CN100501921C - Substrate processing method and substrate processing apparatus - Google Patents
Substrate processing method and substrate processing apparatus Download PDFInfo
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- CN100501921C CN100501921C CNB2007101065605A CN200710106560A CN100501921C CN 100501921 C CN100501921 C CN 100501921C CN B2007101065605 A CNB2007101065605 A CN B2007101065605A CN 200710106560 A CN200710106560 A CN 200710106560A CN 100501921 C CN100501921 C CN 100501921C
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- 238000012545 processing Methods 0.000 title claims description 29
- 238000003672 processing method Methods 0.000 title claims description 24
- 239000007788 liquid Substances 0.000 claims abstract description 366
- 239000000203 mixture Substances 0.000 claims abstract description 95
- 239000003960 organic solvent Substances 0.000 claims description 86
- 238000011282 treatment Methods 0.000 claims description 73
- 238000001035 drying Methods 0.000 claims description 71
- 238000006073 displacement reaction Methods 0.000 claims description 50
- 235000014347 soups Nutrition 0.000 claims description 39
- 238000000034 method Methods 0.000 claims description 36
- 239000012530 fluid Substances 0.000 claims description 31
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- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 465
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 34
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Abstract
After rinsing, while rotating a substrate, a front layer part of a rinsing liquid (DIW) adhering to a substrate surface is drained and removed from the substrate surface. This is followed by supply to the substrate surface of a liquid mixture which is obtained by mixing IPA and DIW together. Since a majority of the rinsing liquid on the substrate surface is removed off from the substrate surface, even when micro patterns are formed on the substrate surface, the liquid mixture replaces the liquid component adhering to the gaps between the patterns. Further, the IPA concentration in the liquid mixture supplied to the substrate surface is set to 50% or below. Hence, it is possible to effectively prevent destruction of the patterns while suppressing the consumption amount .
Description
Technical field
The present invention relates to a kind of substrate surface dried base plate processing method and substrate board treatment that is soaked by liquid that make.In addition, the substrate that becomes process object to be dried comprises that semiconductor wafer, photomask show with glass substrate, CD with substrate with glass substrate, liquid crystal display with glass substrate, plasma etc.
Background technology
Utilize the soup of soup to handle and utilize after the rinsing processing of rinsing liquids such as pure water finishes, in order to remove, from beginning to propose many drying means in the past attached to the rinsing liquid on the substrate surface.As the method for one of them, known have isopropyl alcohol) utilize IPA (IsoPropyl Alcohol: the drying means of organic solvent composition such as.Especially, for the single sheet type substrate board treatment, known have that (the Marangoni effect: (Rotagoni) drying is moved in dried kalimeris brother Buddhist nun effect) and rotation (Spin) dried combine, so-called rotation with utilizing convection current, wherein, above-mentioned convection current is that difference by the surface tension between pure water and the IPA is produced.
Rotate in the mobile drying at this,, spray IPA steam and pure water to substrate respectively by nozzle from the top of rotating substrate center.Then, these nozzles are moved to the radial outside of substrate lentamente, make to begin drying,, thereby make the whole base plate drying so that arid region mind-set periphery from substrate enlarges from the part of the ejection of accepting IPA steam.That is to say, by following action of centrifugal force that substrate rotation produces and, removing pure water from substrate, thus dry substrate because of spraying the kalimeris brother Buddhist nun effect that IPA steam takes place.
In addition, as other drying method for substrate that utilizes IPA, for example known have a drying means of being put down in writing in patent documentation 1.The substrate board treatment of carrying out this drying means is a kind of such device,, after substrate being carried out soup processing and rinsing processing, makes drying substrates by rotation that is.In this device, carry out after the soup processing, supply with IPA mixing pure water and nitrogen from two fluid mixing nozzles simultaneously to substrate, handle thereby carry out rinsing, wherein, above-mentioned IP A mixing pure water is resulting to pure water hybrid IP A.By above-mentioned processing, can remove attached to soup on the substrate surface and foreign particles, and produce watermark at substrate surface can suppress dried the time.
In addition, in the substrate board treatment that patent documentation 2 is put down in writing, the substrate of the IPA aqueous solution that will obtain to pure water hybrid IP A after developing supplied with, and carries out rinsing thus and handles.By above-mentioned processing, can under the situation that can prevent fine resist pattern collapse, carry out rinsing and handle.
In addition, in the cleaning device that patent documentation 3 is put down in writing, after substrate surface is carried out hydrofluoric acid treatment, supply with pure water and carry out clean (rinsing processing) to substrate surface.Then, after the supply that stops pure water, do not have interruptedly or from supply with pure water begin midway supply with IPA to substrate surface.Thus, IPA is dissolved in the pure water on the substrate surface, thereby pure water is replaced by IPA.So, the pure water on the substrate surface by the result that IPA replaces is the watermark that is taken place in the time of can preventing dry substrate.
In addition, in the resist developing method that patent documentation 4 is put down in writing, realize the reduction of the fine dust amount on the substrate surface in the following way.At first, after carrying out the resist development, supply with pure water and carry out pure water cleaning (rinsing processing) to substrate.Then, will comprise Capacity Ratio is that the pure water (the IPA aqueous solution) of about 10% IPA is supplied with to substrate and carried out substrate and clean.Then, make the substrate high speed rotating, thereby make drying substrates by rotation.
Patent documentation 1:JP spy opens 2003-No. 168668 communiques (Fig. 6)
Patent documentation 2:JP spy opens flat 7-No. 122485 communiques (Fig. 4)
Patent documentation 3:JP spy opens flat 9-No. 38595 communiques (Fig. 5)
Patent documentation 4:JP spy opens flat 3-No. 209715 communiques (Fig. 1)
Also have, in recent years, the development of the miniaturization of the relevant pattern that is formed at substrate surface is swift and violent, and follows this miniaturization, and new problem takes place on processing substrate.That is in withering process, the close to each other and problem of collapsing of fine pattern takes place.Specifically, following problem can take place: follow the progress of dried, the interface of liquids and gases on substrate, occurs, so fine pattern be subjected to each other resulting from pattern gap location negative pressure and near and collapse.This size of negative pressure that results from the gap location of pattern depends on the surface tension of liquid, and big more this negative pressure of the surface tension of liquid becomes big more.Therefore, when when effectively preventing the collapsing of pattern, making the substrate surface that is soaked by pure water dry, be necessary to use surface tension less than organic solvents such as the fluid of pure water, for example IPA, and be necessary to make IPA to penetrate into the inside of pattern interval.
Yet, in the mobile drying of rotation,, therefore have following problem owing to substrate is carried out drying when making the rotation of substrate.That is, even supply with IPA steam to substrate surface, owing to the influence of the air-flow of following the substrate rotation to produce, IPA steam also can be discharged from from substrate very soon, therefore IPA is dissolved in fully attached in the pure water on the substrate surface.Consequently, do not wait until that also IPA fully is dissolved in attached in the pure water of the inside of the pattern interval that is formed at substrate surface the time, substrate surface is dried, thereby can't prevent collapsing of pattern fully.
In addition, in the drying means that patent documentation 1 is put down in writing, after carrying out the soup processing, the IPA mixing pure water that is mixed with IPA is used as rinsing liquid, removes attached to soup on the substrate surface and foreign particles.Similarly, in the substrate board treatment that patent documentation 2 is put down in writing, also after carrying out development treatment, the IPA aqueous solution as rinsing liquid, is removed at the resist pattern after the development and residual attached to the developer solution on the substrate surface.Therefore there is following problem: in order to remove these, and will spend the corresponding rinsing time, and the consumption of IPA also becomes many attached to treatment fluid on the substrate surface (soup or developer solution) and useless material.
And then what can contain foreign particles in IPA, therefore following problem may take place: as mentioned above, many as if the supply quantitative change of the IPA that supplies to substrate, the foreign particles that then is included among the IPA can be accumulated on the substrate, thereby makes substrate anti-contaminated.
In addition, in the cleaning device that patent documentation 3 or patent documentation 4 are put down in writing, carry out rinsing handle after with IPA or the IPA aqueous solution when substrate surface is supplied with, the pure water of relative volume is residual attached on the substrate surface.Therefore, if supply with the IPA or the IPA aqueous solution in this state on substrate surface, do not wait until also that then IPA fully is dissolved into attached in the pure water of the inside of the pattern interval that is formed at substrate surface the time, IPA is discharged from outside substrate.Consequently, the pattern collapse in the time of can't fully preventing dry substrate and the generation of watermark.
Summary of the invention
The present invention proposes in view of the above problems, its purpose is, make in the substrate surface dried base plate processing method and substrate board treatment of being soaked at organic solvent compositions such as utilizing IPA, in the consumption that suppresses the organic solvent composition, make substrate surface dry well by liquid.
The present invention a kind ofly carries out the dried base plate processing method to the substrate surface that is soaked by liquid, and, to achieve these goals and following formation.That is, substrate processing method using same comprises: liquid is removed operation, the major part that is attached to the liquid on the described substrate surface is removed from described substrate surface and stays a part of liquid; The displacement operation, on surface, supply with mixed liquor with the maintained substrate of level of approximation posture, the residual liquid component that is attached on the described substrate surface is replaced into described mixed liquor after described liquid is removed operation thereby make, wherein, described mixed liquor be by be attached to described substrate surface on the liquid same composition liquid or with being attached to liquid principal component on the described substrate surface identical liquid and be dissolved in this liquid and the organic solvent composition that surface tension is reduced mixes; Drying process after described displacement operation, is removed described mixed liquor and is made this substrate surface drying from described substrate surface, and the percentage by volume of the described organic solvent composition in the described mixed liquor is below 50%.In addition, substrate board treatment comprises: base plate keeping device, its substrate surface that is soaked by liquid towards above state under, substrate is remained the level of approximation posture; Fluid Supplying apparatus, it supplies with mixed liquor to surface of the substrate that is kept by described base plate keeping device, this mixed liquor be by be attached to described substrate surface on the liquid same composition liquid or with being attached to liquid principal component on the described substrate surface identical liquid and be dissolved in this liquid and the organic solvent composition that surface tension is reduced mixes; Liquid is removed device, its major part that will be attached to the liquid on the described substrate surface is removed from described substrate surface and is stayed a part of liquid, remove device after described substrate surface is removed described liquid by described liquid, the percentage by volume of supplying with the described organic solvent composition the described mixed liquor to described substrate surface from described fluid Supplying apparatus is the mixed liquor below 50%, and make the liquid component that is attached on the described substrate surface be replaced into described mixed liquor, remove described mixed liquor and make described substrate surface drying from described substrate surface then.
In the invention (substrate processing method using same and device) that constitutes like this, substrate surface is being carried out drying (dried) before, supply with mixed liquor to surface with the maintained substrate of level of approximation posture, thereby make residual attached to the mixed liquid displacement of the liquid component on this substrate surface, wherein, above-mentioned mixed liquor be by with the liquid or the principal component that are attached to the liquid same composition on the substrate surface and be attached on the substrate surface liquid phase with liquid, with the organic solvent composition mix (below, simply be called " mixed liquor "), this organic solvent composition (below be called " surface tension reduction material ") is dissolved in this liquid and surface tension is reduced.In addition, utilizing mixed liquor to replace (displacement operation) before, removing from substrate surface and be attached to the most of liquid on the substrate surface and stay a part of liquid.Therefore, even on substrate surface, be formed with fine pattern, also can make surface tension reduce material and fully be dissolved in liquid component attached to the inside of pattern interval.Consequently,, can replace the liquid component that is present in the pattern interval place reliably by comprising the mixed liquor that surface tension reduces material, thus the pattern collapse can prevent from effectively to carry out drying substrates the time.Also have,, can utilize the mixed liquor replacement fluid composition of relatively small amount, thereby can suppress the consumption of organic solvent composition by before the displacement operation, removing most liquid component from substrate surface.And then, can make mixed liquor enter into pattern interval expeditiously, therefore can shorten the time of implementation of displacement operation self.
In addition, be below 50% by the percentage by volume that makes the organic solvent composition in the mixed liquor, prevent pattern collapse when can suppress the consumption of organic solvent composition effectively.That is, when the liquid displacement that utilizes 100% organic solvent to become to assign to will to be attached to the pattern interval place is 100% organic solvent composition, be necessary to supply with 100% organic solvent composition to substrate surface.Therefore, the consumption of organic solvent composition is directly proportional with substrate number to be processed and increases.Therefore becoming needs a large amount of organic solvent compositions, and this can become the main cause that cost increases.Therefore, the organic solvent composition of employing 100% is very practical.On the other hand, if, then can consider such method from suppressing the angle of organic solvent composition consumption, promptly, before drying process, the organic solvent composition to the substrate surface supply relatively small amount that is soaked by liquid makes this organic solvent composition be blended in the liquid thus.Yet, if the amount of the organic solvent composition of supplying with to every substrate is reduced, then promptly allow to the top layer part that the organic solvent composition is blended into the liquid that is attached on the substrate surface, also be difficult to make surface tension to reduce material (organic solvent composition) and enter into pattern interval and surface tension is reduced.
Relative therewith, by percentage by volume from the organic solvent composition to substrate that supply with is mixed liquor below 50%, make the mixed liquid displacement of liquid on the substrate, thereby be attached to liquid (mixed liquor) displacement of the also involved surface tension reduction of the liquid material at pattern interval place.So, carry out replacement Treatment, also can make surface tension reduce material and enter into the gap of pattern, thereby surface tension is reduced even without the organic solvent composition (surface tension reduction material) that utilizes 100%.At this moment, because the percentage by volume that is included in the organic solvent composition in this mixed liquor is below 50%, compares when therefore the amount of existing organic solvent composition is with the replacement Treatment of using 100% organic solvent composition in pattern interval and tail off.Yet, as described later shown in the experimental result, if set the percentage by volume of the organic solvent composition in the mixed liquor greater than 50% o'clock, do not observe that mixed liquor is capillary to be reduced significantly yet, therefore can't look to causing the minimizing significantly of the power of pattern collapse.On the contrary, be accompanied by the increase of the consumption of aforesaid organic solvent composition, surface tension reduces material and is restricted to the quantity delivered of substrate, and is more serious relatively thereby the undesirable element that is taken place becomes.Therefore, be set at below 50%, can in the consumption that suppresses the organic solvent composition, can prevent pattern collapse effectively thus by percentage by volume with the organic solvent composition in the mixed liquor.
And then, reduce by the percentage by volume that makes the organic solvent composition in the mixed liquor, thereby compare when having only the organic solvent composition, can simplify explosion-proof countermeasure to the device of this organic solvent composition.In addition, for the foreign matters such as particle that comprised in the supply fluid that removes the supply of whereabouts substrate, needs use filter etc. is carried out supplying with the filtration treatment of fluid, but, therefore there is the problem that is difficult to from the organic solvent composition, remove foreign matters such as degranulation because the surface tension when having only the organic solvent composition is low.Relative therewith, if organic solvent composition and liquid are mixed, then help removing easily the foreign matter that is included in the mixed liquor.
At this, when removing liquid (carry out liquid and remove operation) from substrate surface, preferably only remove the skin section that is attached to the liquid on the substrate surface.Thus, in the displacement operation, mixed liquor is entered into be formed at the inside of the pattern interval of substrate surface to become easily, thereby the mixed expeditiously liquid of the liquid component that is present in the pattern interval is replaced.In addition, only remove the liquid of skin section, therefore can prevent that the substrate surface part is dried from substrate surface.Can prevent thus because of the dry following bad phenomenon that causes of substrate surface.That is, under making the liquid residue that is present in the pattern interval in, the liquid component of skin section is removed the generation of the pattern collapse in the time of can preventing from thus to remove liquid (liquid is removed operation) from substrate surface.In addition, prevent that substrate surface from exposing externally in the air, thereby can suppress foreign particles attached on the substrate surface.
In addition, get rid of from substrate surface by making substrate rotation and to remove the liquid that is attached on the substrate surface, can be from substrate surface relatively easily and to remove most liquid in the short time.The rotating speed of the substrate when at this moment, liquid is removed operation is preferably set to 300～500rpm.If adopt this substrate rotating speed, then preventing under the dry situation of substrate surface, can in the short relatively time, remove liquid from substrate surface.In addition, be set at 0.5～1sec by the time of implementation of liquid being removed operation, can remove liquid well from substrate surface.That is,, when then can prevent to cause substrate surface Wf local desiccation, can prevent to remove the liquid inadequate situation that becomes from substrate surface because of the time of implementation is too short because of the time of implementation is long if adopt this time of implementation.
At this,,, preferably be set at the percentage by volume of the organic solvent composition in the mixed liquor (below, be called " organic solvent constituent concentration ") more than 5% and below 35% then according to reason as described below if consider from the angle that prevents pattern collapse effectively.That is, as the formula (1), cause when carrying out drying substrates that the anti-power (in the negative pressure that the gap produced of pattern) of pattern collapse depends on attached to the surface tension of the liquid at pattern interval place and the contact angle between substrate surface and the liquid.
2λ×cosθ?…(1)
Wherein, λ is the surface tension attached to the liquid at pattern interval place, and θ is the contact angle between substrate surface and the liquid.
Therefore, according to formula (1) as can be known,, cause that then the power of pattern collapse just becomes more little if the contact angle that is attached between the surface tension of liquid at pattern interval place more little and substrate surface and the liquid is big more.
About the organic solvent constituent concentration be attached to relation between the surface tension of liquid at pattern interval place, and the relation between organic solvent constituent concentration and the contact angle, in experimental result described later, have been described in detail, this contact angle is the contact angle between substrate surface and the liquid, and, according to this experimental result, if progressively increase the combined amount of organic solvent composition to liquid, then the surface tension of mixed liquor sharply descends, the percentage by volume of the organic solvent composition in mixed liquor becomes till about 10%, but liquid (mixed liquor) is to the not significantly reduction of generation of contact angle of substrate surface.Consequently, when the percentage by volume of the organic solvent composition in mixed liquor is 10% left and right sides, cause the power minimalization of pattern collapse.Therefore, be set at about 10% or 10%, prevent pattern collapse when further can suppress the consumption of organic solvent composition effectively by percentage by volume with the organic solvent composition in the mixed liquor.If from this angle, then more preferably be set at the percentage by volume of the organic solvent composition in the mixed liquor more than 5% and below 10%.
In addition, if supply with mixed liquor to substrate surface in rotary plate, then mixed liquor is subjected to acting on the action of centrifugal force of mixed liquor and flows, thereby can make mixed liquor enter into the inside of pattern interval more expeditiously.Consequently, make the mixed reliably liquid displacement of the liquid component that is attached to the pattern interval place, thereby can prevent pattern collapse effectively.
In addition, before the displacement operation, also have and supply with rinsing liquid and implement the rinsing process that rinsing is handled to substrate surface, and, to after rinsing process, be attached to rinsing liquid on the substrate surface as being attached to liquid on the substrate surface, also can and the substrate surface that is soaked by rinsing liquid is carried out drying.If according to this structure, then remove most of rinsing liquid and stay a part of rinsing liquid from the substrate surface that after the rinsing liquid operation, is soaked by rinsing liquid.Therefore can make mixed liquor enter into the inside of pattern interval expeditiously, thereby can make the substrate surface that is soaked by rinsing liquid dry well.Also have, rinsing process is by different with mixed liquor and rinsing liquid that only be made of liquid is carried out, therefore, in the displacement operation, as long as prepare to make the organic solvent composition of the amount that the rinsing liquid that is attached on the substrate surface can mixed liquid displacement, thereby can suppress the consumption of organic solvent composition.
In addition, also can when rinsing process finishes, begin to proceed liquid and remove operation, till the displacement operation is when beginning.Thus, rinsing process, liquid remove operation and the displacement operation is carried out integratedly continuously, thereby can make the mixed apace liquid displacement of the rinsing liquid that is attached on the substrate surface.
And then, before rinsing process, have and implement the soup treatment process that soup is handled to the substrate surface supply of chemical, and in rinsing process, remove the residual soup that is attached on the substrate surface and also can from substrate surface.Thus, substrate surface is implemented a series of clean (soup processing+rinsing liquid processing+replacement Treatment+dried), thereby make substrate surface dry well.
In addition, if drying process is carried out in inert gas environment, then can shorten drying time, and can reduce the oxygen concentration of substrate surrounding environment.Therefore can reduce oxidized material from the stripping of substrate surface to mixed liquor, therefore can prevent the generation of watermark effectively.This inert gas environment is for example realized by environment cut-off and gas supply device are set, wherein, above-mentioned environment cut-off is opposed at the top position and the substrate surface of substrate, and from the substrate surface configured separate, the above-mentioned gas feedway is supplied with inert gas to the space that is formed between environment cut-off and the substrate surface.
In addition, in drying process, make the substrate rotation and get rid of the mixed liquor that is attached on the substrate surface, thereby make in the substrate processing method using same of drying substrates, after the displacement operation and before drying process, on the whole base plate surface, form the mixing liquid layer of immersion liquid (puddle) state by mixed liquor, and then form the hole, and the hole is enlarged to the end edge direction of substrate also can to the surperficial central portion ejection gas of substrate and at the central portion that mixes liquid layer.If according to this structure, can prevent that then mixed liquor from remaining in the surperficial central portion of the substrate in the drying process and becoming the striated foreign particles with droplet-like, thereby can prevent to form watermark.That is, remove when being attached to the mixed liquor on the substrate surface and making it dry making the substrate rotation, the centrifugal force that acts on mixed liquor is just more little the closer to the substrate surface central part, and therefore the endmost surface limit portion from substrate begins progressively dry.At this moment, drop is arranged, and this drop moves to the end edge direction of substrate, make to form watermark sometimes at the mobile vestige place of this drop from the surperficial central portion of substrate is residual around it.Relative therewith, if according to this invention, the central portion that then was pre-formed the mixing liquid layer of the immersion liquid state on substrate surface before carrying out drying process forms the hole, and this hole is progressively enlarged, thereby therefore the mixed liquor of getting rid of the surperficial central portion that is positioned at substrate can prevent the formation of watermark reliably.
In addition, " organic solvent composition " of the present invention as being used for can use alcohol organic solvent.If consider from fail safe, price equal angles, then can adopt isopropyl alcohol, ethanol or methyl alcohol, and preferably adopt isopropyl alcohol (IPA).
If according to this invention, then substrate surface is being carried out drying (drying process) before, supply with mixed liquor to surface with the maintained substrate of level of approximation posture, thereby make attached to the mixed liquid displacement of the liquid component on the substrate surface, wherein, above-mentioned mixed liquor be by with the liquid or the principal component that are attached to the liquid same composition on the substrate surface and be attached on the substrate surface liquid phase with liquid and organic solvent composition mix, this organic solvent composition is dissolved in this liquid and surface tension is reduced.In addition, utilizing mixed liquor to replace (displacement operation) before, removing from substrate surface and be attached to the most of liquid on the substrate surface and stay a part of liquid.Therefore,, also can make the displacement of the mixed reliably liquid of the liquid component that is present in the pattern interval even be formed with fine pattern at substrate surface, thus the pattern collapse can prevent from effectively to carry out drying substrates the time.Also have, by remove most liquid component from substrate surface, can utilize the mixed liquor replacement fluid composition of relatively small amount, thereby can suppress the consumption of organic solvent composition.In addition, be set at below 50%, thereby compare during with the organic solvent composition that uses 100%, when can suppress the consumption of organic solvent composition, can prevent pattern collapse effectively by the percentage by volume that makes the organic solvent composition in the mixed liquor.
Description of drawings
Fig. 1 is the curve chart of the relation between expression IPA concentration and the surface tension γ.
Fig. 2 is the curve chart of the relation between expression IPA concentration and the contact angle θ.
Fig. 3 is the curve chart of the relation between expression IPA concentration and the γ * cos θ.
Fig. 4 is the figure of first execution mode of expression substrate board treatment of the present invention.
Fig. 5 is the block diagram of control structure of the substrate board treatment of presentation graphs 4.
Fig. 6 is the flow chart of action of the substrate board treatment of presentation graphs 4.
Fig. 7 is the sequential chart of action of the substrate board treatment of presentation graphs 4.
Fig. 8 A, Fig. 8 B, Fig. 8 C are the figure of action that schematically shows the drying process device of Fig. 4, wherein, Fig. 8 A represents the state of the substrate surface after rinsing is handled, and Fig. 8 B express liquid is removed the state of the substrate surface after the processing, and Fig. 8 C represents the state of the substrate surface after the replacement Treatment.
Fig. 9 A, Fig. 9 B are the figure of action that schematically shows the drying process device of Fig. 4, wherein, and the situation when Fig. 9 A represents only to supply with IPA, the situation when Fig. 9 B represents to supply with mixed liquor.
Figure 10 is the figure of second execution mode of expression substrate board treatment of the present invention.
Figure 11 is the block diagram of control structure of the substrate board treatment of expression Figure 10.
Figure 12 A, Figure 12 B, Figure 12 C are the figure of the 3rd execution mode of expression substrate board treatment of the present invention.
Figure 13 is the figure of the 4th execution mode of expression substrate board treatment of the present invention.
Figure 14 is the sequential chart of action of the substrate board treatment of expression Figure 13.
Figure 15 is the figure of the 5th execution mode of expression substrate board treatment of the present invention.
Figure 16 is the sequential chart of action of the substrate board treatment of expression Figure 15.
Embodiment
＜organic solvent constituent concentration and cause relation between the power of pattern collapse
Give the influence that power produced that causes pattern collapse in order to investigate the organic solvent constituent concentration, the present inventor has carried out various experiments.As above illustrated, as seen from formula (1), the power that causes pattern collapse depend on surface tension γ attached to the liquid in the gap of pattern (below, only be called " surface tension γ ") and the long-pending size of cos θ, wherein, this cos θ be and substrate surface and liquid between the corresponding value of contact angle (below, only be called contact angle θ).Therefore, the present inventor estimates the relation between the relation between organic solvent constituent concentration and the surface tension γ and organic solvent constituent concentration and the contact angle θ respectively.At this, as with use attached to the liquid of the liquid same composition on the substrate surface DIW (deionized water: deionized water), and, use isopropyl alcohol (IPA) as the organic solvent composition, and DIW and IPA mixed and generated mixed liquor.Surface tension γ and contact angle θ when then, determining the percentage by volume that changes the IPA in the mixed liquor (DIW+IPA) (below, be called " IPA concentration ").
Fig. 1 is the curve chart of the relation between expression IPA concentration and the surface tension γ.In addition, Fig. 2 is the curve chart of the relation between expression IPA concentration and the contact angle θ.Transverse axis among Fig. 1 and Fig. 2 is represented IPA concentration, and IPA concentration is that 0 (vol%) expression is the DIW monomer, and IPA concentration is that 100 (vol%) expression is the IPA liquid monomer.These surface tension γ and contact angle θ are that the LCD-400S that utilizes consonance interface science Co., Ltd. to make measures.Here, (pendant dropmethod) determines surface tension γ by sessile drop method, determines contact angle θ by sessile drop method.In addition, when measuring contact angle θ, utilize and be formed on the substrate that the surface is formed with Poly-Si, determine and finally carried out substrate surface that HF handles and the contact angle between the liquid (mixed liquor, DIW monomer or IPA liquid monomer).
As can be seen from Figure 1, if continue to increase to the IPA of DIW combined amount, then arrive till about 10% up to IPA concentration, be accompanied by the increase to the IPA of DIW combined amount, the surface tension γ of mixed liquor sharply descends.And, being increased to 50% when above in IPA concentration, the surface tension of mixed liquor does not take place significantly to reduce, and shows and IPA liquid monomer surface tension much at one.On the other hand, as can be seen from Figure 2, be accompanied by increase to the IPA of DIW combined amount, till about IPA concentration is increased to 50%, contact angle θ continues to reduce almost evenly, and, in IPA concentration is 10% front and back, the not so big variation of the intensity of variation of contact angle θ.And the surface tension γ and the value cos θ corresponding with contact angle θ that calculate relative each IPA concentration are long-pending, derive the negative pressure (causing the power of pattern collapse) that results from the pattern interval place and the relation between the IPA concentration thus.
Fig. 3 is the curve chart of the relation between expression IPA concentration and the γ * cos θ.As shown in Figure 3, when IPA concentration is 10% left and right sides, γ * cos θ, promptly by the power minimalization that causes pattern collapse shown in the formula (1).This can illustrate by following situation: if continue to increase combined amount to the IPA of DIW, then about IPA concentration is increased to 10% till, the surface tension γ of mixed liquor sharply descends, but contact angle θ does not take place significantly to descend.Can also recognize, the size of the γ when IPA concentration is 10% left and right sides * cos θ, with IPA concentration be 100% o'clock, the size of γ * cos θ when being the IPA liquid monomer much at one.Can judge that thus at the power that causes pattern collapse, use IPA liquid monomer or use IPA concentration are about 10% mixed liquor, it comes to the same thing.
At this, as mentioned above, if this angle from being replaced less than the material of DIW by surface tension attached to the DIW of the pattern interval that is formed at substrate surface, it is very important that then such thing becomes, that is supply with many relatively mixed liquors to substrate when, suppressing the consumption of IPA.Therefore, if consider from reducing this angle that IPA concentration can effectively prevent pattern collapse, then as long as surface tension γ less than DIW and contact angle θ greater than IPA, just help effectively preventing pattern collapse certainly.If from this angle, then IPA concentration is preferably below 50%.And then, when IPA concentration is 10% left and right sides, cause that the power of pattern collapse diminishes, so IPA concentration is preferably more than 5% and below 35%, and then IPA concentration is more preferably more than 5% and below 10%.By IPA concentration is set at this concentration, can obtain the composite effect that two kinds of pattern collapses prevent effect, thereby can prevent pattern collapse effectively, wherein, above-mentioned two kinds of pattern collapses prevent that effect from being, the pattern collapse that obtains by the quantity delivered that increases mixed liquor prevents effect and causes that by reduction the pattern collapse that the power of pattern collapse obtains prevents effect.In addition, in above-mentioned experiment, used isopropyl alcohol (IPA), but, also can obtain essentially identical pattern collapse and prevent effect by using ethanol or methyl alcohol as the organic solvent composition.
Therefore, in substrate processing method using same of the present invention and substrate board treatment, use the mixed liquor of said components, thereby when can suppress the consumption of organic solvent composition, can make the substrate surface that is soaked by liquid dry well.Below, with reference to accompanying drawing, concrete execution mode is described.
＜the first execution mode 〉
Fig. 4 is the figure of first execution mode of expression substrate board treatment of the present invention.In addition, Fig. 5 is the block diagram of control structure of the substrate board treatment of presentation graphs 4.This substrate board treatment is a kind of single sheet type substrate board treatment that is used for clean, and wherein, above-mentioned clean is used to remove the polluter attached to the surperficial Wf of substrate W such as semiconductor wafer.Specifically, this is a kind of following device: the surperficial Wf that is formed at the substrate W on the surperficial Wf for the fine pattern of Poly-Si, carried out after soup processing that utilizes soups such as hydrofluoric acid and the rinsing processing that utilizes rinsing liquids such as pure water or DIW, carry out replacement Treatment described later for the substrate W that is soaked by rinsing liquid, then substrate W is carried out dried.
This substrate board treatment has: rotary chuck 1, its with substrate its surperficial Wf towards above state under remain the level of approximation posture, and make substrate rotation; Liquid nozzle 3 and rinsing liquid nozzle 5, their supply of chemical and rinsing liquids respectively above the substrate W that keeps at rotary chuck 1.In addition, rinsing liquid nozzle 5 can to substrate W supply with selectively as the DIW of rinsing liquid and will with handle the back attached to the liquid of the liquid on the substrate surface Wf (DIW) same composition be dissolved in this liquid and organic solvent composition that surface tension is reduced mixes and the mixed liquor that obtains carrying out rinsing.
The swinging strut 11 of rotary chuck 1 is connected with the rotating shaft of the chuck rotating mechanism 13 that comprises motor, so rotary chuck 1 can be around the vertical axis rotation by the driving of chuck rotating mechanism 13.These swinging struts 11, chuck rotating mechanism 13 are contained in the housing 2 cylindraceous.Be fastenedly connected parts by bolt etc., be connected with discoid rotating platform 15 integratedly in the upper end of swinging strut 11.Therefore, make rotating platform 15 around the vertical axis rotation, and drive chuck rotating mechanism 13 is according to carrying out from the action command of the control unit 4 of controlling whole device by drive chuck rotating mechanism 13.Like this, in this embodiment, the function of chuck rotating mechanism 13 performances " whirligig " of the present invention.
Near the periphery of rotating platform 15, erect a plurality of chuck pins 17 be provided with the periphery that is used to control substrate W.In order to keep circular substrate W reliably, as long as the chuck pin 17 more than 3 is set, and this chuck pin 17 is that periphery along rotating platform 15 is to be configured at interval with the equal angular.Each chuck pin 17 has: base plate supports portion, and it is from the periphery of supported underneath substrate W; The substrate maintaining part, it is pushed by the peripheral end face of the substrate supported W of base plate supports portion and keeps substrate W.Each chuck pin 17 constitutes in switchable mode between pressed state and release condition, and under pressed state, the substrate maintaining part is pushed the peripheral end face of substrate W, and under release condition, the substrate maintaining part is removed from the peripheral end face of substrate W.
When rotating platform 15 is carried out the handing-over of substrate W, make a plurality of chuck pins 17 be in release condition, and when substrate W is carried out clean, make a plurality of chuck pins 17 be in pressed state.By making chuck pin 17 be in pressed state, can make a plurality of chuck pins 17 control the periphery of substrate W, thereby keep this substrate W across given interval with the level of approximation posture from rotating platform 15.Thus, substrate W with its surface (pattern formation face) Wf towards the top, lower surface W b is held towards the state of below.So, in this embodiment, the function of chuck pin 17 performances " base plate keeping device " of the present invention.
And then, around housing 2, be equipped with regularly and be subjected to liquid member 21.Setting is provided with spaced walls member 23a cylindraceous, 23b, 23c on the liquid member 21 being subjected to.Space between the inwall of the outer wall of housing 2 and spaced walls member 23a forms the first sump pit 25a, space between the inwall of the outer wall of spaced walls member 23a and spaced walls member 23b forms the second sump pit 25b, and the space between the inwall of the outer wall of spaced walls member 23b and spaced walls member 23c forms the 3rd sump pit 25c.
Bottom at the first sump pit 25a, the second sump pit 25b and the 3rd sump pit 25c is formed with leakage fluid dram 27a, 27b, 27c respectively, and each leakage fluid dram is connected with mutually different discharging tube.For example, in this embodiment, the first sump pit 25a is the groove that is used to reclaim used soup, so the recovery discharging tube that utilizes again with being used for released liquor is connected.In addition, the second sump pit 25b is the groove that is used to discharge used rinsing liquid, so be connected with the discarded discharging tube that is used for waste treatment.And then the 3rd sump pit 25c is the groove that is used to discharge used mixed liquor, so be connected with the discarded discharging tube that is used for waste treatment.
Above each sump pit 25a～25c, be provided with splashing board 6.Splashing board 6 with encirclement be rotated chuck 1 remain flat-hand position substrate W around mode, relative rotation axi (vertical axis) but the setting of free lifting ground.This splashing board 6 has the approximate rotational symmetric shape of rotating shaft of relative rotary chuck 1, and has 3 baffle plates 61,62,63 that disposed laterally from radially inner side in the mode with rotary chuck 1 formation concentric circles.3 baffle plates 61,62,63 are set to from outermost baffle plate 63 to the most inboard baffle plate 61 step-down highly successively, and the upper end of each baffle plate 61,62,63 disposes in the mode in the plane that all is located at vertical and extends.
Splashing board 6 is connected with baffle plate elevating mechanism 65, and according to the action command from control unit 4, the lifting of baffle plate elevating mechanism 65 is driven with transmission device (for example, cylinder etc.) action, thereby can make splashing board 6 relative rotary chuck 1 liftings.In this embodiment, by the driving of baffle plate elevating mechanism 65, can make splashing board 6 interim ground liftings, thereby the treatment fluid that the substrate W from rotation can be splashed is discharged to respectively first～the 3rd sump pit 25a～25c.
Be formed with the first guide portion 61a of groove shape on the top of baffle plate 61, the section of this first guide portion 61a is " く " shape, and open to the inside.And, carrying out soup when handling, make splashing board 6 be positioned at the highest position (below, be called " first height and position "), the soup that splashes from the substrate W of rotation is blocked by the first guide portion 61a, and it is directed among the first sump pit 25a.Specifically, at first height and position, the mode on every side that is enclosed in the substrate W that keeps on the rotary chuck 1 with the first guide portion 61a disposes splashing board 6, thereby the soup that will splash from the substrate W of rotation by baffle plate 61 is directed to the first sump pit 25a.
In addition, be formed with rake 62a on the top of baffle plate 62, this rake 62a tilts along oblique upper to the inside from radial outside.And, when carrying out rinsing and handle, make splashing board 6 be positioned at the position lower (below, be called " second height and position ") than first height and position, make thus to be tilted the 62a of portion from the rinsing liquid that splashes of substrate W of rotation and to block, and it is directed among the second sump pit 25b.Specifically, at second height and position, the mode on every side that is enclosed in the substrate W that keeps on the rotary chuck 1 with rake 62a disposes splashing board 6, thereby make between the rinsing liquid that splashes of substrate W of the rotation upper end and the upper end of baffle plate 62 by baffle plate 61, and it is directed among the second sump pit 25b.
Equally, be formed with rake 63a on the top of baffle plate 63, this rake 63a tilts along oblique upper to the inside from radial outside.And, when carrying out replacement Treatment, make splashing board 6 be positioned at the position lower (below, be called " the 3rd height and position ") than second height and position, make thus to be tilted the 63a of portion from the mixed liquor that splashes of substrate W of rotation and to block, and it is directed among the 3rd sump pit 25c.Specifically, at the 3rd height and position, the mode on every side that is enclosed in the substrate W that keeps on the rotary chuck 1 with rake 63a disposes splashing board 6, thereby make between the mixed liquor that splashes of substrate W of the rotation upper end and the upper end of baffle plate 63 by baffle plate 62, and it is directed among the 3rd sump pit 25c.
And then, make splashing board 6 be positioned at the position lower than the 3rd height and position (below, be called " retreating position "), thereby make rotary chuck 1 outstanding from the upper end of splashing board 6, can make base board delivery device (not shown) be loaded into untreated substrate W on the rotary chuck 1 thus or the substrate W that will handle from rotary chuck 1 reception.
Be connected with fluid supply unit 7 on rinse nozzle 5, this fluid supply unit 7 is used for optionally supplying with rinsing liquid (DIW) and mixed liquor (DIW+ organic solvent composition) to this rinse nozzle 5.Fluid supply unit 7 has the chest portion 70 (mixed liquor generating apparatus) that is used to generate mixed liquor, and the mixed liquor that is generated in chest portion 70 can be pressed and delivered to rinse nozzle 5.In addition, fluid supply unit 7 also can directly be pressed and delivered to rinse nozzle 5 as rinsing liquid with DIW.As the organic solvent composition, can adopt to be dissolved in the material that DIW (surface tension is 72mN/m) reduces surface tension, for example, (surface tension is 21～23mN/m) to isopropyl alcohol.In addition, the organic solvent composition not only is defined in isopropyl alcohol (IPA), also can adopt various organic solvent compositions such as ethanol, methyl alcohol.In addition, the organic solvent composition not only is defined in liquid, also the steam of various alcohols can be dissolved among the DIW as the organic solvent composition, thereby generate mixed liquor.So, in this embodiment, the function of rinse nozzle 5 performances " fluid Supplying apparatus " of the present invention.
Equally, at storage groove 72 end that is used for supplying with the IPA ingress pipe 74 of IPA liquid in storage groove 72 is installed, and the other end of IPA ingress pipe 74 is connected to IPA supply source SS via open and close valve 74a.And then, in the path of IPA ingress pipe 74 flowmeter 74b is installed midway, and measures the flow that imports to the IPA liquid of storage groove 72 from IPA supply source SS by flowmeter 74b.And control unit 4 is controlled the switching of open and close valve 74a based on the flow of measuring by flowmeter 74b, makes the flow of the IPA that flows through IPA ingress pipe 74 become target flow (desired value).
In this embodiment, effectively prevent to be formed at the angle of collapsing of the pattern of substrate surface Wf when suppressing the consumption of IPA, for example so that the volume ratio of IPA and DIW becomes the mode of 1:9, promptly so that the concentration of IPA becomes 10% mode, adjust the IPA (IPA liquid) import in the storage groove 72 and the flow of DIW.So reduce the concentration of IPA, thereby compare, can simplify explosion-proof countermeasure the device of IPA with 100% IPA.In addition, for the foreign matters such as particle that comprised in the supply fluid that removes whereabouts substrate W supply, need to carry out supplying with the filtration treatment of fluid (mixed liquor), but because the surface tension of 100%IPA is low, thereby have the problem that is difficult to from IPA except that foreign matters such as degranulations by filter described later.Relative therewith, if IPA and DIW are mixed, then help removing easily the foreign matter that is included in the mixed liquor.
In addition, be inserted with the other end of the mixed liquor supply pipe 75 that an end is connected with mixing valve 71, supply to mixing valve 71 thereby can will be housed in the mixed liquor of preserving in the groove 72 via mixed liquor valve 76 at storage groove 72.Mixed liquor supply pipe 75 is provided with; Constant displacement pump 77, its mixed liquor that will be housed in the storage groove 72 is transported in the mixed liquor supply pipe 75; Thermoregulator 78, it regulates the temperature that is transported to the mixed liquor in the mixed liquor supply pipe 75 by constant displacement pump 77: filter 79, it removes the foreign matter in the mixed liquor.And then, the densimeter 80 that is used to monitor IPA concentration is installed on mixed liquor supply pipe 75.
In addition, branch is connected with an end of mixed liquor circulation pipe 81 between the mixed liquor valve 76 of mixed liquor supply pipe 75 and densimeter 80, and on the other hand, the other end of mixed liquor circulation pipe 81 is connected with storage groove 72.Circulation valve 82 is installed on this mixed liquor circulation pipe 81.And when the device running, constant displacement pump 77 and thermoregulator 78 are driven all the time, and during not supplying with mixed liquor to substrate, mixed liquor valve 76 is closed, and circulation simultaneously is unlocked with valve 82.Thus, the mixed liquor from storage groove 72 is transferred by constant displacement pump 77 turns back in the storage groove 72 by mixed liquor circulation pipe 81.That is to say that during not supplying with mixed liquor to substrate W, mixed liquor circulates in the circulating path that is made of storage groove 72, mixed liquor supply pipe 75 and mixed liquor circulation pipe 81.
On the other hand, when substrate W supplies with mixed liquor, mixed liquor valve 76 is unlocked, and circulation simultaneously is closed with valve 82.Thus, will supply with to mixing valve 71 from the mixed liquor that storage groove 72 transfers out.In addition, mixing valve 71 is connected with rinse nozzle 5 via pipe arrangement 51, thereby the mixed liquor that supplies to mixing valve 71 is sprayed to substrate W from rinse nozzle 5.
So, during not supplying with mixed liquor, by making the mixed liquor circulation DIW and IPA are stirred, thereby can make DIW and IPA be in mutual well-mixed state to substrate W.In addition, after mixed liquor valve 76 is opened, can be apace supply with and reconcile to fixed temperature and removed the mixed liquor of foreign matter to rinse nozzle 5.
In addition, at the upstream side (DIW supply source WS side) of the open and close valve 73a of DIW ingress pipe 73, branch is connected with an end of DIW supply pipe 83, and simultaneously, the other end of DIW supply pipe 83 is connected with mixing valve 71.On this DIW supply pipe 83, rinsing liquid valve 84 is installed.According to this structure, then if, then can supply with DIW and mixed liquor (DIW+IPA) selectively to rinse nozzle 5 according to the switching of the control command control valve 76,84 of control unit 4.That is, close mixed liquor valve 76 and open rinsing liquid valve 84, thereby DIW is supplied to rinse nozzle 5 via mixing valve 71.On the other hand, open mixed liquor valve 76 and close rinsing liquid valve 84, thereby mixed liquor is supplied to rinse nozzle 5 via mixing valve 71.
In addition, on rinse nozzle 5, be connected with nozzle moving mechanism 53 (Fig. 5), and, according to driving nozzle moving mechanism 53, thereby rinse nozzle 5 is being moved back and forth between ejection position above the central portion of substrate W and the position of readiness kept out of the way to the side from the ejection position from the action command of control unit 4.
Then, with reference to Fig. 6～Fig. 8 C, the clean action of the substrate board treatment that constitutes is like that as mentioned above described.Fig. 6 is the flow chart of action of the substrate board treatment of presentation graphs 4.In addition, Fig. 7 is the sequential chart of action of the substrate board treatment of presentation graphs 4.In addition, Fig. 8 A, Fig. 8 B, Fig. 8 C are the schematic diagrames of action of the substrate board treatment of presentation graphs 4.
At first, control unit 4 makes splashing board 6 be positioned at retreating position, and makes rotary chuck 1 outstanding from the upper end of splashing board 6.Then, under this state,, then substrate W is carried out clean (soup processing+rinsing processing+replacement Treatment+dried) if untreated substrate W is moved into (step S1) in the auto levelizer by base board delivery device (not shown).At this, be formed with the fine pattern that for example constitutes at substrate surface Wf by Poly-Si.Therefore, in this embodiment, substrate surface Wf towards above state under, substrate W is moved in the auto levelizer, and keeps on the rotary chuck 1.
Then, control unit 4 is configured in first height and position (position shown in Figure 4) with splashing board 6, and substrate W is carried out soup handle.That is, make liquid nozzle 3 move to the ejection position, and make the substrate W that on rotary chuck 1, keeps with given rotating speed (for example 500rpm) rotation (step S2) by the driving of chuck rotating mechanism 13.Then, open soup valve 31 and supply with hydrofluoric acid to substrate surface Wf as soup from liquid nozzle 3.Supply to hydrofluoric acid on the substrate surface Wf and be subjected to action of centrifugal force and spread, handle (step S3, soup treatment process) thereby utilize hydrofluoric acid that whole base plate surface Wf is carried out soup.The hydrofluoric acid that throws away from substrate W is directed into the first sump pit 25a, thereby can suitably utilize again.
If the soup processing finishes, then liquid nozzle 3 is moved to position of readiness.Then, splashing board 6 is configured in second height and position, and substrate W is carried out rinsing handle.That is, make rinse nozzle 5 move to the ejection position, and open rinsing liquid valve 84 and supply with rinsing liquid (DIW) to the surperficial Wf of the substrate W of rotation from rinse nozzle 5.Thus, rinsing liquid is subjected to action of centrifugal force and spreads, and handles (step S4, rinsing process) thereby whole base plate surface Wf is carried out rinsing.Consequently, residually remove from substrate surface Wf by rinsing liquid attached to the hydrofluoric acid on the substrate surface Wf.The used rinsing liquid that throws away from substrate W is directed into the second sump pit 25b and goes out of use.In addition, the rotating speed of the substrate W when carrying out the rinsing processing for example is set at 100～1000rpm.
If the rinsing processing finishes, then control unit 4 is 300～500rpm with the speed setting of substrate W.In addition, close rinsing liquid valve 84, and mixed liquor valve 76 is only opened preset time.Thus, the mixed liquid of rinsing liquid that remains in rinse nozzle 5 and pipe arrangement 51 inside is extruded, and is discharged to the nozzle outside.Mixed liquor valve 76 is closed afterwards.In addition, be attached with the rinsing liquid (Fig. 8 A) of relative volume on the substrate surface Wf after rinsing is handled, but by making substrate W rotate predefined given setting-up time, thereby most of rinsing liquid is thrown away and removes from substrate surface Wf, and make a part of rinsing liquid remain in substrate surface Wf upward (step S5: liquid is removed operation).Specifically, be in such state (skin section is removed state) this moment, that is, inner residual in the gap of fine pattern FP have rinsing liquid, and have only the rinsing liquid of skin section to be removed (Fig. 8 B) from substrate surface Wf.Consequently, whole base plate surface Wf by with handle attached to rinsing after substrate surface Wf on the liquid film of thickness thin in comparison of liquid film (liquid film that constitutes by rinsing liquid) cover.If adopt above-mentioned substrate W rotating speed, then can be in the short relatively time and can prevent to realize under the dry situation of substrate surface Wf that skin section removes state.Therefore, the time of implementation of liquid being removed operation for example was set at for 0.5～1 second.If adopt this setting-up time, can prevent to cause substrate surface Wf local desiccation because of the time of implementation is long, simultaneously, can prevent to cause removing to handle and become insufficient from the rinsing liquid of substrate surface Wf because of the time of implementation is too short.
So, finish if liquid is removed operation, then control unit 4 is 500～1000rpm with the speed setting of substrate W, and splashing board 6 is configured in the 3rd height and position.Then, open mixed liquor valve 76, make from rinse nozzle 5 ejection mixed liquors (DIW+IPA).At this, generating in advance in chest portion 70 has mixed liquor (mixed liquor generation operation), and to substrate surface Wf ejection, wherein, above-mentioned mixed liquor is that volume ratio hybrid IP A and the DIW with 1:9 forms to this mixed liquor from rinse nozzle 5.In addition,, before liquid is removed operation, be discharged to the nozzle outside, therefore the situation of rinsing liquid and mixed liquor can not take place to supply with continuously to substrate surface Wf owing to remain in the rinsing liquid of rinse nozzle 5 and pipe arrangement 51 inside after the rinsing processing.Because the rinsing liquid of skin section is removed from substrate surface Wf, the mixed liquor that therefore supplies to substrate surface Wf enters into pattern interval inside easily.That is, make mixed liquor enter into the rinsing liquid of the skin section of pattern interval, be removed from substrate surface Wf in advance, so mixed liquor can enter into pattern interval inside expeditiously owing to hinder.Also have because the relative high speed rotating of substrate W, so mixed liquor be subjected to acting on mixed liquor centrifugal force influence and flow, so can make mixed liquor enter into pattern interval inside more expeditiously.Consequently, shown in Fig. 8 C, attached to the mixed reliably liquid displacement of the liquid component (rinsing liquid) of the gap location of fine pattern FP (step S6: the displacement operation).The used mixed liquor that throws away from substrate W is directed into the 3rd sump pit 25c and goes out of use.
Then, control unit 4 is held open the state of mixed liquor valve 76, and making the rotation of substrate W stop or making the speed setting of substrate W is below the 100rpm.,, mixed liquor is supplied on the substrate surface Wf like this, thereby on the Wf of whole base plate surface, form the mixing liquid layer (step S7) of immersion liquid state making substrate W static or relatively under the state with low speed rotation.Be formed on substrate surface Wf by mixing liquid layer and go up (immersion liquid processing), thereby can suppress foreign particles attached on the substrate surface Wf with this immersion liquid state.
Afterwards, control unit 4 improves the rotating speed of chuck rotating mechanism 13, thereby makes substrate W high speed rotating (for example, 2000～3000rpm).Thus, got rid of attached to the mixed liquor on the substrate surface Wf, thus dried (Rotary drying) (the step S8: drying process) of execution substrate W.At this moment, in the gap of pattern, there has been mixed liquor.Therefore, when can prevent the generation of pattern collapse and watermark, also can shorten drying time and improve production capacity.In addition, like this by shortening drying time and reduce oxidized material stripping to attached in the liquid component on the substrate W (mixed liquor), thereby can suppress the generation of watermark more effectively.If the dried of substrate W is finished, control unit 4 control card disc spins the mechanisms 13 and rotation of substrate W is stopped (step S9) then.Then, make splashing board 6 be positioned at retreating position, thereby make rotary chuck 1 outstanding from the top of splashing board 6.Then, the substrate plate send device to take out of the substrate W that handled from device, thereby finishes (step S10) for a series of clean of a substrate W.
As mentioned above, if according to this execution mode, the most rinsing liquid (DIW) that then will be attached on the substrate surface Wf is removed and is stayed a part of rinsing liquid from substrate surface Wf.Therefore can make IPA (surface tension reduction material) fully be dissolved into liquid component (rinsing liquid) attached to pattern interval inside.Its result can make attached to the liquid of involved IPA (mixed liquor) displacement reliably of the liquid component of pattern interval inside, thus the pattern collapse can prevent from effectively to carry out drying substrates time the and the generation of watermark.Also have, remove most rinsing liquid from substrate surface Wf before in the displacement that utilizes mixed liquor to carry out (displacement operation), thereby can replace rinsing liquid, therefore can suppress the consumption of IPA by the mixed liquor of relatively small amount.And then, owing to can make mixed liquor enter into pattern interval inside expeditiously, thus the time of implementation of displacement operation self can be shortened.
In addition,, then only remove the rinsing liquid of skin section, therefore can make mixed liquor enter into pattern interval inside easily from substrate surface Wf if according to this execution mode.In addition, liquid film be left behind simultaneously on substrate surface Wf with film like, only remove the rinsing liquid of skin section from substrate surface Wf, thereby prevent substrate surface Wf local desiccation.Therefore can prevent from carrying out that pattern collapse takes place when liquid is removed operation.In addition, can prevent that substrate surface Wf from exposing externally in the air, and can suppress foreign particles attached on the substrate surface Wf.
In addition, if according to this execution mode,, therefore can make DIW attached to the gap location of pattern efficiently by the material displacement of surface tension less than DIW then because IPA concentration is set at below 50%.That is,, then need a large amount of IPA if will utilize 100% IPA (IPA liquid) to replace DIW attached to the gap location of fine pattern FP, therefore, if consider that from suppressing the cost increasing angles then the consumption of each pairing IPA of substrate can be restricted.But, if the amount of the IPA that supplies with to each substrate is reduced, then shown in Fig. 9 A like that, even if make IPA be blended into skin section, also be difficult to make surface tension to reduce material (IPA) and enter into the gap of fine pattern FP and surface tension is reduced attached to the DIW on the substrate surface Wf.
Relative therewith, shown in Fig. 9 B, by being that mixed liquor below 50% supplies to substrate W with IPA concentration, thereby the mixed liquid displacement of the rinsing liquid on the substrate (DIW) also is replaced into attached to the rinsing liquid of the gap location of fine pattern FP and comprises the liquid (mixed liquor) that surface tension reduces material.So, even without utilizing 100%IPA (surface tension reduction material) to carry out replacement Treatment, also can make surface tension reduce material and enter into the gap of fine pattern FP and surface tension is reduced.At this moment, because IPA concentration is below 50%, the therefore amount of the IPA that exists in pattern interval is compared with the replacement Treatment of utilizing 100%IPA and to be become still less.But, as can be known clear and definite from Fig. 1, if make IPA concentration, do not observe that mixed liquor is capillary to be reduced significantly greater than 50% o'clock yet, therefore can not look to causing the significantly minimizing of the power of pattern collapse.On the contrary, be accompanied by the increase of the consumption of aforesaid IPA, be restricted to the quantity delivered of the mixed liquor of substrate W, more serious relatively thereby the undesirable element that is taken place becomes.Therefore, by IPA concentration is set at below 50%, can in the consumption that suppresses IPA, can prevent pattern collapse effectively thus.
That is to say, according to this execution mode, (1) then removes the most of rinsing liquid on substrate surface Wf and stay a part of rinsing liquid from substrate surface Wf, (2) employing IPA concentration is the mixed liquor below 50%, thereby can make attached to the mixed reliably liquid displacement of the liquid component at pattern interval place.That is,, can remove obstruction from substrate surface Wf and make mixed liquor enter into the rinsing liquid of pattern interval by the effect of above-mentioned (1).On this basis, by the effect of above-mentioned (2), can supply with the liquid that the surface tension that comprises relative volume reduces material (IPA) to substrate surface Wf.Therefore, can make attached to the mixed expeditiously liquid displacement of the liquid component at pattern interval place, thereby can prevent pattern collapse effectively.
And then, as can be known clear and definite from Fig. 3, when IPA concentration is 10% left and right sides, cause the power minimalization of pattern collapse.Therefore, if consider, then shown in present embodiment, preferably IPA concentration is set at about 10% or 10% from the angle that in the consumption that suppresses IPA, prevents pattern collapse effectively.More specifically will, preferably be set at IPA concentration more than 5% and below 35%, more preferably be set at more than 5% and below 10%.By such setting IPA concentration, can obtain the composite effect that two kinds of pattern collapses prevent effect, thereby can prevent pattern collapse effectively, wherein, above-mentioned two kinds of pattern collapses prevent that effect from being, the pattern collapse that obtains by the quantity delivered that increases mixed liquor prevents effect and causes that by reduction the pattern collapse that the power of pattern collapse obtains prevents effect.
＜the second execution mode 〉
Figure 10 is the figure of second execution mode of expression substrate board treatment of the present invention.In addition, Figure 11 is the block diagram of control structure of the substrate board treatment of expression Figure 10.A great difference point between the substrate board treatment of this second execution mode and first execution mode is, is provided with the cut-off component 9 of the function of performance " environment cut-off " of the present invention in the top position of rotary chuck 1.In addition, because other structure and action are identical with first execution mode basically, therefore,, and omit its explanation at the identical Reference numeral of this mark.
Cut-off component 9 is a kind ofly to have the disc-shaped component of peristome at central part, is positioned at the top position of rotary chuck 1.The lower surface of this cut-off component 9 (bottom surface) forms the opposed faces with the approximate parallel opposed of substrate surface Wf, and its planar dimension forms the size more than or equal to the diameter of substrate W.Cut-off component 9 approximately horizontally is installed in the bottom of swinging strut 91, wherein, this swinging strut 91 has the approximate cylinder shape, and, the arm 92 that swinging strut 91 is extended along horizontal direction keeps, and makes that this swinging strut 91 can be around the vertical axis rotation at the center of passing through substrate W.On arm 92, be connected with cut-off component rotating mechanism 93 and cut-off component elevating mechanism 94.
According to the action command from control unit 4, cut-off component rotating mechanism 93 makes the vertical axis rotation of swinging strut 91 around the center of passing through substrate W.In addition, according to the rotation of the substrate W that is rotated chuck 1 maintenance, cut-off component rotating mechanism 93 makes cut-off component with direction of rotation identical with substrate W and the rotation of approximately uniform rotating speed.
In addition, according to the action command from control unit 4, cut-off component elevating mechanism 94 can make cut-off component 9 opposed with it or make cut-off component 9 oppositely away from rotating platform 15 near rotating platform 15.Specifically, control unit 4 is by making cut-off component elevating mechanism 94 action, thereby substrate board treatment being moved into when taking out of substrate W, makes cut-off component 9 rise to the position of leaving of rotary chuck 1 top.On the other hand, when substrate W is implemented given processing, make cut-off component 9 drop to given opposed locations (position shown in Figure 10), this given opposed locations is set in the extremely near position of surperficial Wf from the substrate W that is rotated chuck 1 maintenance.In this embodiment, from substrate W is begun rinsing handle finish dried till, make cut-off component 9 be positioned at opposed locations.
Central portion at cut-off component 9 is provided with nozzle 95.Swinging strut 91 is processed to hollow shape, and inserts in inside and to be connected with feed tube for liquid 96.And, be connected with nozzle 95 in the lower end of feed tube for liquid 96.Feed tube for liquid 96 is connected with fluid supply unit 7 via pipe arrangement 51, and supplies with rinsing liquid and mixed liquor by fluid supply unit 7, thereby can spray rinsing liquid and mixed liquor selectively from nozzle 95.In addition, the structure of fluid supply unit 7 is identical with first execution mode.Like this, if according to this execution mode, then nozzle 95 is brought into play the function of " fluid Supplying apparatus " of the present invention.
In addition, the gap between the outside wall surface of the internal face of swinging strut 91 and feed tube for liquid 96 forms gas feed path 97 cylindraceous.This gas feed path 97 is connected with gas supply source GS via open and close valve 98, thereby can supply with nitrogen to the space that forms between cut-off component 9 and substrate surface Wf.In addition, in this embodiment, supply with nitrogen from gas supply source GS, but also can spray air or other inert gas.Like this, if according to this execution mode, the function of gas supply source GS performance " gas supply device " of the present invention.
In having the substrate board treatment of structure as mentioned above, substrate W is carried out clean in such a way.That is, to substrate surface Wf supply of chemical, and substrate W is carried out soup handle from liquid nozzle 3.Then, cut-off component 9 is positioned in opposed locations from leaving the position, and cut-off component 9 is accompanied by the rotation of substrate W and rotates.Then, supply with nitrogen from gas feed path 97, thereby make the space that is clipped between cut-off component 9 and the substrate surface Wf become nitrogen environment.In addition, substrate W is implemented rinsing handle (rinsing process) from nozzle 95 ejection rinsing liquids (DIW).Carrying out after rinsing handles,, only throw away and be removed (liquid is removed operation) from substrate surface Wf attached to the skin section in the rinsing liquid on the substrate surface Wf by the rotation of substrate W.
Then, from nozzle 95 ejection mixed liquors (DIW+IPA), thereby replace (displacement operation) to residual attached to the rinsing liquid on the substrate surface Wf by mixed liquor.And then, making under the static or relative state of substrate W, supply with mixed liquor, thereby on the Wf of whole base plate surface, form the mixing liquid layer of immersion liquid state to substrate surface Wf with low speed rotation.Like this, if be formed with the mixing liquid layer on substrate surface Wf, then control unit 4 improves the motor rotary speed of rotary chuck 13 and cut-off component rotating mechanism 93, thereby makes substrate W and cut-off component 9 high speed rotating.Thus, Wf gets rid of mixed liquor from substrate surface, thereby carries out the dried (Rotary drying) (drying process) to substrate W.In this dried, make the space that is clipped between cut-off component 9 and the substrate surface Wf become nitrogen environment, therefore can promote drying, thereby can shorten drying time substrate W.
As mentioned above, then same if according to this execution mode with first execution mode, before replacing operation, remove attached to the most rinsing liquid on the substrate surface Wf and stay a part of rinsing liquid.Therefore, can make attached to the displacement of the mixed reliably liquid of the liquid component of pattern interval inside, thus the pattern collapse can prevent from effectively to carry out drying substrates time the and the generation of watermark.And then, make the space that is formed between cut-off component 9 and the substrate surface Wf become nitrogen environment, thereby can reduce the oxygen concentration of the surrounding environment of substrate W, therefore can suppress oxidized material such as Si from substrate surface Wf stripping to rinsing liquid and mixed liquor.Thus, can prevent from effectively on substrate surface Wf, watermark to take place.
＜the three execution mode 〉
Figure 12 A, Figure 12 B, Figure 12 C are the figure of the 3rd execution mode of expression substrate board treatment of the present invention.A great difference point between the substrate board treatment of the 3rd execution mode and first and second execution mode is, after the displacement operation and before drying process, carries out dry pretreatment procedure.In addition, because other structure and action are identical with second execution mode basically, therefore,, and omit its explanation at the identical Reference numeral of this mark.
In this embodiment, utilizing mixed liquor to replace (displacement operation) afterwards and substrate W is being carried out drying (drying process) before, carry out dry pretreatment procedure as described below.At first, supply with mixed liquor, thereby on the whole base plate surface, form the mixing liquid layer 21 (Figure 12 A) of immersion liquid state to substrate surface Wf.Then, from the surperficial central portion ejection nitrogen of gas jetting nozzle 8 to substrate W.In addition, this moment substrate W is rotated with low speed (for example 50rpm).Like this, shown in Figure 12 B,, mix the crowded radial outside that falls back on substrate W of mixed liquor quilt of the central portion of liquid layer 21 by from the nitrogen of gas jetting nozzle 8 to substrate surface Wf ejection, thereby form hole 22 at the central portion that mixes liquid layer 21, and its surface portion is dried.
Then, then the surperficial central portion to substrate W sprays nitrogen, thereby shown in Figure 12 C, the hole 22 that forms is enlarged gradually to the end edge direction (left and right directions of this figure) of substrate W, so the mixed liquor that mixes the center side of liquid layer 21 is extruded and the arid region is progressively enlarged gradually to the edge of substrate avris from center side.Thus, can with the surperficial central portion of substrate W not the mode of residual mixed liquor remove the mixed liquor of the surperficial central portion that is attached to substrate W.Like this, in this embodiment, the function of gas jetting nozzle 8 performances " gas discharge device " of the present invention.
So, some dry pretreatment procedures finish, and then make substrate W high speed rotating and carry out dried (Rotary drying) to substrate W.At this moment, same with second execution mode, also can make cut-off component 9 near substrate surface Wf, and make the space that is clipped between cut-off component 9 and the substrate surface Wf become nitrogen environment.Thus, when drying time can be shortened, can suppress the stripping of oxidized material.
As mentioned above, if according to this execution mode, then by carrying out aforesaid dry pretreatment procedure, can prevent that mixed liquor remains in the surperficial central portion of substrate W and becomes the striated foreign particles with droplet-like in the process of carrying out drying process, thereby can prevent from substrate surface Wf, to form watermark.That is, when carrying out drying (Rotary drying) by substrate W being rotated remove attached to the mixed liquor on the substrate surface Wf, the centrifugal force that acts on mixed liquor is just more little the closer to the surperficial central portion of substrate W, and is therefore progressively dry from the endmost surface limit of substrate W.At this moment, drop is arranged, and this drop moves to the end edge direction of substrate W, make to form watermark sometimes at the mobile vestige place of this drop from the surperficial central portion of substrate W is residual around it.Relative therewith, if according to this execution mode, the central portion that then was pre-formed the mixing liquid layer 21 of the immersion liquid state on substrate surface Wf before carrying out drying process forms hole 22, and this hole 22 is progressively enlarged, thereby therefore the mixed liquor of getting rid of the surperficial central portion that is positioned at substrate W can prevent the formation of watermark reliably.Particularly under the low situation of IPA concentration, can become greatly the relative 100%IPA of contact angle θ of substrate surface Wf, therefore be in the situation that is easy to generate striated foreign particles and watermark.Therefore, in order to prevent striated foreign particles and watermark, become very effective and carry out aforesaid dry pretreatment procedure.
＜the four execution mode 〉
Figure 13 is the figure of the 4th execution mode of expression substrate board treatment of the present invention.A great difference point between the substrate board treatment of the 4th execution mode and first execution mode is, in the first embodiment, utilize identical fluid Supplying apparatus (rinsing liquid nozzle 5) to come to supply with rinsing liquid (DIW) and mixed liquor (IPA+DIW) to substrate W, relative therewith, in this embodiment, can from respectively independently nozzle (fluid Supplying apparatus) supply with rinsing liquid and mixed liquor respectively to substrate surface Wf.
In this embodiment, be provided with rinse nozzle 55 and mixed liquor nozzle 57, they can supply with rinsing liquid and mixed liquor respectively from the top that is rotated the substrate W that chuck 1 keeps.Rinse nozzle 55 is connected with the rinsing liquid supply source via rinsing liquid valve 55a, and on the other hand, mixed liquor nozzle 57 is connected with the mixed liquor supply source via mixed liquor valve 57a.Therefore, control unit 4 can spray rinsing liquid and mixed liquor respectively to substrate surface Wf from rinse nozzle 55 and mixed liquor nozzle 57 independently by the switching of control rinsing liquid valve 55a and mixed liquor valve 57a.In addition, on rinse nozzle 55 and mixed liquor nozzle 57, be connected with nozzle moving mechanism (not shown), by the driving of nozzle moving mechanism, rinse nozzle 55 and mixed liquor nozzle 57 are moved respectively between ejection position above the central portion of substrate W and the position of readiness kept out of the way to the side from the ejection position.Like this, in this embodiment, the function of mixed liquor nozzle 57 performances " fluid Supplying apparatus " of the present invention.And, in this embodiment, substrate W is carried out clean by following mode.
Figure 14 is the sequential chart of action of the substrate board treatment of expression Figure 13.At this, the rotating speed of the substrate that sets in each operation when carrying out clean is identical with first execution mode (Fig. 7).Carrying out after soup handles, opening rinsing liquid valve 55a and supply with rinsing liquid to substrate surface Wf from rinse nozzle 55.Thus, substrate surface Wf is implemented rinsing and handle (rinsing process).Then, close rinsing liquid valve 55a, and (300～500rpm) only rotate given setting-up time (0.5～1 second) with given rotating speed to make substrate W.Thus, the rinsing liquid on the substrate surface Wf is got rid of roughly from substrate surface Wf and is removed (liquid is removed operation).Then, open mixed liquor valve 57a and supply with mixed liquor to substrate surface Wf from mixed liquor nozzle 57.On substrate surface Wf, owing to removed the rinsing liquid of skin section, so mixed liquor enters into pattern interval inside easily, thus can mixed liquid displacement (displacement operation) attached to the rinsing liquid at pattern interval place.If utilize the replacement completion of mixed liquor, then under the state that is held open mixed liquor valve 57a, the rotation of substrate W is stopped or making substrate W with low speed rotation (100rpm), on substrate surface Wf, form the mixing liquid layer of immersion liquid state thus.Then, make substrate W high speed rotating, thereby make substrate W drying (drying process).
As mentioned above, then same if according to this execution mode with first execution mode, before carrying out the displacement operation, remove attached to the most of rinsing liquid on the substrate surface Wf and stay a part of rinsing liquid.Therefore, can make attached to the displacement of the mixed reliably liquid of the liquid component (rinsing liquid) of pattern interval inside, thus the pattern collapse can prevent from effectively to carry out drying substrates time the and the generation of watermark.And then, if according to this execution mode, then from respectively independently nozzle supply with rinsing liquid and mixed liquor to substrate surface Wf.Therefore, in rinse nozzle 55 and mixed liquor nozzle 57, mixed liquor and rinsing liquid can residually not arranged respectively.Therefore, do not need as first execution mode, carrying out before liquid removes operation, to be discharged to nozzle outside and mixed liquor is pressed and delivered in the rinse nozzle 5 for the rinsing liquid that will remain in rinse nozzle 5 and pipe arrangement 51 inside.Consequently, the processing action of valve on-off action etc. can be simplified, and the use amount that can save mixed liquor, thereby the consumption of IPA can be further suppressed.
In addition, also same in this embodiment with second execution mode, making under cut-off component and the opposed situation of substrate surface Wf, substrate is carried out clean also can.At this moment, as long as two nozzles are set, promptly spray the rinse nozzle of rinsing liquid and the mixed liquor nozzle of ejection mixed liquor at the central portion of cut-off component.And then, same with the 3rd execution mode, after the displacement operation and before drying process, carry out dry pretreatment procedure and also can.
＜other 〉
In addition, the present invention not only is defined in above-mentioned execution mode, and in the scope that does not break away from its aim, various changes that can be except that above-mentioned execution mode.For example, in the above-described embodiment, implemented for the substrate W that is rotated chuck 1 maintenance after the wet processed such as soup processing and rinsing liquid processing, directly in same apparatus, the substrate W that is soaked by rinsing liquid has been carried out utilizing the replacement Treatment and the dried (Rotary drying) of mixed liquor, but also replacement Treatment and dried can have been separated and carried out from wet processed.And then, also replacement Treatment can be separated and carried out from dried.
In addition, in the above-described embodiment, with chest portion 70 as the mixed liquor generating apparatus, and in chest portion 70 mixing material (DIW) and organic solvent composition (IPA), thereby generated mixed liquor, still, the mixed liquor generating apparatus is not limited thereto.For example, as shown in figure 15, generating mixed liquor at the internal mix organic solvent composition of liquid delivery path from liquid to fluid Supplying apparatus such as nozzles that carry also can (the 5th execution mode).
Figure 15 is the figure of the 5th execution mode of expression substrate board treatment of the present invention.In addition, Figure 16 is the sequential chart of action of the substrate board treatment of expression Figure 15.In this embodiment, rinse nozzle 59 is connected with the rinsing liquid supply source via rinsing liquid valve 59a.In addition, on the hybrid position in downstream on the liquid delivery path that connects rinse nozzle 59 and rinsing liquid supply source, that be positioned at rinsing liquid valve 59a, be connected with the IPA supply source via IPA valve 59b.By this structure, if close IPA valve 59b and open rinsing liquid valve 59a, then rinsing liquid (DIW) supplies to rinsing liquid nozzle 59.In addition, if open rinsing liquid valve 59a and IPA valve 59b, then DIW and IPA are mixed at hybrid position, thereby supply with mixed liquor (IPA+DIW) to rinsing liquid nozzle 59.In addition and since other structure and the action identical with first execution mode basically, so following be that the center describes with the distinctive points.
In this embodiment, as shown in figure 16, when rinse nozzle 59 is supplied with mixed liquor, rinsing liquid valve 59a and IPA valve 59b all are unlocked.Promptly, in the latter stage of rinsing process, in order to be discharged to the nozzle outside attached to rinse nozzle 59 and the inner rinsing liquid (DIW) of liquid delivery path (pipe arrangement in the downstream of rinsing liquid valve 59a) with residual, and open IPA valve 59b when opening rinsing liquid valve 59a, therefore supply with mixed liquors to rinse nozzle 59.Thus, when after liquid is removed operation, carrying out the displacement operation, can not spray mixed liquor from rinse nozzle 59 ejection rinsing liquids (only spraying DIW).Therefore, then same if according to this execution mode with first execution mode, can implement clean to substrate W, thereby can obtain the action effect identical with first execution mode.
In addition, the mixed liquor generating apparatus not only is defined in the situation that is set at substrate board treatment inside, and also can supply with mixed liquor to substrate surface Wf via the fluid Supplying apparatus that in substrate board treatment, is provided with, this mixed liquor is independently to generate in other devices of setting in addition with substrate board treatment.
In addition, in the above-described embodiment, remove attached to the liquid on the substrate surface Wf (rinsing liquid) by making substrate W rotate to get rid of, but the method for removing of liquid not only is defined in this from substrate W.For example, can remove most liquid from substrate surface Wf thus, and stay the part of this liquid to attached to the ejection of the liquid on substrate surface Wf gas.In addition, scraper plate etc. scraped get member and be configured in from substrate surface Wf away from giving on the height and position of set a distance, and make to scrape and get the relative substrate of member and relatively move, get member and scrape to get attached to the skin section of the liquid on the substrate surface Wf to remove and also can thereby utilize to scrape from substrate surface Wf.
In addition, in the above-described embodiment, adopt hydrofluoric acid and, but also can utilize BHF (buffer hydrofluoric acid: buffered hydrofluoric acid) handle and also can as soup.
And then, in the above-described embodiment, the substrate surface Wf that is soaked by rinsing liquid has been carried out drying, but also can being applied to the substrate surface Wf that soaks for the liquid of quilt except that rinsing liquid, the present invention carries out dried base plate processing method and substrate board treatment.
In addition, in the above-described embodiment, adopt DIW and, but also can adopt carbonated water (DIW+CO as rinsing liquid
2) wait comprise to substrate surface Wf do not have the chemical cleaning effect composition liquid and as rinsing liquid.At this moment, also can use by the liquid that mixes with liquid (carbonated water) and organic solvent composition as mixed liquor attached to the rinsing liquid same composition on the substrate surface Wf.In addition, adopt carbonated water and as rinsing liquid, simultaneously, mixed liquor adopts by also can as the DIW of the principal component of carbonated water and the liquid that the organic solvent composition mixes.And then, adopt DIW and as rinsing liquid the time, mixed liquor adopts the liquid that is mixed by carbonated water and organic solvent composition also can.In a word, as long as adopt with the liquid that mixes attached to the identical liquid of the liquid principal component on the substrate surface Wf and organic solvent composition as mixed liquor.In addition, as rinsing liquid, except DIW, carbonated water, can also adopt ammoniacal liquor, hydrochloric acid of hydrogeneous water, concentration thin (for example about 1ppm) etc.
The present invention can be applied to the surface of various substrates is implemented the substrate board treatment and the substrate processing method using same of dried, and these various substrates comprise that semiconductor wafer, photomask show with glass substrate, CD with substrate with glass substrate, liquid crystal display with glass substrate, plasma etc.
Claims (17)
1. a substrate processing method using same carries out drying to the substrate surface that is soaked by liquid, it is characterized in that, comprising:
Liquid is removed operation, the major part that is attached to the liquid on the described substrate surface is removed from described substrate surface and stays a part of liquid;
The displacement operation, on surface, supply with mixed liquor with the maintained substrate of level of approximation posture, the residual liquid component that is attached on the described substrate surface is replaced into described mixed liquor after described liquid is removed operation thereby make, wherein, described mixed liquor be by be attached to described substrate surface on the liquid same composition liquid or with being attached to liquid principal component on the described substrate surface identical liquid and be dissolved in this liquid and the organic solvent composition that surface tension is reduced mixes;
Drying process after described displacement operation, is removed described mixed liquor and is made this substrate surface drying from described substrate surface,
The percentage by volume of the described organic solvent composition in the described mixed liquor is below 50%.
2. substrate processing method using same as claimed in claim 1 is characterized in that,
Remove in the operation at described liquid, only remove the skin section that is attached to the liquid on the described substrate surface from described substrate surface.
3. substrate processing method using same as claimed in claim 1 is characterized in that,
Remove in the operation at described liquid, make described substrate rotation, and get rid of and remove the liquid that is attached on the described substrate surface from described substrate surface.
4. substrate processing method using same as claimed in claim 3 is characterized in that,
Remove in the operation at described liquid, the rotating speed of described substrate is 300～500rpm.
5. substrate processing method using same as claimed in claim 3 is characterized in that,
The time of implementation that described liquid is removed operation was 0.5～1 second.
6. substrate processing method using same as claimed in claim 1 is characterized in that,
The percentage by volume of the described organic solvent composition in the described mixed liquor is more than 5% and below 35%.
7. substrate processing method using same as claimed in claim 6 is characterized in that,
The percentage by volume of the described organic solvent composition in the described mixed liquor is below 10%.
8. substrate processing method using same as claimed in claim 1 is characterized in that,
In described displacement operation, make described substrate rotation, simultaneously described mixed liquor is supplied with to described substrate surface.
9. substrate processing method using same as claimed in claim 1 is characterized in that,
Before described liquid is removed operation, also have rinsing liquid is supplied with and the rinsing process of enforcement rinsing processing to described substrate surface,
To be attached to described rinsing liquid on the described substrate surface behind the described rinsing process, and the described substrate surface that is soaked by described rinsing liquid carried out drying as the liquid that is attached on the described substrate surface.
10. substrate processing method using same as claimed in claim 9 is characterized in that,
Described liquid is removed operation and is begun to continue to carry out when described rinsing process finishes, when described displacement operation begins till.
11. substrate processing method using same as claimed in claim 9 is characterized in that,
Before described rinsing process, also have soup is supplied with and the soup treatment process of enforcement soup processing to described substrate surface,
In the described rinsing process, remove the residual soup that is attached on the described substrate surface from described substrate surface.
12. substrate processing method using same as claimed in claim 1 is characterized in that,
Described drying process carries out in inert gas environment.
13. as each described substrate processing method using same in the claim 1～12, it is characterized in that,
In described drying process, get rid of the described mixed liquor that is attached on the described substrate surface by making described substrate rotation, thereby make described substrate surface drying,
After described displacement operation and before described drying process, also has dry pretreatment procedure, in this drying pretreatment procedure, on whole described substrate surface, form the mixing liquid layer of immersion liquid state by described mixed liquor, and then form the hole at the central portion of described mixing liquid layer, and described hole is enlarged to the end edge direction of described substrate to the surperficial central portion ejection gas of described substrate.
14. a substrate board treatment is characterized in that, comprising:
Base plate keeping device, its substrate surface that is soaked by liquid towards above state under, substrate is remained the level of approximation posture;
Fluid Supplying apparatus, it supplies with mixed liquor to surface of the substrate that is kept by described base plate keeping device, this mixed liquor be by be attached to described substrate surface on the liquid same composition liquid or with being attached to liquid principal component on the described substrate surface identical liquid and be dissolved in this liquid and the organic solvent composition that surface tension is reduced mixes;
Liquid is removed device, and its major part that will be attached to the liquid on the described substrate surface is removed from described substrate surface and stayed a part of liquid,
Remove device after described substrate surface is removed described liquid by described liquid, the percentage by volume of supplying with the described organic solvent composition the described mixed liquor to described substrate surface from described fluid Supplying apparatus is the mixed liquor below 50%, and make the liquid component that is attached on the described substrate surface be replaced into described mixed liquor, remove described mixed liquor and make described substrate surface drying from described substrate surface then.
15. substrate board treatment as claimed in claim 14 is characterized in that,
Also have whirligig, this whirligig makes the substrate rotation that is kept by described base plate keeping device,
Described whirligig is removed device as described liquid and is made described substrate rotation, thereby gets rid of and remove the liquid that is attached on the described substrate surface from described substrate surface.
16., it is characterized in that also having as claim 14 or 15 described substrate board treatments:
The environment cut-off, its top position and described substrate surface at described substrate is opposed, and with described substrate surface configured separate;
Gas supply device, it supplies with inert gas in the space that is formed between described environment cut-off and the described substrate surface.
17. substrate board treatment as claimed in claim 15 is characterized in that,
Make described substrate rotation by described whirligig, thereby get rid of described mixed liquor and make described drying substrates from described substrate surface,
This substrate board treatment also has gas discharge device, and this gas discharge device sprays gas to the surperficial central portion by the substrate that described base plate keeping device kept,
Utilize described mixed liquor replace after and before described substrate surface is carried out drying, supply with described mixed liquor from described fluid Supplying apparatus to described substrate surface, and on whole described substrate surface, form the mixing liquid layer of immersion liquid state by described mixed liquor, and then, form hole to the surperficial central portion ejection gas of described substrate at the central portion of described mixing liquid layer from described gas discharge device, and described hole is enlarged to the end edge direction of described substrate.
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| CN105470109A (en) * | 2014-09-30 | 2016-04-06 | 株式会社思可林集团 | Substrate processing method and substrate processing apparatus |
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| US8323065B2 (en) | 2008-07-22 | 2012-12-04 | Lg Display Co., Ltd. | Organic electro-luminescence display device and manufacturing method thereof |
| US8486201B2 (en) * | 2009-07-16 | 2013-07-16 | Lam Research Ag | Method for drying a semiconductor wafer |
| US20120103371A1 (en) * | 2010-10-28 | 2012-05-03 | Lam Research Ag | Method and apparatus for drying a semiconductor wafer |
| JP6304592B2 (en) * | 2014-03-25 | 2018-04-04 | 株式会社Ｓｃｒｅｅｎホールディングス | Substrate processing method and substrate processing apparatus |
| US10490426B2 (en) | 2014-08-26 | 2019-11-26 | Lam Research Ag | Method and apparatus for processing wafer-shaped articles |
| CN105047529A (en) * | 2015-05-28 | 2015-11-11 | 上海集成电路研发中心有限公司 | Method for improving wet process wettability of small-size and high aspect ratio structures |
| WO2017029862A1 (en) * | 2015-08-18 | 2017-02-23 | 株式会社Ｓｃｒｅｅｎホールディングス | Substrate treatment method and substrate treatment device |
| CN106546067B (en) * | 2015-09-18 | 2022-08-19 | 海南椰国食品有限公司 | Low-temperature integrated drying method for replacing bacterial cellulose gel film |
| CN108237116A (en) * | 2018-01-23 | 2018-07-03 | 滁州英诺信电器有限公司 | Cleaning before PC material film platings |
| JP7030633B2 (en) * | 2018-06-29 | 2022-03-07 | 株式会社Ｓｃｒｅｅｎホールディングス | Board processing equipment and board processing method |
| CN110707022B (en) * | 2019-09-06 | 2022-07-29 | 长江存储科技有限责任公司 | Wafer cleaning device |
| CN111739829B (en) * | 2020-08-26 | 2020-11-17 | 华海清科(北京)科技有限公司 | Wafer drying method and system |
| CN114289174B (en) * | 2021-11-17 | 2023-11-24 | 镇康县振兴矿业开发有限责任公司 | Quality improvement and silicon reduction process and device for iron ore concentrate |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105470109A (en) * | 2014-09-30 | 2016-04-06 | 株式会社思可林集团 | Substrate processing method and substrate processing apparatus |
| TWI609725B (en) * | 2014-09-30 | 2018-01-01 | 思可林集團股份有限公司 | Substrate processing method and substrate processing apparatus |
| CN105470109B (en) * | 2014-09-30 | 2018-07-27 | 株式会社思可林集团 | Substrate processing method using same and substrate board treatment |
| US10121648B2 (en) | 2014-09-30 | 2018-11-06 | SCREEN Holdings Co., Ltd. | Substrate processing method and substrate processing apparatus |
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