 | | 25 | NMP | 44.9 |
| Example 5 | MEA | 30 | | 25 | DMSO | 44.9 |
| Example 6 | | 20 | | 25 | DMI | 54.9 |
| Example 7 | MIPA | 30 | | 25 | Sulfolane | 44.9 |
| Comparative Examples 1 | | 5 | BTG+ | 15+30 | GBL | 49.9 |
| Comparative Examples 2 | | 9 | BTG+ | 10+40 | DMAc | 40.9 |
| Comparative Examples 3 | TEA | 40 | BTG+PGMEA | 35+20 | DMF | 4.9 |
| * abbreviation is expressed as follows N-octyl group-2-Pyrrolidone that all examples and Comparative Examples all contain 0.1wt%: MEA: monoethanolamine as surfactant *, MIPA: monoisopropanolamine, DEA: diethanolamine, TEA: triethanolamine, EDG: diethylene glycol monobutyl ether, BDG: diethylene glycol monobutyl ether, BTG: triethylene glycol monobutyl ether, DPM: dipropylene glycol monomethyl ether, PGME: propylene glycol monomethyl ether, PGMEA: acetic acid propylene glycol monomethyl ether, DMSO: dimethyl sulfoxide (DMSO), the NMP:N-methyl pyrrolidone, DMI: methylimidazole ketone, GBL: gamma-butyrolacton, DMAc: dimethyl acetamide, DMF: dimethyl formamide | ||||||
The stripping performance of table 2 remover
| The Cr substrate | The Al substrate | |||||||
| Hard stoving temperature, ℃ | Hard stoving temperature, ℃ | |||||||
| 120 | 140 | 160 | 180 | 120 | 140 | 160 | 180 | |
| Example 1 | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ |
| Example 2 | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ |
| Example 3 | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ |
| Example 4 | ○ | ○ | ○ | △ | ○ | ○ | ○ | △ |
| Example 5 | ○ | ○ | ○ | ○ | ○ | ○ | ○ | △ |
| Example 6 | ○ | ○ | ○ | ○ | ○ | ○ | ○ | △ |
| Example 7 | ○ | ○ | ○ | △ | ○ | ○ | ○ | ○ |
| Comparative Examples 1 | ○ | ○ | △ | × | ○ | ○ | △ | × |
| Comparative Examples 2 | ○ | ○ | △ | × | ○ | △ | × | × |
| Comparative Examples 3 | ○ | △ | △ | × | ○ | △ | × | × |
The serviceable life of table 3 remover
| The substrate quantity of peeling off | Hard stoving temperature ℃ (the Cr substrate is 70 ℃ of immersions) | ||||
| 120 | 140 | 160 | 180 | ||
| Example 1 | 0 | ○ | ○ | ○ | ○ |
| 2,000 | ○ | ○ | ○ | △ | |
| 4,000 | ○ | ○ | △ | △ | |
| Example 2 | 0 | ○ | ○ | ○ | ○ |
| 2,000 | ○ | ○ | ○ | △ | |
| 4,000 | ○ | ○ | △ | △ | |
| Example 3 | 0 | ○ | ○ | ○ | ○ |
| 2,000 | ○ | ○ | ○ | ○ | |
| 4,000 | ○ | ○ | △ | △ | |
| Example 4 | 0 | ○ | ○ | ○ | ○ |
| 2,000 | ○ | ○ | ○ | △ | |
| 4,000 | ○ | ○ | △ | △ | |
| Example 5 | 0 | ○ | ○ | ○ | ○ |
| 2,000 | ○ | ○ | ○ | △ | |
| 4,000 | ○ | ○ | ○ | △ | |
| Example 6 | 0 | ○ | ○ | ○ | ○ |
| 2,000 | ○ | ○ | ○ | △ | |
| 4,000 | ○ | ○ | △ | × | |
| Example 7 | 0 | ○ | ○ | ○ | ○ |
| 2,000 | ○ | ○ | ○ | △ | |
| 4,000 | ○ | ○ | △ | △ | |
| Comparative Examples 1 | 0 | ○ | ○ | △ | × |
| 2,000 | ○ | △ | × | × | |
| 4,000 | ○ | △ | × | × | |
| Comparative Examples 2 | 0 | ○ | △ | × | × |
| 2,000 | ○ | △ | × | × | |
| 4,000 | △ | × | × | × | |
| Comparative Examples 3 | 0 | ○ | △ | × | × |
| 2,000 | ○ | × | × | × | |
| 4,000 | × | × | × | × | |
The Al of table 4 corrosion and the amount (unit: ppb) of Cr ion
| Peel off the quantity of Cr substrate | Peel off the quantity of | |||||
| 10 | 20 | 30 | 10 | 20 | 30 | |
| Example 1 | 1.39 | 4.88 | 19.29 | 4.29 | 6.47 | 22.72 |
| Example 2 | 2.51 | 9.97 | 24.39 | 3.33 | 8.41 | 31.55 |
| Example 3 | 4.78 | 10.12 | 25.12 | 4.19 | 9.52 | 38.18 |
| Example 4 | 5.66 | 11.1 | 42.9 | 6.24 | 12.94 | 40.52 |
| Example 5 | 6.06 | 17.24 | 31.15 | 7.12 | 16.65 | 29.63 |
| Example 6 | 4.12 | 11.26 | 39.5 | 4.02 | 14.99 | 30.1 |
| Example 7 | 5.91 | 18.37 | 50.63 | 5.87 | 10.23 | 58.12 |
| Comparative Examples 1 | 5.99 | 21.98 | 101.3 | 7.95 | 25.83 | 145.62 |
| Comparative Examples 2 | 3.84 | 15.6 | 95.25 | 8.61 | 19.21 | 181.14 |
| Comparative Examples 3 | 4.2 | 18.51 | 74.9 | 5.89 | 21.68 | 85.37 |
As shown in table 4, to compare with Comparative Examples 1 to 3, the remover of example 1 to 7 seldom corrodes Al or Cr ion.Thus, can understand that remover according to the present invention seldom corrodes lower metal layer during stripping technology.
Table 5 is because the weight change (unit: g) of evaporation remover
| Evaporation time, hour | ||||||
| 0 | 1 | 2 | 5 | 10 | 20 | |
| Example 2 | 0 | -0.024 | 1.089 | 3.172 | 6.548 | 27.015 |
| Example 3 | 0 | 0.065 | 1.315 | 3.749 | 6.295 | 19.144 |
| Example 5 | 0 | -0.265 | 1.531 | 4.764 | 7.970 | 31.426 |
| Comparative Examples 2 | 0 | 0.151 | 1.541 | 5.171 | 10.115 | 40.819 |
Table 6 is because the change of component of evaporation remover
| Evaporation time, hour | Organic amine compound, % | Proton glycol ethers compound, % | Non-proton multipolarity compound, % | |
| Example 1 | 0 | 20 | 25 | 54.9 |
| 10 | 19.1 | 24.2 | 56.6 | |
| 20 | 18.1 | 23.6 | 58.2 | |
| Example 2 | 0 | 20 | 25 | 54.9 |
| 10 | 19.2 | 24.8 | 55.9 | |
| 20 | 18.3 | 24.1 | 57.5 | |
| Example 5 | 0 | 30 | 25 | 44.9 |
| 10 | 27.7 | 24.5 | 47.7 | |
| 20 | 26.4 | 23.8 | 49.7 | |
| Comparative Examples 2 | 0 | 9 | 10+40 | 40.9 |
| 10 | 6.9 | 9.7+35.1 | 48.2 | |
| 20 | 4.6 | 9.5+30.1 | 55.7 |
Compare with the remover of Comparative Examples 2, example 1,2 and 5 remover weight and change of component are seldom.Thus, the variation that the component of remover of the present invention is caused by heating seldom even peel off thus for a long time, also can keep its stripping performance, and is easy to by distillation recycle.In addition, when peeling off for a long time, remover of the present invention evaporates seldom, and the replacement cycle of remover prolongs thus, and economic worth is provided, and has improved the manufacturing cost of semiconductor devices thus.In addition, can reduce by the pollution of the danger of catching fire that causes of evaporation remover, working environment and to the damage of exhaust duct filtrator.
Content (the unit: %) of the organic amine compound that table 7 amine titrator is measured
| The substrate quantity of peeling off | Time, hour | ||||||||
| 1 | 2 | 5 | 10 | 20 | 20-1 * | 40 | 40-1 * | ||
| Example 1 | 0 | 19.99 | 19.75 | 19.37 | 18.89 | 17.21 | 19.97 | 17.05 | 19.89 |
| 2,000 | 19.98 | 19.78 | 19.31 | 18.89 | 17.18 | 19.99 | 17.11 | 19.91 | |
| 4,000 | 19.99 | 19.72 | 19.28 | 18.89 | 17.02 | 20.01 | 16.99 | 19.90 | |
| Example 2 | 0 | 19.98 | 19.99 | 19.65 | 18.62 | 17.01 | 19.95 | 16.89 | 20.01 |
| 2,000 | 19.97 | 19.86 | 19.62 | 18.63 | 17.06 | 19.94 | 16.99 | 20.03 | |
| 4,000 | 19.96 | 19.89 | 19.65 | 18.62 | 17.04 | 19.95 | 16.98 | 20.04 | |
| Example 3 | 0 | 20.00 | 19.98 | 19.95 | 18.65 | 17.38 | 20.10 | 16.74 | 19.97 |
| 2,000 | 20.02 | 19.95 | 19.95 | 18.63 | 17.54 | 20.03 | 16.79 | 19.96 | |
| 4,000 | 20.01 | 19.92 | 19.92 | 18.59 | 17.55 | 20.05 | 16.81 | 19.97 | |
* the organic amine compound of supplement consumed after 20 or 40 hours is respectively measured the content of amine then after 10 minutes.
As shown in table 7, As time goes on, the content of organic amine compound reduces.Yet, used for a long time by organic amine compound is added to as can be seen that (for example, 20 hours or 40 hours in) the remover, the organic amine compound of remover can return to its original bulk.Thus, used the content of the organic amine compound of remover for a long time by using the measurement of amine titrator, the organic amine compound of supplement consumed then, the stripping performance of remover can recover, and makes the serviceable bife maximum of remover thus.The content of the organic amine compound that use amine titrator is measured forms the basis according to stripping agent controller of the present invention.
Table 8 is by the content (unit: %) of the organic amine compound of GC measurement
| Component | Time, hour | |||||
| 0 | 20 | 20-1 * | 40 | 40-1 * | ||
| Example 1 | Organic amine compound (MEA) | 20 | 17.9 | 19.8 | 17.1 | 19.9 |
| Proton glycol ethers compound (EDG) | 25 | 24.1 | 24.4 | 24.1 | 24.6 | |
| Non-proton multipolarity compound (DMSO) | 54.9 | 58.6 | 55.7 | 58.7 | 55.4 | |
| Example 2 | Organic amine compound (MEA) | 20 | 17.05 | 19.9 | 16.8 | 19.8 |
| Proton glycol ethers compound (DPM) | 25 | 24.6 | 24.2 | 24.1 | 24.85 | |
| Non-proton multipolarity compound (NMP) | 54.9 | 58.25 | 55.8 | 59.0 | 55.25 | |
* the organic amine compound of supplement consumed after 20 or 40 hours is respectively measured the content of amine then after 10 minutes.
In table 8, use the GC measurement to comprise the content of each composition of organic amine compound.Reference table 7 and 8, the content of the organic amine compound of measuring by the amine titrator, with the numerical value of measuring by GC much at one.Thus, obviously the amine titrator is to the content of measuring organic amine compound of great use.
Component (the unit: %) of table 9 distillation and regeneration back remover
| Component | New remover | Useless remover # | After the distillation | After the regeneration | ||
| Example 1 | Organic amine compound (MEA) | 20 | 16.3 | 8.2 | 20 | |
| Proton glycol ethers compound (EDG) | 25 | 24.1 | 23.6 | 25.1 | ||
| Non-proton multipolarity compound (DMSO) | 54.9 | 59.5 | 68.1 | 54.8 | ||
| Example 2 | Organic amine compound (MEA) | 20 | 16.1 | 8.3 | 19.9 | |
| Proton glycol ethers compound (DPM) | 25 | 24.2 | 23.8 | 24.9 | ||
| Non-proton multipolarity compound (NMP) | 54.9 | 59.6 | 67.8 | 55.1 | ||
| Comparative Examples 1 | Organic amine compound (MEA) | 5 | 1.3 | 0.7 | Non-renewable | |
| Proton glycol ethers compound | | 15 | 15.1 | 18.1 | ||
| PGME | 30 | 29.2 | 81.1 * | |||
| Non-proton multipolarity compound (GBL) | 49.9 | 54.3 | ||||
* because their peak value is overlapping, so the content of reaction product and the content addition of PGME between MEA and the GBL.
The useless remover of # represents to simulate the remover that 4,000 8 inches Semiconductor substrate has been carried out the condition of stripping technology.
The stripping performance of the new remover of table 10, useless remover and regeneration remover
| Substrate | The Cr substrate | The Al substrate | |||||||
| Hard stoving temperature, ℃ | 120 | 140 | 160 | 180 | 120 | 140 | 160 | 180 | |
| Example 1 | New remover | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ |
| Useless remover * | ○ | ○ | △ | △ | ○ | ○ | △ | △ | |
| The regeneration remover | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | |
| Example 2 | New remover | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ |
| Useless remover * | ○ | ○ | △ | △ | ○ | ○ | △ | △ | |
| The regeneration remover | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | |
| Comparative Examples 1 | New remover | ○ | ○ | △ | × | ○ | ○ | △ | × |
| Useless remover * | ○ | △ | × | × | ○ | △ | △ | × | |
| The regeneration remover | ○ | △ | × | × | ○ | △ | × | × | |
* useless remover represents to simulate remover has carried out the condition of stripping technology to 4,000 8 inches Semiconductor substrate remover.
As shown in table 9, example 1 and 2 is replenished the regeneration remover obtain and new remover by distillation and composition and is had much at one component according to the present invention.
In addition, as shown in table 10, example 1 and 2 demonstrates and new remover stripping performance much at one by distillation and the additional regeneration remover that obtains of composition according to the present invention as can be seen.Thus, can be according to remover of the present invention by distillation and composition compensation regeneration.
Table 11 is according to the variation of the type stripping performance of surfactant
| Surfactant types | Substrate | Hard stoving temperature, ℃ | |||
| 160 | 180 | 200 | 220 | ||
| LP-100 | Cr | ○ | ○ | ○ | ○ |
| Al | ○ | ○ | ○ | ○ | |
| Koremul 290 | Cr | ○ | ○ | △ | × |
| Al | ○ | △ | △ | × | |
| ETHOQUAD C/25 | Cr | ○ | △ | △ | × |
| Al | ○ | △ | × | × | |
| NOIGEN EA120 | Cr | ○ | △ | × | × |
| Al | ○ | ○ | × | × | |
Table 12 is according to the type and the capillary variation of the content (unit: dynes/cm) of surfactant
| The content of surfactant, wt% | The type of surfactant | |||
| LP-100 | Koremul 290 | ETHOQUAD C/25 | NOIGEN EA 120 | |
| 0 | 85 | 85 | 85 | 85 |
| 0.1 | 21 | 72 | 72 | 64 |
| 0.5 | ＜5 | 61 | 61 | 60 |
| 1 | ＜5 | 48 | 48 | 49 |
Reference table 11, the remover that contains non-ionic surfactant alkyl pyrrolidine ketonic compound (LP-100) as can be seen demonstrates the highest stripping performance.
In addition, as shown in table 12, the remover that contains the alkyl pyrrolidine ketonic compound (LP-100) of promising non-ionic surfactant demonstrates minimum dynamic surface tension.In addition, obviously the alkyl pyrrolidine ketonic compound (LP-100) of 0.5wt% is enough.Thus, the remover that contains as the alkyl pyrrolidine ketonic compound of surfactant provides good wetting effect, and has improved stripping performance.
As mentioned above, can easily peel off under the severe condition of dry corrosion, wet corrosion and/or ashing down according to remover of the present invention low temperature at short notice, the metal byproducts of lower metal layer of being corroded stains, experienced the resist layer of chemistry and/or physical change, made the corrosion minimum of lower metal layer during the stripping technology.In addition, according to only water cleaning of remover of the present invention, need in cleaning step subsequently, not use organic solvent as isopropyl alcohol or dimethyl sulfoxide etc.In addition, owing to remover of the present invention evaporates seldom during heating process, so the replacement cycle of remover can prolong.In addition, remover of the present invention can be easily by evaporation and composition compensation regeneration.
Remover recirculation device of the present invention can be easily by evaporation and the useless remover of composition compensation regeneration.
Stripping agent controller of the present invention can automatically be controlled the component of remover, and automatically remover is provided to peel-off device.
Claims (9)
1. remover, comprise organic amine compound, proton glycol ethers compound, non-proton multipolarity compound and alkyl pyrrolidine ketonic compound, wherein the content of organic amine compound is 10～35wt%, the total content of proton glycol ethers compound and non-proton multipolarity compound is 60～85wt%, the content of alkyl pyrrolidine ketonic compound is 0.1～5wt%, all based on the general assembly (TW) of remover, wherein the alkyl pyrrolidine ketonic compound is to be selected from N-cyclohexyl-2-Pyrrolidone for each, N-octyl group-2-Pyrrolidone, at least a in N-dodecyl-2-Pyrrolidone.
2. according to the remover of claim 1, wherein the content of alkyl pyrrolidine ketonic compound is 0.3～1wt% of remover general assembly (TW).
3. according to the remover of claim 1, wherein organic amine compound is at least one that is selected from following group: Armeen, secondary aliphatic amine, aliphatic tertiary amine, aliphatic cyclic amine, aromatic amine, heterocyclic amine and hydramine.
4. according to the remover of claim 1, wherein proton glycol ethers compound is at least one that is selected from following group: glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethyleneglycol monophenylether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, dipropylene glycol monomethyl ether, the single ether of dipropylene glycol, the single propyl ether of dipropylene glycol and dipropylene glycol monobutyl ether.
5. according to the remover of claim 1, wherein non-proton multipolarity compound is following at least a for being selected from: dimethyl sulfoxide (DMSO), dimethyl acetamide, dimethyl formamide, methylimidazole alkane ketone and sulfolane.
6. method of peeling off resist, wherein the substrate of resist layer deposit on it contacts with any remover of claim 1 to 5.
7. method of peeling off anti-/ erosion agent, the substrate of resist figure that wherein sequentially is deposited with predetermined material layer figure on it and is used as the etching mask of formation material layer figure contacts with any remover of claim 1 to 5.
8. according to the method for claim 7, wherein before substrate contact remover, use plasma on the resist figure, to carry out cineration technics.
9. according to the method for claim 7 or 8, wherein material layer is formed by at least one that is selected from following group: silicon, tantalum, titanium, chromium, molybdenum, tungsten, tin, nickel, aluminium, monox, silicon nitride and tin indium oxide.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR32505/1998 | 1998-08-11 | ||
| KR1019980032505A KR100306649B1 (en) | 1997-12-03 | 1998-08-11 | Resist stripper, resist stripping method using the stripper, resist stripper recycling apparatus, and resist stripper controlling apparatus |
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| CN 03154358 Division CN1276307C (en) | 1998-08-11 | 1999-08-11 | Stripping agent, stripping method, thereof, stripping agent circulator and stripping agent controller |
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| CN1196032C true CN1196032C (en) | 2005-04-06 |
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| CN 03154358 Expired - Lifetime CN1276307C (en) | 1998-08-11 | 1999-08-11 | Stripping agent, stripping method, thereof, stripping agent circulator and stripping agent controller |
| CN 99119693 Expired - Lifetime CN1196032C (en) | 1998-08-11 | 1999-08-11 | Stripping agent, stripping method, stripping agent circulation equipment and stripping agent controller |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 03154358 Expired - Lifetime CN1276307C (en) | 1998-08-11 | 1999-08-11 | Stripping agent, stripping method, thereof, stripping agent circulator and stripping agent controller |
Country Status (1)
| Country | Link |
|---|---|
| CN (2) | CN1276307C (en) |
Families Citing this family (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101017738B1 (en) * | 2002-03-12 | 2011-02-28 | 미츠비시 가스 가가쿠 가부시키가이샤 | Photoresist stripping composition and cleaning composition |
| CN100364061C (en) * | 2003-06-04 | 2008-01-23 | 花王株式会社 | Removing agent composition and removing/cleaning method using same |
| JP2005173369A (en) * | 2003-12-12 | 2005-06-30 | Tokyo Ohka Kogyo Co Ltd | Method for removing resist pattern |
| CN1950755B (en) * | 2004-05-07 | 2011-05-11 | 株式会社东进世美肯 | composition for removing photoresist |
| DE102004054527B4 (en) * | 2004-11-05 | 2006-10-12 | Siemens Ag | Process for the preparation of an isolated conductor of an insulated conductor and release agent |
| KR101266883B1 (en) * | 2006-03-03 | 2013-05-23 | 주식회사 동진쎄미켐 | A recycling method for resist stripper scrapped and a recycling device for same |
| KR101266897B1 (en) * | 2006-03-03 | 2013-05-23 | 주식회사 동진쎄미켐 | A recycling method for resist stripper scrapped and a recycling device for same |
| CN101226346B (en) * | 2007-12-27 | 2010-06-09 | 周伟 | Demoundiing technique of photoresist as well as a first composition, a second composition and demoulding agent water solution used in said technique |
| CN102109777B (en) * | 2010-12-15 | 2012-08-22 | 绵阳艾萨斯电子材料有限公司 | Regeneration liquid of plasma display barrier wall slurry |
| 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 |
| JP6033033B2 (en) * | 2012-10-11 | 2016-11-30 | 日本リファイン株式会社 | Method and apparatus for regenerating resist stripping solution |
| CN103258756B (en) * | 2013-04-26 | 2015-09-09 | 京东方科技集团股份有限公司 | A kind of assessment method of stripping ability of peel-off device and assessment system |
| 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 |
| CN108862431A (en) * | 2018-05-29 | 2018-11-23 | 四川久远化工技术有限公司 | A kind of reuse stripper refining system of stripper regeneration technology section |
| CN108926860B (en) * | 2018-07-20 | 2021-12-21 | 上海化工研究院有限公司 | Waste stripping liquid regeneration device and application thereof |
| CN113463426B (en) * | 2021-06-17 | 2023-03-17 | 江苏鑫源烟草薄片有限公司 | Stripping agent recovery system |
-
1999
- 1999-08-11 CN CN 03154358 patent/CN1276307C/en not_active Expired - Lifetime
- 1999-08-11 CN CN 99119693 patent/CN1196032C/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| CN1276307C (en) | 2006-09-20 |
| CN1248730A (en) | 2000-03-29 |
| CN1530757A (en) | 2004-09-22 |
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