CN1841213A - Developing method and method of manufacturing a semiconductor device - Google Patents

Abstract

The invention relates to a developing method for developing the light-sensitive erosion resistance film, wherein said method comprises: first developing said erosion resistant film; washing the erosion resistant film with washing liquid that oxidant to the erosion resistant film or be alkali; developing the washed erosion resistant film; and washing the erosion resistant film.

Description

The manufacture method of developing method and semiconductor device

The application is that the application number submitted on January 28th, 2003 is the dividing an application of Chinese patent application " manufacture method of substrate processing method using same and device, developing method and semiconductor device " of 03102209.X.

The cross reference of related application

The application is based on following Japanese patent application: the No.P2002-57764 that the No.P2002-17937 that on January 28th, 2002 submitted to and on March 4th, 2002 submit to, and require the right of priority of these two patented claims, their full content is contained in this for your guidance.

Technical field

The present invention relates to use the substrate processing method using same for the treatment of fluid treatment substrate, and substrate board treatment, particularly in making the process of semiconductor device etc., after development treatment, then implement to clean substrate processing method using same, the substrate board treatment that uses when handling.

Background technology

In the manufacturing of semiconductor device, liquid crystal display, electronic-circuit-component etc., comprise in the process of circuit of element, distribution etc. in formation,, on substrate, carry out development treatment in order to form pattern, thereafter, order is cleaned processing and dried etc.

If the manufacturing process of semiconductor device, then at first, on semiconductor substrate, form machined membrane (for example, dielectric film, distribution use conducting film), photosensitive photoresist film with known method.On this photoresist film implement development treatment thereafter.At this, as known in the art, on the photosensitive photoresist film on the semiconductor substrate, after by the pattern of exposure, provide developer solution to form pattern with groove (レ チ Network Le) projection exposure regulation.

After carrying out development treatment, on the surface of semiconductor substrate, residual developer solution, the dissolving product that in development treatment, produces, and small particle etc.If this so-called impurity, pollutant left behind, then the pattern of photoresist is used as mask, at machined membrane (for example, dielectric film, as the conducting film of the material of wiring layer) on apply in the process of etching and processing, can produce the error of size, decrease in yield in the manufacturing of semiconductor device.

Thereby order implement to clean is handled and dried, for the state that the surface working of semiconductor substrate is become to clean, need remove residual, the dissolving product that produces of developer solution in development treatment, and small particle etc.

In method of cleaning in the past,,, make stopping of developing reaction Yi Bian,, developer solution is replaced into detergent remover by detergent remover is flowed from the direction of central portion to periphery from fixing nozzle ejection detergent remover Yi Bian make the substrate high-speed rotation.In addition, simultaneously, the dissolving product that removes developer solution, in development treatment, produces in the eccysis of substrate upper punch, and molecule etc.

In recent years, carried out the miniaturization, highly integrated of semiconductor device, and the technological development of the heavy caliberization of semiconductor substrate.Follow the heavy caliberization of semiconductor substrate, that is, the area of substrate increases, and when the method for cleaning that uses in the past, produces many problems.

The ejiction opening of nozzle is set to be fixed on the position of central portion top of semiconductor substrate.Thereby, on semiconductor substrate, by the detergent remover of nozzle ejection, the central portion of directly contact and near, the degree height that developer solution is replaced, and dissolving product and small particle also can be removed clean effect height effectively.

But at the periphery of semiconductor substrate, detergent remover not directly and with sufficient pressure is flushed to, with the central portion of semiconductor substrate, and near compare, clean effect and reduce.Thereby at the edge part of semiconductor substrate, and residual, in addition, it is clean and residual that dissolving product and small particle are not removed yet not by displacement for the part of developer solution, produces so-called clean spot.

In addition, in method of cleaning in the past, comprising dried, is to make the substrate high-speed rotation.Thereby, follow the heavy caliberization of substrate, the further rational load of increment brings harmful effect to the pattern of the photoresist that forms through development treatment.

For example, using the heavy caliber substrate more than the 300mm to make under the situation of semiconductor device,, be subjected to the influence of the current of centrifugal force and detergent remover at the periphery of semiconductor substrate, the damage of the photoresist pattern that formed by development treatment takes place significantly, perhaps the crooked phenomenon of pattern.Thus, after development treatment, more and more need not make substrate rotating, clean and handle and dried.

Follow the miniaturization of semiconductor element size, in developing method in the past because between pattern developer solution infiltrate insufficient, so there is the problem of the pattern dimension unevenness of the part in the chip.In addition, follow the heavy caliberization of substrate, in developing method in the past, be created in the unevenness of pattern dimension in the real estate, become big problem.

, usually in semi-conductive manufacturing process as the developer solution of photonasty resist, use the alkaline aqueous solution of tetramethylammonium hydroxide (TMAH) etc.Because developer solution is an aqueous solution, so not enough to being hydrophobic photonasty resist surface moist.Therefore, during near surface, developer solution is difficult to be diffused between resultant of reaction and the photonasty resist surface at the resultant reactant of neutralization reaction, and alkali ion concentration is different locally, result viewing to developing powder in different places and difference.

For example, pattern in existence is configured in broad dissolving zone and be configured in around under the situation of pattern on the almost not dissolved zone, in the pattern in being configured in broad dissolving zone, because near the amount of the resultant of reaction that exists pattern is many, developer solution is difficult to be diffused between resultant of reaction and the photonasty resist, so hinder the carrying out that develops, compare with the pattern that is configured on the almost not dissolved on every side zone, had the linear dimension chap this problem (difference in size of density pattern).

Summary of the invention

One example according to the present invention, the developing method of the development that the photonasty of desired pattern resist film is arranged of exposing comprises: the above-mentioned photonasty resist film that is exposed is carried out the 1st development treatment; To having carried out the photonasty resist film of the 1st development treatment, provide this resist film surface is had oxidisability, or the detergent remover of alkalescence, carry out the 1st and clean processing; Carry out the 2nd development treatment to having finished the 1st above-mentioned photonasty resist film of cleaning processing; The above-mentioned photonasty resist that has carried out the 2nd development treatment is carried out the 2nd clean processing.

One example according to the present invention, the developing method of development that the photonasty of desired pattern resist film is arranged exposes, comprise: on above-mentioned photonasty resist film, provide developer solution, developer solution on the above-mentioned photonasty resist film is flowed, wherein, between the start time and concluding time of the step that above-mentioned developer solution is flowed, comprise the passing through the time of bottom surface that developer solution reaches the above-mentioned photonasty resist film zone that above-mentioned relatively developer solution can dissolve.

One example according to the present invention, the developing method of development that the photonasty of desired pattern resist film is arranged exposes, comprise: on above-mentioned photonasty resist film, provide developer solution, developer solution on the above-mentioned photonasty resist film is flowed, wherein, the start time that above-mentioned developer solution is flowed is after developer solution reaches time of passing through of bottom surface in the above-mentioned photonasty resist film zone that above-mentioned relatively developer solution can dissolve.

One example according to the present invention, the developer solution that uses when the photonasty resist film that development is exposed provides the method for cleaning of nozzle, comprising: provide nozzle that developer solution is provided to above-mentioned developer solution; Oxidizing liquid is offered the developer solution that developer solution is provided on substrate provide nozzle to clean.

Description of drawings

Fig. 1 is the overall diagram of showing the processing substrate mechanism relevant with embodiment 1.

Fig. 2 is a planimetric map of showing the formation of the clean processing usefulness nozzle relevant with embodiment 1.

Fig. 3 A and Fig. 3 B are the diagrams of showing the substrate processing method using same relevant with embodiment 1.

Fig. 4 is a sectional drawing of showing the substrate processing method using same relevant with embodiment 1.

Fig. 5 A and Fig. 5 B are the diagrams of showing the effect of embodiment 1.

Fig. 6 is the overall diagram of showing the processing substrate mechanism relevant with embodiment 2.

Fig. 7 is a planimetric map of showing the formation of the clean processing usefulness nozzle relevant with embodiment 2.

Fig. 8 is a sectional drawing of showing the substrate processing method using same relevant with embodiment 2.

Fig. 9 A and Fig. 9 B are the diagrams of showing the effect of embodiment 2.

Figure 10 is a sectional drawing of showing the substrate processing method using same relevant with embodiment 2.

Figure 11 is the process flow diagram of displaying according to the processing sequence of the developing method of embodiment 3.

Figure 12 is the process chart of showing according to the developing method of embodiment 3.

Figure 13 A and Figure 13 B are the process charts of showing according to the developing method of embodiment 3.

Figure 14 A and Figure 14 B are the process charts of showing according to the developing method of embodiment 3.

Figure 15 A and Figure 15 B are the process charts of showing according to the developing method of embodiment 3.

Figure 16 A and Figure 16 B are the process charts of showing according to the developing method of embodiment 3.

That Figure 17 is that medelling show to observe is adopted is that KrF is just obtaining during the dissolving situation of the developer solution of (Port ジ) type resist, from the curve map of the intensity of reflected light of general substrate.

Figure 18 A and Figure 18 B are the sectional drawings that the resist film in developing is showed in medelling.

Figure 19 is the process flow diagram of showing according to the development treatment order of embodiment 4.

Figure 20 is the diagram of displaying according to the summary formation of the development processing apparatus of embodiment 5.

Figure 21 is the process flow diagram of showing according to the development treatment of embodiment 6.

Figure 22 shows the process chart according to the development treatment of embodiment 6.

Figure 23 represents the diagram from the intensity of reflected light variation of showing the resist film in the development.

Figure 24 is with time shaft beginning, developer solution flow, the develop diagram of the differentiation that finishes of representing to develop.

Figure 25 shows that liquid flows regularly and the diagram of the relation of deviation (ぱ ら つ I).

Figure 26 is the diagram that expression comes the intensity of reflected light of the resist film in the autography to change.

Figure 27 shows that liquid flows regularly and the diagram of the relation of deviation.

Figure 28 is the process flow diagram of showing according to the development treatment of embodiment 7.

Figure 29 is the diagram of displaying according to the summary formation of the development processing apparatus of embodiment 7.

Figure 30 is the formation of nozzle is used in expression according to the processing substrate of embodiment 1 a planimetric map.

Figure 31 shows the planimetric map of using the formation of nozzle according to the processing substrate of embodiment 2.

Embodiment

Below, with reference to the description of drawings embodiments of the present invention.

(embodiment 1)

In the present embodiment,, form the size of regulation and the pattern of shape, carry out development treatment, clean and handle for the processed zone on substrate, and dried.In addition, in the present embodiment, on a substrate, use can be carried out development treatment continuously, clean development processing apparatus processing procedure, so-called sheet leaf formula of processing and dried in a device.

In the inside of this development processing apparatus, be provided with and can carry out development treatment, clean and handle substrate continuously, and the processing unit of dried.In present embodiment, in this processing unit, use each corresponding processing mechanism to carry out development treatment, clean and handle, and a series of processing procedure of dried.

In this processing unit,,, be provided with development treatment mechanism in order to carry out known scanning development treatment as an example.In that possess on the part of this development treatment mechanism can be up and down and the development nozzle of the movable type that moves on the horizontal direction, Yi Bian feasiblely spray developer solution (treating fluid), Yi Bian on the scanning substrate.On this develops with nozzle,, be provided with the ejiction opening of elongated rectangular shape of slit for the processed zone on substrate provides developer solution with uniform amount.

In addition, except above formation, on processing unit, as shown in figure 10, also be provided with clean processing mechanism.Below, be described in detail in Fig. 1 and carry out development treatment, clean to handle, and the formation of the clean processing mechanism that is provided with in the processing unit of dried, and action.

And then, in Fig. 1, suppose to show the main component part relevant with clean processing mechanism 100.

Carrying out development treatment and cleaning in the unit of handling, possesses clean processing mechanism 100 shown in Figure 1.In clean processing mechanism 100, as main component part, possess sucker (チ ヤ Star Network) 101, clean usefulness nozzle 102 that fixed support is used, and scanning mechanism 111.The sucker 101 that these fixed supports are used, and clean with nozzle 102, by nozzle 102 being moved, nozzle 102 is relatively moved with respect to substrate by scanning mechanism 111.

In clean processing mechanism 100, after carrying out development treatment, substrate 103 is placed and is fixed on the sucker 101 that fixed support uses, and from cleaning the detergent remover that regulation is provided with nozzle 102, processing is implemented to clean in the surface of substrate 103.And then substrate 103 as an example, supposes that diameter is 300mm.

In the present embodiment, as mentioned above, used the clean of movable type with nozzle 102.Specifically, clean with nozzle 102, the surface of substrate 103 can be moved almost parallel relatively.In addition,, clean, constitute by 3 nozzle 102a, 102b, 102c with nozzle 102 as an example.

In the present embodiment, as shown in Figure 2, clean, be constituted as 3 nozzle 102a～102c are adjoined each other, be combined into one with nozzle 102.

In the present embodiment, nozzle 102a, and nozzle 102c are for substrate 103 ejection detergent removers.In addition, nozzle 102b blows the air of paying high pressure to the substrate of substrate 103.And then nozzle 102a～102c can distinguish independently operation, thus ejection or blow out detergent remover or pressure-air.

At this, clean with nozzle 102, on the direction of scanning, provide nozzle 102a, air to provide order that nozzle 102b, detergent remover provide nozzle 102c reciprocally in abutting connection with configuration according to detergent remover.

In addition, as shown in Figure 2, each nozzle 102a～102c is formed elongated oblong-shaped, with substrate 103 opposed bottom surface on, be formed with the ejiction opening 104 of a plurality of detergent removers of ejection detergent remover, perhaps the blow-off outlet 105 used of air.At this, each detergent remover supply nozzle 102a, 102c are by the configuration abreast of 2 row.

In addition, provide at each detergent remover on the bottom surface of nozzle 102a, 102c, be arranged with the ejiction opening 104 of a plurality of circles.At this, ejiction opening 104 is formed circle, can spray each detergent remover with high pressure to the outside.And ejiction opening 104 provides at each detergent remover and is arranged in 2 row among nozzle 102a, the 102c mutually, makes reciprocally to form parallel row.Dispose detergent remover the zone of a plurality of ejiction openings 104 of nozzle 102a being provided is the 1st ejection zone.Dispose detergent remover the zone of a plurality of ejiction openings 104 of nozzle 102c being provided is the 2nd ejection zone.

In cleaning the process of handling, spray the detergent remover of regulation from the ejiction opening 104 of detergent remover.Detergent remover provides nozzle 102a, 102c separately, and on the direction vertical with the direction of scanning, the processed zone on substrate 103 provides the detergent remover of regulation the samely.At this moment, as mentioned above, each detergent remover provides nozzle 102a, 102c, by the configuration abreast of two row.Ejiction opening 104 in each nozzle, also is arranged in 2 row in parallel to each other.Thereby, Yi Bian on substrate, make nozzle scan, Yi Bian from the ejiction opening 104 of the detergent remover of circle, with high pressure ejection detergent remover, roughly a rectilinear form ground provides detergent remover to the processed zone of substrate 103.

In addition, provide among the nozzle 102b at air, blow-off outlet 104 is formed shape of slit.Thus, can with the direction of direction of scanning approximate vertical on, not interruptedly not continuously, blow to the processed zone of substrate 103 equally and pay a pressure-air.And then blow-off outlet is the 1st to blow out the zone.

As mentioned above, clean and to be constituted as, on the processed zone on the substrate 103, provide each detergent remover not interruptedly continuously, and roughly linear with nozzle 102, and the air of high pressure.

And then in the present embodiment, for the substrate 103 that is applicable to diameter 300mm, as an example, the bottom surface of nozzle 102a to 102c is constructed to, and has horizontal width W respectively _1a, W _1b, W _1c=5mm, vertical length L ₁=305mm.In addition, then all if these 3 nozzles are used integratedly by cleaning with nozzle 102, be configured to the bottom surface and have horizontal wide W ₁=15mm, vertical length L ₁The size of=305mm.

At this, it is desirable to especially, the longitudinal length L that cleans with nozzle 102 ₁, the diameter of substrate 103 (for example, 300mm), is made as big several mm, thereby spreads all over the whole surface of substrate 103, the air of each detergent remover and high pressure is provided reliably relatively.

And then in the clean mechanism of Shi Yonging, the formation of cleaning with nozzle 102 is not limited to as shown in Figure 4, sequentially sprays/blow out dry air 109, the detergent remover B110 of detergent remover A108, high pressure from the place ahead, direction of scanning one side in the present embodiment.For example, the formation of cleaning with nozzle 102 also can be the dry air 109 that sequentially sprays/blow out detergent remover A108, high pressure from the place ahead, direction of scanning one side.In addition, cleaning with nozzle 102 formations also can be to begin sequentially to dispose dry air 109, the detergent remover B110 of high pressure from the place ahead, direction of scanning one side.By dry air and the detergent remover that high pressure is provided simultaneously, because can isolate detergent remover and developer solution, so can clean substrate.

In addition, in the clean processing mechanism of Shi Yonging, the formation of cleaning with nozzle 102 is to change the quantity and the configuration of nozzle aptly in the present embodiment.Specifically, according to clean purposes, changing detergent remover provides and use nozzle, and air provides the quantity of usefulness nozzle, can combined transformation formation separately, and their configuration.For example, can clean the nozzle that usefulness is provided with the detergent remover of nozzle 102 by combined transformation, and air provides the nozzle configuration separately of usefulness, make according to pressure-air, Ozone Water, pressure-air, perhaps, the order of pressure-air, hydrogen water (Shui Sushui), pressure-air provides to the processed zone of substrate 103.

In the present embodiment, use clean processing as described above, on substrate, clean processing.In the present embodiment, use above-mentioned processing unit, as an example, in the process of making semiconductor device, in order on the photonasty photoresist film on the semiconductor substrate, to form pattern, at first, implement the development treatment operation successively, then, clean treatment project.Thereby, on substrate,, suppose to use semiconductor substrate as an example.

And then, in the present embodiment,, use the semiconductor substrate of diameter with 300mm as an example.

In addition, though diagram especially, in clean processing mechanism 100, the position of regulation is provided with the nozzle at the back side (=substrate 103 following) of clean substrate 103, detergent remover etc. be can spray aptly, dissolving product and small particle etc. removed by the back side of substrate 103.At this moment, the structure of the nozzle at the back side of clean substrate 103 is not particularly limited, and can use known structure.In addition, especially, this nozzle is configured on the position at the back side of substrate 103 etc. and gets final product, and makes the periphery at the back side of cleaning substrate 103.

Below, the clean disposal route for present embodiment specifically describes with Fig. 3, Fig. 4.At this, use the processing unit that possesses clean processing mechanism 100 shown in Figure 1.

On semiconductor substrate, be pre-formed machined membrane (for example: dielectric film, perhaps distribution conducting film) successively, then on them, form the photonasty photoresist film of chemical amplifying type.Thereafter, use KrF exciplex laser etc. in light source, the groove by exposure usefulness carries out the reduced projection exposure, the patterned illumination of given size and shape on photoresist.

Then, each semiconductor substrate applies thermal treatment to photoresist film, thereafter, uses the development nozzle of above-mentioned movable type, implements so-called scanning development treatment, forms the pattern of given size and shape on photoresist film.At this, make and develop with the certain speed scanning of nozzle with 60mm/sec, the photoresist film on semiconductor substrate provides the developer solution of regulation simultaneously, carries out known blade (パ De Le) development treatment, forms pattern on photoresist film.

And then, in the developer solution that photoresist is used, use (=pH value: 13.4) in the alkaline tetramethylammonium aqueous solution.

Below, carrying out development treatment after the stipulated time, semiconductor substrate is cleaned processing, developing reaction is stopped, and the dissolving product that is produced by developer solution, development treatment, and molecule etc. is removed to foreign side's flushing of semiconductor substrate.

At this, it is rotated, under the state that is still on the sucker 101 that fixed support uses, semiconductor substrate applied to clean handle, remove the dissolving product that produces by developer solution, development treatment, and molecule etc., implement dried, on semiconductor substrate, form the pattern of photoresist with given size and shape thereafter.

After, specify clean disposal route.In the present embodiment, spread all over all surfaces of semiconductor substrate, clean with nozzle 102 scannings,, remove the dissolving product that produces by developer solution, development treatment Yi Bian clean processing Yi Bian make, and molecule etc.

Specifically, shown in Fig. 3 A, 3B, at first, make and clean with the end of nozzle 102 near semiconductor substrate, thereafter, in the film certain intervals of the developer solution 107 on maintenance and semiconductor substrate 106, on one side to the parallel scanning movably of the other end, Yi Bian clean processing.At this moment, clean with 102 scan periods of nozzle making, as shown in Figure 4, provide nozzle 102a, air that nozzle 102b is provided, and clean nozzle 102c is provided, detergent remover A108, high pressure dry air 109 are provided on substrate by detergent remover, and detergent remover B110.And then, on semiconductor substrate 106, be formed with not shown resist film.

In the present embodiment, as mentioned above, detergent remover nozzle 102, its longitudinal length L1 (for example: 305mm), at the diameter of semiconductor substrate 106 (for example: 300mm).Then, and provide detergent remover 108,110, and the width of the direction of the direction of scanning quadrature in the zone of dry air 109, surpass the diameter of semiconductor substrate 106.Thus, be constituted as, on the surface of semiconductor substrate 106 is all, provide detergent remover 108,110 dry airs 109.Thereby, when blowing pair high pressure dry air 109, clean with nozzle 102 scannings if make as described above, then all provide detergent remover A108 to the surface of semiconductor substrate 106, and detergent remover B110.

In the present embodiment, as an example, in detergent remover A108, use Ozone Water as the detergent remover of oxidisability.In addition, in detergent remover B110, use hydrogen water as the detergent remover of reductibility.At this moment, the ozone concentration in the Ozone Water, and the hydrogen concentration in the hydrogen water is made as 0.1～5ppm.

In addition, as shown in Figure 4, the dry gas 109 of high pressure, to the film of the developer solution on the semiconductor substrate 106 107, played the effect of so-called air curtain, promptly, with the thickness of hundreds of nm to hundreds of μ m, blocking is by the nozzle 102a that is positioned at the both sides of cleaning usefulness nozzle 102, and the detergent remover A108 and the detergent remover B110 of nozzle 102c ejection, arrives the only degree of residual liquid film.In this case, the dry air 109 of high pressure blows out with wind speed 0.1 to 10m/sec, as air curtain, need be arranged to make the only remaining liquid film of detergent remover A108 such block needed pressure and flow.

In addition, at this moment, clean, begin to the height below the 3mm approachingly with surface, keep and photoresist film 112 discontiguous certain intervals from the developer solution on the semiconductor substrate 106 107 with nozzle 102.Thereafter, as mentioned above, detergent remover A108, detergent remover B110 are provided, and high pressure dry air, and meanwhile from a side's of semiconductor substrate 106 a end to the other end, make and clean the surface that spreads all over semiconductor substrate 106 with nozzle 102 and scan universally.Thereby, on semiconductor substrate 106, in processed zone, according to detergent remover A108, high pressure dry air 109, and the order of detergent remover B110, provide respectively.

In the present embodiment,, suppose to clean with nozzle 102 and the development nozzle of developer solution 107 is provided, scan on the path equidirectional as an example.In addition, at this moment, clean nozzle 102, identical with the development that developer solution 107 is provided with the translational speed of nozzle, suppose certain velocity sweeping with 60mm/sec.

In this case, with the situation that developer solution 107 is provided relatively because on equidirectional, scan on same path with identical certain speed, thereby all on the surface of semiconductor substrate 106, the feasible developer solution 107 that provides can be provided begin, be impartial to the time that is replaced into detergent remover A108.Thereby, on photoresist film, form in the process of pattern, interregional at each, though produce difference in the moment that developing reaction begins, but make on the surface of semiconductor substrate 106 all on the time equalization of developer solution effect, can on photoresist film, form pattern accurately.

And then in the present embodiment, what is called is replaced into detergent remover to developer solution, and expression changes the composition of developer solution by the composition of detergent remover, and developer solution is stopped the effect of photoresist.

In addition, at this moment, (for example: pure water), carry out the clean processing at the back side of semiconductor substrate 106 spray detergent remover from the nozzle (illustrating especially) of cleaning the above-mentioned back side.Like this, when cleaning, clean the back side on the surface of carrying out semiconductor substrate 106.Thus, the developer solution of removing from surface one side of semiconductor substrate 106, dissolving product, and molecule etc., comprise the back side not remain on the semiconductor substrate 106, can positively discharge.In addition, owing to clean treatment surface one side and the back side one side simultaneously, thereby can obtain the clean effect of semiconductor substrate 106 reliably with shorter time.

Clean processing as mentioned above, then, remove the film of the detergent remover on the pattern that remains in photoresist.At this, make semiconductor substrate 106 high-speed rotation in scope with velocity of rotation 1000 to 20000rpm, remove the film of detergent remover.

And then, in the present embodiment,, make to clean to relatively move with nozzle 102 for semiconductor substrate 106, each detergent remover can be provided, and the dry air of high pressure.Thereby, fixing cleaning with nozzle 102, make each detergent remover ejection under this state, the sucker 101 that each fixed support is used moves semiconductor substrate 106, can also provide each detergent remover 103,110, dry air 109 in the processed zone on semiconductor substrate 106 as mentioned above.

In the method for cleaning of present embodiment, at substrate, promptly on the developer solution 107 on the semiconductor substrate 106, along the direction of scanning, according to detergent remover A108, pressure-air 109, and the ejection of the order of detergent remover B110, perhaps blow and pay, and its effect is as follows.

In clean nozzle 102, the detergent remover A108 of nozzle 102 ejections is provided from detergent remover, the developer solution 107 that fills with on semiconductor substrate 106 is replaced into detergent remover A108, and, the dissolving product that produces with developer solution, by development treatment, and molecule etc. washes to foreign side from semiconductor substrate 106.

At this moment, on the liquid level of the ejection of detergent remover A108, blow a pair high pressure dry air 109 by brute force, with as method of cleaning in the past, only provide detergent remover, compare by being rotated in situation about spreading in the face from the top, on the surface of semiconductor substrate 106 all on, to detergent remover A107 pressurization, can improve clean effect equably.

Specifically,, blow the dry air 109 of paying high pressure,,, be discharged to the foreign side of semiconductor substrate 106 reliably by direction pressurization to periphery by the developer solution 107 of detergent remover A108 displacement by nozzle 102b is provided from air.In addition, the dry air 109 of high pressure prevents these objects that are discharged from attached on the semiconductor substrate 106, particularly attached to having carried out on the zone of clean processing.But, at this moment, the dryer air 109 of high pressure, on semiconductor substrate 106, with the direction of direction of scanning approximate vertical on be not interrupted, and be linked to be a rectilinear form, need to generate so-called air curtain.

And then, after blowing the dry air 109 of paying high pressure, by spraying detergent remover B110 continuously, remain in a spot of developer solution 107 on the pattern of photoresist to foreign side's flushing of semiconductor substrate 106.At this moment, have on the zone of high pressure dry air 109 blowing to pay, to spray detergent remover B110 continuously, simultaneously, prevent to dissolve product, molecule, and precipitate etc. is to the adhering to of photoresist pattern, can and removes to foreign side's flushing of semiconductor substrate 106 for these.

As mentioned above, in the present embodiment, in detergent remover A108, use Ozone Water with oxidisability character.This Ozone Water makes the dissolving product, the molecule that produce in the process of carrying out development treatment, and the precipitate oxidation.Particularly oxidation of organic compounds decomposes its molecular configuration, has the effect that makes the particle sectionalization.Therefore, after development treatment, suppress organism to adhering to again of photoresist etc., can reduce the generation of the position of resist pattern generation defective significantly.

At this moment, Ozone Water can be used with the low concentration of 1ppm.If this concentration, Ozone Water then can not have damage to the pattern of photoresist.In this case, because only play the effect of the side wall portion of etching photoresist pattern, thus can reduce the roughness (=locality deviation) of the pattern dimension of photoresist, in face, the inhomogeneity effect of the size that can be improved.

In addition, as mentioned above, in the present embodiment, in detergent remover B110, use hydrogen water with reductibility character.

As mentioned above with behind the Ozone Water decomposing organic matter,, there is the situation of not rinsing the organic particle that left behind etc. well of adhering on the surface of photoresist film.If on the pattern of this organic particle attached to photoresist, then on the resist pattern, can produce defective locations (deviation of pattern dimension), in the etching work procedure of back, can produce the error of size and shape.

For this problem, shown in present embodiment, after Ozone Water is provided,, reduce the surface of this organic particle etc. by ejection hydrogen water, separate from the surface of photoresist film once more.Thus, other comprise pollutant and impurity, are washed into the outside of semiconductor substrate 106, can further clean processing reliably.

In the present embodiment, in detergent remover A108, use Ozone Water, in addition, in detergent remover B110, use hydrogen water, they sequentially are provided to developer solution 107 on the semiconductor substrate 106 continuously.In this case, Ozone Water is the aqueous solution of oxidisability, and on the other hand, hydrogen water is the reductibility aqueous solution.If Ozone Water and hydrogen water mix mutually, then the characteristic of each solution is cancelled out each other, and the function as detergent remover is reduced, and causes that cleaning effect reduces.Thereby, in cleaning the process of handling, when using the detergent remover of relative character continuously, need to reduce the amount of sneaking into, prevent the function reduction of detergent remover, prevent the decline of the clean effect that causes thus.

For this problem, in the present embodiment, to detergent remover A108 (for example, Ozone Water), detergent remover B110 (for example: hydrogen water), blow and pay high pressure dry air 109, form air curtain, reduce the amount of sneaking into mutually, can prevent the reduction of detergent remover function, thereby can prevent to clean the reduction of effect.

Like this, under the situation of the detergent remover that uses relative character, in order to isolate two kinds of detergent removers, if blow the dry air of paying high pressure etc., forming so-called air curtain, suppress sneaking between the detergent remover, is effective keeping on the high clean effect definitely then.

And then, in the present embodiment, though in detergent remover A, used Ozone Water, and in detergent remover B, used hydrogen water, if can obtain the effect identical, can change the detergent remover of other kind with them.For example, can in detergent remover A, use Ozone Water, in detergent remover B, use pure water, clean processing as mentioned above.In addition, in the pure water that is used to detergent remover B, add surfactant etc., can more effectively remove impurity, and pollutant etc.

In addition, in the present embodiment, by blowing the dry air 109 of paying high pressure, the film of the film of detergent remover A108 and detergent remover B110 is pressurized, under dry air, is pressed into the thickness of hundreds of nm to hundreds of μ m.That is,,, detergent remover A103, detergent remover B110 are suppressed at trace in the zone that high pressure dry air 109 passes through at semiconductor substrate 106.Thereby, thereafter,, make its high-speed rotation (=velocity of rotation: 1000 to 4000rpm) get rid of detergent remover even be not as method in the past, also pay the effect of semiconductor substrate 106 dried easily.This situation, on semiconductor substrate 106, because do not add the load (=centrifugal force of physics, the current of detergent remover etc. etc.), even so using heavy caliber (for example: diameter 300mm) under the situation of semiconductor substrate, also easily and the pattern of photoresist is not paid with damaging the effect of dried.

Below, with reference to Fig. 5 A, Fig. 5 B, the effect of present embodiment is described with comparing with the situation of using method of cleaning in the past.

At this, at first, as mentioned above, make on one side the clean nozzle scan of use that uses in the present embodiment, one side as an example, provide according to the order of Ozone Water, air, hydrogen water, carry out the clean processing of substrate,, measure the homogeneity of photoresist pattern dimension thereafter, and the number of defect location.In addition,,, repeat 3 times and carry out so clean processing, in each is handled, measure the dimensional homogeneity in the real estate as an example at this, and the number of pattern defect location.In Fig. 5 A, Fig. 5 B, write down to use and cleaned processing separately 3 times of the present embodiment method, and the result of method of cleaning in the past, the effect of present embodiment is investigated by the mean value of relatively these 3 times clean processing and the value of method of cleaning in the past.Its result in the present embodiment, can obtain the effect shown in Fig. 5 A, Fig. 5 B as can be known.

In Fig. 5 A, showed, in the method for present embodiment, and method of cleaning in the past separately in, in the face of substrate (=wafer), measure the result of the dimensional homogeneity of photoresist pattern.In the method for present embodiment, shown in Fig. 5 A, the method for cleaning comparison with in the past can improve dimensional homogeneity 20%.At this, dimensional homogeneity should be that the pattern of same size is an object, be measured with a plurality of points of these patterns in design, shows the degree of the deviation of the size that obtains as its result.

In addition, in Fig. 5 B, showed, in the method for present embodiment, and method of cleaning in the past separately in, be determined at the result of the number of the defective locations that produces on the photoresist pattern.In the present embodiment, shown in Fig. 5 B, on substrate (=wafer), measured the number of the defective locations of photoresist pattern, compared, can also reduce 65% with the situation of using method of cleaning in the past.At this, defective locations is illustrated on the photoresist pattern because of the impurity that adheres to organism etc., pollutant etc., produces the state of error etc. dimensionally.

Like this, in the present embodiment, with heavy caliber (for example: semiconductor substrate diameter 300mm) is corresponding, and then and with in the past method of cleaning relatively, in the development treatment of photoresist etc., can improve clean effect.

And then, in development treatment and clean the processing, can use the clean nozzle 120 that becomes one with nozzle 121 with nozzle 102 and development shown in Figure 30.As shown in figure 30, nozzle 120 possesses and cleans with nozzle 102 and development nozzle 121.Developing, the ejiction opening 122 that sprays developer solution is formed slit-shaped with in the nozzle 121.With the length of the direction of the direction of scanning quadrature of ejiction opening 122, at the maximum gauge of substrate, perhaps longest edge long more than.Thus, can with the direction of direction of scanning approximate vertical on, uninterruptedly continuously, one in the same way the processed zone of substrate 103 developer solution is provided.And then ejiction opening 121 is the 3rd ejection zones.And then, develop with the position of nozzle 121, as shown in figure 30, the relative scanning direction is not limited to clean the place ahead one side with nozzle 102.For example, develop with nozzle 121, the relative scanning direction also can be configured in rear one side of cleaning with nozzle 102.

The situation of this nozzle, development treatment and clean the processing are not carried out side by side.During development treatment,, do not carry out the ejection of detergent remover and blowing out of gas with nozzle 102 from cleaning from developing with nozzle 121 ejection developer solutions.In addition, when cleaning processing, carry out the ejection of detergent remover and blowing out of gas with nozzle 102, do not spray developer solution with nozzle 121 from developing from cleaning.

And then, in the above-described embodiment, use developer solution to be illustrated as treating fluid.But,, also can use etching solution etc. as treating fluid.

(embodiment 2)

In the present embodiment, the same with embodiment 1, on the processed zone of substrate, in order to form the pattern of given size and shape, carry out development treatment, clean and handle, and dried.In addition, in the present embodiment, on a substrate, use can be carried out development treatment continuously, clean and handle in a device, and the development processing apparatus of so-called leaf formula of the processing procedure of dried.

In the inside of this development processing apparatus, be provided with substrate is carried out development treatment continuously, cleans and handle, and the processing unit of dried.In the present embodiment, in such processing unit, use each corresponding processing mechanism to carry out development treatment, clean and handle, and a succession of processing procedure of dried.

In this processing unit,,, be provided with development treatment mechanism in order to carry out known scanning development treatment as an example.On the part of this development treatment mechanism, possess have can about, and the development nozzle of the movable type that moves on the horizontal direction, Yi Bian feasiblely spray developer solution, Yi Bian on substrate, scan.Nozzle is used in this development, is constituted as elongated rectangular slit-shaped, is used for providing developer solution with uniform amount on the processed zone of substrate.

In addition, except above formation, on processing unit, as shown in Figure 6, also be provided with clean processing mechanism.Below, use Fig. 6, describe in detail to be set at and carry out development treatment, the clean processing, and the formation of the clean processing mechanism in the processing unit of dried, and action.

And then, in Fig. 6, showed the main component part relevant with clean processing mechanism 200.

Carry out development treatment, and cleaning in the unit of handling, possessing clean processing mechanism 200 shown in Figure 6.In clean Processing Structure 200, as main component part, possess the sucker 201 that fixed support is used, and clean nozzle 202.In addition, the sucker 201 that these fixed supports are used, and clean nozzle 202 is constituted as movable type, can move independently of one another.

In clean processing mechanism 200, after carrying out development treatment, substrate 203 is placed and is fixed on the sucker 201 that fixed support uses, and provides the detergent remover of regulation from cleaning nozzle 202, the surface of substrate 203 is implemented to clean handle.

And then substrate 203 as an example, supposes that diameter is 300mm.In the present embodiment, clean nozzle 202, constitute by 5 nozzle 202a～202e.Travel mechanism 215 makes surperficial parallel move of nozzle 202 relative to substrate 203.

In addition, though do not illustrate especially, in clean processing mechanism 200, the position of regulation is provided with the nozzle at the back side (following) of cleaning substrate 203, sprays detergent remover etc. aptly, can remove dissolving product and small particle by the back side of substrate 203.At this moment, the structure of the nozzle at the back side of clean substrate 203, there is no particular limitation, can be suitable for known structure.In addition, this nozzle as long as be arranged on the position of the back side one side etc. of substrate 203, makes the periphery at the back side of cleaning substrate 203 get final product.

In the present embodiment, as mentioned above, use the clean nozzle 202 of movable type.Specifically, clean nozzle 202, the surface of substrate 203 in the certain interval of maintenance, can be moved abreast relatively.In addition,, clean nozzle 202, constitute by 5 nozzle 202a～202e as an example.

In the present embodiment, as shown in Figure 7, clean nozzle 202 is constituted as 5 nozzle 202a～202e is made up with adjoining each other.

In the present embodiment, 3 nozzle 202a, 202c, 202e blow out the zone as the 1st to the 3rd respectively, pressure-air are blown a processed zone of paying substrate 203.In addition, nozzle 202b, and nozzle 202d provide the nozzle of usefulness as detergent remover, respectively the processed zone ejection detergent remover on substrate 203.

And then, can manipulating nozzles 202a～202e, make it to spray independently respectively or blow and pay detergent remover A, a B, and pressure-air.

At this, in clean nozzle 202,, provide nozzle 202a, the 1st detergent remover to provide nozzle 202b, the 2nd air to provide nozzle 202c, the 2nd detergent remover nozzle 202d, the 3rd air that nozzle 202e is provided in abutting connection with ground configuration the 1st air successively along the direction of scanning.

In addition, as shown in Figure 7, each nozzle 202a～202e is formed elongated rectangular slit-shaped, with substrate 203 opposed bottom surface on, be formed with the ejiction opening 204 of a plurality of detergent removers of ejection detergent remover, and the blow-off outlet 205 used of air.

At this, each detergent remover provides nozzle 202b, 202d, is configured to 2 row abreast.In addition, provide at each detergent remover on the bottom surface of nozzle 202b, 202d, the ejiction opening 204 of circular detergent remover is formed the so-called porous structure structure form of a plurality of and mutual arrangement.At this, the ejiction opening 204 of detergent remover is formed toroidal, can spray each detergent remover to the outside with high pressure.In addition, the ejiction opening 204 of detergent remover as the row that formation is parallel to each other, provides nozzle 202b, 202d at each detergent remover, is arranged in 2 row mutually.

In cleaning the process of handling, from the ejiction opening 204 of detergent remover, the detergent remover of ejection regulation simultaneously, detergent remover provides nozzle 202b, 202d separately, on the direction vertical with the direction of scanning, the processed zone on substrate 203 provides the detergent remover of regulation the samely.At this moment, as mentioned above, each detergent remover provides nozzle 202b, 202d, is arranged in 2 row in parallel to each other.And the ejiction opening 204 of detergent remover is also lined up 2 row in parallel to each other in nozzle separately.Thereby a scan edge on one side from the ejiction opening 204 of the detergent remover of circle, sprays each detergent remover with high pressure, can provide to the processed zone of substrate 203 with a rectilinear form roughly.The zone that disposes the ejiction opening 204 of nozzle 202b is the 1st ejection zone.The zone that disposes a plurality of ejiction openings 104 of nozzle 202d is the 2nd ejection zone.

In addition, provide going up separately of nozzle 202a, 202c, 202e at the 1st～the 3rd air, air is formed elongated rectangular shape of slit with blow-off outlet 205.Thus, on the direction vertical, can the samely blow the air of paying high pressure not interruptedly not continuously to the processed zone of substrate 203 with the direction of scanning.The zone that is formed with the 1st air and provides the blow-off outlet 205 of nozzle 202a is the 3rd to blow out the zone.The zone that is formed with the 2nd air and provides the blow-off outlet 205 of nozzle 202c is the 1st to blow out the zone.The zone that is formed with the 3rd air and provides the blow-off outlet 205 of nozzle 202e is the 2nd to blow out the zone.

As described above, clean nozzle 202 and be constituted as,, do not interrupt continuously to the processed zone of substrate 203, and shape ground always roughly, each detergent remover is provided, and pressure-air.

And then the same with embodiment 1 in the present embodiment, the bottom surface of nozzle 202a～202e is constituted as, and has width (W respectively _2a, W _2b, W _2c, W _2d, W _2e)=5mm, longitudinal length L ₂=305mm.In addition,, then cleaning all of nozzle 202, becoming and have bottom width W if these 5 integrated uses of nozzle ₂=25, longitudinal length L ₂The structure of the size of=305mm.

At this, preferably the length L longitudinally of cleaning nozzle 202 ₂Being arranged to the diameter of relative substrate 203 (for example, 300mm) counts mm greatly, makes the whole surface that spreads all over substrate 203 that detergent remover is provided reliably, and pressure-air.

In addition, in the clean processing mechanism of Shi Yonging, the formation of cleaning nozzle 202 is to change the quantity and the configuration of nozzle aptly in the present embodiment.Specifically,, change the nozzle that detergent remover provides usefulness, and air provides the quantity with nozzle according to clean purpose, can combined transformation formation separately, and their configuration.

In the present embodiment, use clean processing mechanism as described above, substrate is cleaned treatment process.In the present embodiment, the same with embodiment 1, the process of making semiconductor device as an example, is illustrated substrate processing method using same.In this case,, implement the development treatment operation successively, then implement to clean treatment process in order on the photonasty photoresist film on the semiconductor substrate, to form pattern.Thereby, on substrate,, suppose to use semiconductor substrate as an example.

And then in the present embodiment, as an example, semiconductor substrate uses the semiconductor substrate with 300mm diameter.

Below, specifically describe the clean disposal route of present embodiment with Fig. 8.At this, suppose to use the processing unit that possesses clean processing mechanism 200 shown in Figure 8.

On semiconductor substrate, use known method in advance, order forms antireflection film, then forms the photonasty resist film of chemical amplifying type thereon., in light source use KrF exciplex laser instrument etc., use groove, carry out the reduced projection exposure, the size of irradiation regulation and the pattern of shape on photoresist film by exposure thereafter.

Then, each semiconductor substrate is implemented thermal treatment to photoresist film, thereafter, with the development nozzle of above-mentioned movable type, implements so-called scanning development treatment, forms the pattern of given size and shape on photoresist film.At this, develop with the certain speed scanning of nozzle Yi Bian make with 60mm/sec, Yi Bian the photoresist film on semiconductor substrate provides the developer solution of regulation, carry out known blade development treatment, on photoresist film, form pattern.

And then, in the developer solution that photoresist is used, use the tetramethylammonium aqueous solution (pH value: 13.4) of alkalescence.

Then, carrying out development treatment after the stipulated time, semiconductor substrate is being implemented to clean handle, developing reaction is stopped, and developer solution, and the dissolving product that is produced by development treatment, and the foreign side that molecule etc. is flushed to semiconductor substrate removes.

At this, it is rotated, and make it under state static on the sucker 201 that fixed support is used, semiconductor substrate is implemented to clean handle, the dissolving product of removing developer solution, producing by development treatment, and molecule etc., implement dried, on semiconductor substrate, form the pattern of the photoresist of size with regulation and shape thereafter.

Below, specifically describe clean disposal route.In the present embodiment, spread all over the surface of whole semiconductor substrate, clean nozzle 202 scannings, form on one side to clean and handle, remove developer solution, by the dissolving product of development treatment generation Yi Bian make, and molecule etc.And then the surface of so-called semiconductor substrate is meant the face that is formed with semiconductor element.

Specifically, the same with embodiment 1, make an end of cleaning at first close semiconductor substrate 206 1 sides of nozzle 202, thereafter, with semiconductor substrate 206 on the film of developer solution 207 keep certain intervals in, it is moved to the other end is parallel, clean processing while scan.At this moment, clean 202 scan periods of nozzle making, as shown in Figure 8, provide nozzle 202a, 202c, 202e from 3 air, and two detergent removers provide nozzle 202b, 202d, as an example, provide the dry air 208,210,212 of high pressure respectively to developer solution 207, detergent remover A209, detergent remover B211.And then symbol 216 is photoresist films.

In the present embodiment, as mentioned above, clean nozzle 202, its longitudinal length L ₂(for example: 305mm) (for example: 300mm) at the diameter of semiconductor substrate 206.And, with the width of the direction of the direction of scanning quadrature in the zone that dry air 208,210,212 and detergent remover 209,211 are provided, more than the diameter of semiconductor substrate 206.Thus, be constituted as to the whole surface of semiconductor substrate 206 dry air 208,210,212 and detergent remover 209,211 are provided.Thereby, if when blowing the dry air 208,210,211 of paying high pressure, making and clean nozzle 202 and scan as mentioned above, then detergent remover A209, and detergent remover B211 can be provided for the whole surface of semiconductor substrate 203.

In the present embodiment, provide nozzle 202a, 202c, 202e,, blow the dry air 208,210,212 of paying high pressure as an example from each air.In addition, in the present embodiment,, in detergent remover A209, use Ozone Water, in addition, in detergent remover B211, use hydrogen water as the detergent remover of reductibility as the detergent remover of oxidisability as an example.At this moment, Ozone Water, and the concentration of hydrogen water suppose it is 0.1～5ppm.

In addition, as shown in Figure 8, the dry air 208,210,212 of high pressure uses as so-called air curtain separately.The dry air 208,212 of high pressure, the film of the developer solution 207 on semiconductor substrate 206 blows to be paid, on the direction of scanning, from cleaning the both sides of nozzle 202, covering is by the detergent remover A209 of nozzle 202b ejection, and, play from outside their effect of blocking by the detergent remover B211 that nozzle 202d sprays.In addition, the dry air 210 of high pressure to the film of the developer solution on the semiconductor substrate 206 207, blocks detergent remover A209, and between the detergent remover B211, to residual hundreds of nm only to the liquid film of the thickness of hundreds of μ m.

In this case, the dry air 208,210,212 of high pressure blows out with wind speed 0.1 to 10m/sec, separately as mentioned above, and the pressure and the flow that need work as air curtain.

In addition, at this moment, clean nozzle 202, the surface of the developer solution 207 from the semiconductor substrate 206 approaches to the following height of 3mm, keeps certain interval in the degree of the pattern contact of discord photoresist.Thereafter, from cleaning nozzle 202, as mentioned above, detergent remover A209, detergent remover B211 are provided on one side, and the dry air 208,210,212 of high pressure, on one side from a side's of semiconductor substrate 206 end to the other end, the surface that spreads all on the whole semiconductor substrate 206 is scanned.Thereby, on semiconductor substrate 206,, become dry air 208, detergent remover A209 (for example, Ozone Water), the dry air 210 of high pressure, detergent remover B211 that high pressure is provided successively in processed zone, and the dry air 212 of high pressure.

In the present embodiment,, clean nozzle 202 as an example, suppose and development that developer solution 207 is provided with nozzle same path of scanning on equidirectional.In addition, at this moment, suppose to clean nozzle 202, identical with the translational speed of the nozzle that developer solution 207 is provided, with the certain speed scanning of 60mm/sec.

In this case, compare, by on same direction with the situation that developer solution 207 is provided, on same path, scan with identical certain speed, on the whole surface of semiconductor substrate 206, the feasible developer solution 207 that provides can be provided begin, to the time that is replaced into detergent remover A209 or for impartial.Thereby, on photoresist film, form in the process of pattern, interregional at each, though poor in the moment generation that developing reaction begins, but make the time equalization of developer solution effect on whole of semiconductor substrate 206, can on photoresist film, form pattern accurately.

And then in the present embodiment, what is called is replaced into detergent remover to developer solution, is meant that the composition with detergent remover changes the composition of developer solution, and developer solution is stopped the effect of photoresist.

In addition, at this moment, from the nozzle (not illustrating especially) of cleaning the above-mentioned back side, the ejection detergent remover (for example: pure water), carry out the clean processing at the back side of semiconductor substrate 206.Like this, when cleaning, clean the back side on the surface of carrying out semiconductor substrate.Thus, the developer solution of removing from the surface of semiconductor substrate 206, dissolving product, and molecule etc. do not have residually on semiconductor substrate, can discharge reliably.In addition, by cleaning treatment surface one side simultaneously, and the back side one side, can carry out the clean processing of semiconductor substrate 206 in the short time reliably.

Clean processing as mentioned above like that, then, air etc. is offered the surface of semiconductor substrate 206, remove detergent remover only remaining on the pattern of photoresist film.Like this, in the present embodiment, do not make semiconductor substrate 206 rotations and make the detergent remover vaporization, can carry out dried.Thereby, even use heavy caliber (for example: the situation of semiconductor substrate 300mm) etc., the damage of the pattern of photoresist does not take place yet, the perhaps breakage of pattern etc. can be carried out dried.

And then in the present embodiment, as long as relative substrate, that is, semiconductor substrate 106 relatively moves clean nozzle 202, provides the dry air of each detergent remover and high pressure to get final product.Thereby, fixedly the detergent remover nozzle 202, each detergent remover of ejection under this state, with sucker 201 semiconductor substrate 206 is moved for each fixed support, the dry air 208,210,212 of each detergent remover 209,211, high pressure as mentioned above also can the processed zone on semiconductor substrate 106 be provided.

In the method for cleaning of present embodiment, to substrate, promptly, developer solution 207 on the semiconductor substrate 206, along the direction of scanning, according to high pressure dry air 208, detergent remover A209, high pressure dry air 210, detergent remover B211, and the order of the dry air 212 of high pressure, spray or blow and pay, and its effect is as follows.

In clean nozzle 202, if provide nozzle 202a to blow the dry air 208 of paying high pressure from the 1st air, the developer solution 207 on the semiconductor substrate 206 that then pressurizes is suppressed to hundreds of μ m with this film thickness.

At this moment, high pressure dry air 208 forms air curtain, have to prevent developer solution 207 once more attached to the effect on the zone of cleaning after handling, and then and, have trying to be the first of the detergent remover A209 that prevents subsequently, that is, and attached to the effect on the zone of not cleaning.

In addition, provide nozzle 202b, ejection detergent remover A209 from the 1st detergent remover of cleaning nozzle 202.Developer solution on the semiconductor substrate 206 is replaced into the composition of detergent remover A209.And then detergent remover A209 is flushed to the dissolving product in the solution and molecule the foreign side of semiconductor substrate 206.

At this moment, blow the dry air 208 of paying high pressure from the 1st air supply nozzle 202a, as mentioned above, suppress the film thickness of the developer solution 207 on the semiconductor substrate 206, the amount of developer solution 207 reduces, and then and, because pressurized, make and clean the effect raising.

And then, provide nozzle 202c by the 2nd air, blow the dry air 210 of paying high pressure.The 1st detergent remover provides the lower zone of nozzle 202b, separates both sides by air curtain, blocks on the direction of scanning.Thereby the zone of detergent remover A209 effect is in the zone that is limited in being cut apart by the dry air 208,210 of high pressure.Developer solution 207 in this zone, as mentioned above, film thickness is limited, and its amount is compared also considerably less with detergent remover A209.In this case, in cleaning the process of handling, the amount of the detergent remover A209 that is consumed by developer solution 207 reduces, and begins to keep the concentration of detergent remover A209 for certain when supplying with.Thereby by cleaning the scanning of nozzle 202, moment (for example: Ozone Water), on the whole surface of semiconductor substrate 206, can clean processing with the short time is replaced into detergent remover A209 to developer solution 207.

In addition, along air curtain, discharge by the foreign side to semiconductor substrate 206 between the gap by the developer solution 207 of detergent remover A209 displacement and detergent remover, make clean nozzle 202 scannings after, can prevent that developer solution 207 grades from returning on the substrate.

But, at this moment, the dry air 208,210 of high pressure, with the direction of the direction approximate vertical of scanning on the semiconductor substrate 206 on, need not discontinuously, be linked to be a rectilinear form, form air curtain.

Provide in the nozzle 202 at detergent remover, then high pressure dry air 210 sprays in proper order, perhaps blows and pays a detergent remover B211, high pressure dry air 212.

In the present embodiment, use Ozone Water at detergent remover A209.This Ozone Water makes the dissolving product, the molecule that produce in the process of carrying out development treatment, and oxidation such as precipitate.Have oxidation of organic compounds especially, make its molecular configuration decompose the effect of sectionalization particle.Therefore, after development treatment, suppress organism to adhering to again of photoresist etc., can reduce the generation of the defective locations of resist pattern significantly.

In addition, at this moment, Ozone Water can be used with the low concentration of 1ppm.If this concentration, then Ozone Water can not have damage to the pattern of photoresist.In this case, because the side wall portion of the pattern of etching photoresist only reduces the roughness (=locality deviation) of resist pattern dimension, in face, the effect of the dimensional homogeneity that can be improved.

In addition, as mentioned above, in the present embodiment, in detergent remover B211,, use hydrogen water as the detergent remover of character with reductibility.

As mentioned above after, on the surface of photoresist film, adhere to and clean and the particle of residual organic etc. by the Ozone Water decomposing organic matter.If on the pattern of this organic particle attached to photoresist, can on the resist pattern, produce defective locations (deviation of=pattern dimension), in etching work procedure thereafter, can produce the error of size and shape.

For this problem, as present embodiment, after Ozone Water is provided,, reduce the surface of this organic particle etc. by ejection hydrogen water, once more, from the surface isolation of photoresist film.Thus, comprise other pollutant and impurity,, can further reliably lowly clean processing to foreign side's flushing of semiconductor substrate 206.

In the present embodiment, in detergent remover A209, use Ozone Water, in detergent remover B211, use hydrogen water, continuously they are offered developer solution 207 on the semiconductor substrate 206 successively.In this case, Ozone Water is the aqueous solution of oxidisability, and on the other hand, hydrogen water is the aqueous solution of reductibility.In cleaning the process of handling, if Ozone Water and hydrogen water are sneaked into mutually, then solution properties is separately offset, and can make the function reduction as detergent remover, causes cleaning effect and descends.

Thereby, when using the detergent remover of relative like this character, the same with embodiment 1, in order to separate two kinds of detergent removers, blow the dry air of paying high pressure, if between form dry air and suppress sneaking between the detergent remover, then have the effect that clean effect is remained on certain altitude.

And then, in the present embodiment, in detergent remover A, use Ozone Water, in detergent remover B, use hydrogen water in addition, but, then can change into the detergent remover of other kind if can obtain the liquid of the effect the same with them.For example, in detergent remover A, use Ozone Water, in detergent remover B, use pure water, can use as mentioned above to clean and handle.In addition, the pure water being used for detergent remover B adds surfactant, can more effectively remove impurity and pollutant.

In the present embodiment, as mentioned above,, and during the detergent remover B211 ejection,, blow the dry air 208,212 of paying high pressure and clean processing in their both sides, front and back at detergent remover A209.At this moment, the dry air 208,211 of high pressure works as air curtain, and on the direction of scanning of cleaning nozzle 202, from detergent remover A209, and block the front and back of detergent remover B211.Thereby detergent remover A209 and detergent remover B211 to foreign side's diffusion, are not offered developer solution 207 by the concentrated area, and the pressure height can further improve clean effect.

Below, with reference to Fig. 9 A, Fig. 9 B, increase the effect of present embodiment and the situation comparative descriptions of use method of cleaning in the past.

At this, at first, as mentioned above, make on one side the clean nozzle scan of use that uses in the present embodiment, as an example, on one side air, Ozone Water, air, hydrogen water, air be provided in proper order, carry out the clean processing of substrate,, measure the dimensional homogeneity of photoresist pattern thereafter, and the number of defective locations.In addition, the same at this with the situation of embodiment 1, as an example, repeat 3 times and carry out so clean processing, in each is handled, measure the dimensional homogeneity in the substrate, and the number of the defective locations of pattern.In Fig. 9 A, Fig. 9 B, write down 3 clean each that handle of the method for using present embodiment, and the result of method of cleaning in the past, the effect of present embodiment is relatively investigated the mean value of these 3 times clean processing and the value of method of cleaning in the past.Its result in the present embodiment, can obtain the effect shown in Fig. 9 A, Fig. 9 B as can be known.

In Fig. 9 A, showed, in the method for present embodiment, and in the past method of cleaning separately in, in the face of substrate (=wafer), measure the inhomogeneity result of the size of photoresist pattern.In the method for present embodiment, the same with embodiment 1 shown in Fig. 9 A, compare with method of cleaning in the past, can improve dimensional homogeneity about 20%.At this, dimensional homogeneity in design, is should be that the pattern of same size is an object, measures with a plurality of points of these patterns, shows the degree of the deviation of the size that its result obtains.

In addition, in Fig. 9 B, showed, in the method for present embodiment, and method of cleaning in the past separately in, measure the result of the number occur in the defective locations on the photoresist pattern.In the present embodiment, the same with embodiment 1 shown in Fig. 9 B, on substrate, measured the number of the defective locations of photoresist pattern, compare with the situation of using method of cleaning in the past, also can reduce 65%.At this, defective locations, expression produces the state of error dimensionally because of the impurity that adheres to organism etc. on the photoresist pattern, pollutant etc.

Like this, in the present embodiment, with heavy caliber (for example: semiconductor substrate diameter 300mm) is corresponding, and then and compare with method of cleaning in the past, in development treatment of photoresist etc., can improve clean effect.

In the present embodiment, produce bubble, play the physical property effect, can also further improve and clean effect by making this bubble in the inside of detergent remover.In this case, as shown in figure 10, in the zone that the air curtain 208,210 of both sides separates, before the developer solution 207 that reaches on the semiconductor substrate 206, in detergent remover A209 by nozzle 202b ejection, the part (=little air) 213 of the high pressure dry air 210 that blows out from the 2nd air nozzle 202c is sneaked into, can in detergent remover A209, produce bubble 214.This bubble 214 in the inner pressure differential that produces of detergent remover A209, attached to the dissolving product on the patterned surfaces of photoresist, and applies impact on the molecule etc., removes them easily, can further improve clean effect.

This situation in clean nozzle 202, in a side of the dry air 208,210 of high pressure, applies processing and makes part of air blow side out to adjacent detergent remover A209 one at least.

Specifically, the both sides of nozzle 202b are provided at the 1st detergent remover, from nozzle 202a, and the air blow-off outlet 205 of nozzle 202c, blow out the air of high pressure, form air curtain, and then and, at least processing makes and the part of high pressure dry air 208,210 blows side out to adjacent detergent remover A209 one.At this, be constructed so that at least in a certain side of nozzle 202a and 202c and air ejiction opening 205 is provided with the interval of regulation, blow-off outlet (for example: poroid) is being set near nozzle 202b one side, blow out the dry air 208 of high pressure, perhaps the part of the dry air 210 of high pressure.

And then, though, make among the detergent remover A209 and produce bubble, clean processing as an example, also can produce bubble among the detergent remover B211 and clean processing with applying processing with the same main points of clean nozzle 202, making.In addition, shown in present embodiment, the dry air 208,210,212 of each high pressure works, and on semiconductor substrate 206, developer solution 207 is suppressed at seldom amount.Under these circumstances, detergent remover A209, promptly Ozone Water does not make its density loss in liquid, reaches the photoresist film in the developing reaction, and its top layer part becomes by the state by the Ozone Water oxidation.

Like this, by the also top layer part of oxidation photoresist film, can further prevent reliably adhering to again of organic particle.Thereby in the present embodiment, dissolving product, molecule, precipitate etc. even have, also can be removed organism effectively, in cleaning the process of handling, can significantly reduce the generation of the defective locations of developing pattern.

In addition, in the present embodiment, pay high pressure dry air 208,210,212 by blowing, the film of detergent remover A209, and the film of detergent remover B211 is pressurized, under air curtain, is suppressed to the thickness of hundreds of nm to tens of μ m.That is, in semiconductor substrate 206, in the zone that high pressure dry air 208,210,212 passes through, detergent remover A209, detergent remover B211 are suppressed in trace.Thereby, thereafter,,, on semiconductor substrate 206, at least also can pay the dried effect identical with it even do not make its high-speed rotation (=velocity of rotation: 1000 to 4000rpm) get rid of detergent remover as method in the past.This situation, on semiconductor substrate 206, because do not suffer physical loads (=for example: the current of centrifugal force, detergent remover etc. etc.), even (for example: under the situation of semiconductor substrate diameter 300mm) use heavy caliber, also easily and ground such as not damaged, after cleaning processing, can give the pattern of photoresist with drying effect.

Like this, in the present embodiment, with heavy caliber (for example: semiconductor substrate diameter 300mm) is corresponding, and then and, with method in the past, that is, the situation that the semiconductor substrate high-speed rotation is cleaned is compared, and can obtain equal above clean effect.

And then, in development treatment and clean the processing, also can use the clean nozzle 220 that becomes one with nozzle 221 with nozzle 202 and development shown in Figure 31.As shown in figure 31, nozzle 220 possesses and cleans with nozzle 202 and development nozzle 221.Developing with in the nozzle 221, the ejiction opening 222 of ejection developer solution is formed shape of slit.With the length of the direction of the direction of scanning quadrature of ejiction opening 222, at the maximum gauge of substrate, perhaps more than the longest edge.Thus, with the direction of direction of scanning approximate vertical on, can not interrupt continuously, the same ground provides developer solution to the processed zone of substrate.And then ejiction opening 221 is the 3rd ejection zones.And then, develop with the position of nozzle 221, as shown in figure 31, the relative scanning direction is not limited in the place ahead one side of cleaning with nozzle 202.For example, develop with nozzle 121, the relative scanning direction also can be configured in rear one side of cleaning with nozzle 202.

Under the situation of this nozzle, do not carry out development treatment side by side and clean processing.When development treatment,, do not carry out the ejection of detergent remover and blowing out of gas with nozzle 202 from cleaning from developing with nozzle 221 ejection developer solutions.In addition, when cleaning processing, carry out the ejection of detergent remover and blowing out of gas with nozzle 202, do not spray developer solution with nozzle 221 from developing from cleaning.

As mentioned above,, and in the embodiment 2, compare, can effective carry out the clean processing of substrates such as semiconductor substrate with method of cleaning in the past at embodiment 1.

More than, in embodiment 1 and embodiment 2,, be an example with semiconductor substrate as substrate, the manufacturing process of semiconductor device is illustrated.But, in these embodiments, in addition, even under the situation of using crystal liquid substrate, exposure with mask substrate etc., also can be in development treatment, and clean and be suitable in handling etc., can improve the yield rate of various products.

(embodiment 3)

Figure 11 is the process flow diagram of processing sequence of showing the developing method of embodiments of the present invention 3.In addition, be the process chart of processing sequence of showing the developing method of embodiments of the present invention 3 from Figure 12 to Figure 16.

The developing method of embodiments of the present invention 3 is described with Figure 11 to Figure 16.

(step S101)

As shown in figure 12, in the substrate 300 that comprises semiconductor substrate, on interarea, be coated with formation chemically amplified corrosion-resisitng agent (photonasty resist film) by antireflection film, on the chemically amplified corrosion-resisitng agent film, use KrF exciplex laser instrument, by exposure groove reduced projection exposure circuit pattern.Substrate 300 being carried out after PEB handles, by the conveyance aut.eq., substrate 300 is by the top of conveyance to the substrate maintaining part 301 of developing apparatus, is attracted to be fixed on the substrate maintaining part 301.In when flushing, and when dry etc., by rotating mechanism 302 substrate 300 is rotated as required.

The developing apparatus of present embodiment further possesses the flooding nozzle of making 303, and developer solution provides nozzle 304 from an end of substrate 300 scanning mechanism to other end scanning.Flooding nozzle 303, when the flushing of substrate 300 or development when stopping, the liquid and the weakly alkaline liquid that having the oxidisability of ultrapure water, Ozone Water, oxygen water (sour plain water) etc. from the ejiction opening ejection.Developer solution has the limit also longer than the maximum gauge of substrate 300 with nozzle 304, provides developer solution to substrate 300 equably.And then, flooding nozzle, prevent the damage of the oxidizing liquid that sprays or alkalescent liquid to the photosensitive type resist of substrate interarea, in order to make acting on this substrate of this detergent remover even, wish to possess the mechanism that the detergent remover of the ejection of making shakes and prevent in the local mitigation mechanism that strengthens of the force of the inner detergent remover of nozzle ejiction opening.

(step S102)

Below as shown in FIG. 13A, make flooding nozzle 303 move to the position of the height of stipulating apart from substrate 300.When substrate 300 is rotated, to substrate 300, spray the following Ozone Water 306 of 2 ozone concentration 5ppm in second as above-mentioned Treatment Solution from flooding nozzle 303.Therebetween, flooding nozzle 303 moves on substrate 300 interareas, and Ozone Water 306 is shaken, and is provided to as far as possible equably on the interarea as substrate 300.Then, shown in Figure 13 B, make substrate 300 rotate dry substrate 300 surfaces.

At this, though in order to be formed uniformly liquid film on substrate, carry out above-mentioned treatment process, this pretreatment procedure not necessarily.In addition, liquid film be can be formed uniformly,, oxygen water, hydrogen water, nitric acid used then as pretreatment liquid if compare also with Ozone Water, and aquae hydrogenii dioxidi, alkali ion waters etc. also can.

(step S103)

Then, shown in Figure 14 A, 14B, as the 1st development treatment, at the film that forms the developer solution of the photonasty resist film on the substrate processing 300 on the substrate 300.At this, rectilinear form developer solution jetting nozzle 304 is scanned to the other end from an end of substrate 300, by with curtain shape ground ejection developer solution 307, on substrate 300, form development liquid film 307.As shown in Figure 14B, developer solution provides the length of the direction vertical with the direction of scanning of nozzle 304, because longer than the diameter of substrate 300, thereby can form the film of developer solution 307 on whole of substrate 300.

The development liquid film forms operation, is not limited to method shown here.For example, shown in Figure 15 A, 15B, there is one side to provide nozzle 304 that developer solution is provided, Yi Bian make substrate 304 rotate the method that on whole of substrate 300, forms development liquid film 307 from the developer solution of rectilinear form.Figure 15 is the diagram of displaying according to the variation of the development liquid film formation method of the embodiment 3 of the present application.Figure 15 A is a sectional drawing, and Figure 15 B is a planimetric map.

In addition, shown in Figure 16 A, Figure 16 B, having on one side from 312 pairs of substrates 300 of nozzle of straight tube shape provides developer solution 307, and substrate 300 is rotated, the method for formation development liquid film 307 etc. on 300 whole of substrates.Except method shown here, can also make in various manners.Figure 16 is the diagram of variation of development liquid film formation method of showing the embodiment 3 of the present application.Figure 16 A is a sectional drawing, and Figure 16 B is a planimetric map.

(step S104)

Clean to handle as the 1st, after forming the development liquid film on the substrate interarea about 5 seconds, from flooding nozzle 303, the ejection pure water made substrate rotating simultaneously, the development liquid film on the flushing substrate 300.Then, Yi Bian substrate 300 is slowly run, Yi Bian spray low concentration ozone water.

(step S105)

Then, make substrate 300 high-speed rotation, the surface of dry substrate 300.

Also can be from flooding nozzle 303, in the time of ejection low concentration ozone water, make substrate rotating about 10 seconds, after cleaning, make the substrate high-speed rotation with low concentration ozone water, make drying substrates.

As detergent remover, used non-confrontational erosion agent to produce the Ozone Water of the low concentration that surpasses the damage more than the permissible range in the present embodiment with oxidisability.If same effect is arranged,, also can use the oxygen water of dissolved oxygen in pure water etc. as detergent remover with oxidisability.And then if same effect is arranged, non-confrontational erosion agent has above the damage more than the allowable value, also can use weak alkaline aqueous solution.

(step S106)

Then, as the 2nd development treatment, at the developer solution that forms the resist film on the substrate processing 300 on the substrate 300.At this, linearity developer solution jetting nozzle is scanned to the other end from an end of substrate, by with curtain shape ground ejection developer solution, form the development liquid film on the substrate.

Also can in the process of the 2nd development treatment, on the substrate interarea, stir developer solution if desired.In this case, for example, the stirring means of established development liquid film, can be on substrate, to dispose cowling panel, by making this cowling panel rotate the method that produces air-flow and making method that substrate self rotates and ticker by the outside applies the method etc. of vibration to liquid, so long as have the effect that developer solution is flowed on whole of substrate, which type of method can.

(step S107)

As the 2nd clean the processing, in about 25 seconds after forming the development liquid film on substrate 300 interareas,, in the time of the ejection pure water, substrate 300 is rotated with 500rpm from flooding nozzle 303.And then, as the detergent remover after the 2nd development, in the present embodiment, though used pure water, but if higher clean effect were arranged, then as detergent remover, would use reducing liquid, oxidizing liquid (Ozone Water, oxygen water), alkaline ionized water, faintly acid ionized water, supercritical water, carbonated water, hydrogen water, pure water etc., what is all right.In addition, if can improve clean effect, can also make up these liquid aptly.

(step S108, S109)

After making the substrate high-speed rotation, making drying substrates, finish developing procedure and reclaim substrate with the conveyance aut.eq..

The problem points and the reason thereof of developing method in the past are described.The photosensitive type resist of chemical amplifying type by the exposure and the thermal treatment of desired pattern, forms fine alkali soluble zone and alkaline indissoluble zone in resist film.If these alkali soluble zone and alkaline indissoluble zone touch alkaline-based developer, then in the general developing procedure of common KrF resist in the needed time, the alkali soluble zone is dissolved in the alkali, and does not dissolve in alkaline indissoluble zone.In development,, be sandwiched between resist pattern, be subjected to resist indissoluble zone, and, stay this place from the intermolecular interaction of the resultant of reaction of same dissolving as alkaline indissoluble zone from the resultant of reaction of alkali soluble region generating.If particularly processing dimension is fine, then the resist pattern dimension is also fine, thereby the size with alkaline indissoluble zone in alkali soluble zone also diminishes, and intermolecular interaction enhancing more and more is difficult to be diffused in the liquid atmosphere.In addition, resultant of reaction because of the binding force effect from the electrostatic potential of substrate, is also stayed the there after the dissolving.Its result, can prevent that alkali ion further is diffused into can hold the resist zone,, meanwhile, develops and is hindered different local different in resist near surface alkalescence concentration, and developing powder changes according to the position.

The static developer solution that fills with on substrate through using the developer solution on detergent remover (pure water) the displacement substrate behind the official hour immediately, stops development.In the method, because being stuck in the real estate of the locality of resultant of reaction as described above produces, finish until developing, do not remove it, institute so that develop is hindered, and produces difference in face on the speed of developing.Particularly because change, so different in the amount of the resultant of reaction of zone that pattern is dredged and close region generating according to how many developing powders of the amount of resultant of reaction.Therefore cause the different phenomenon of resist near surface of alkali ion concentration in zone that pattern is dredged and close zone, in a word, the resist near surface in zone that pattern is dredged and close zone causes different these phenomenons of developing powder.Its result, the problem of generation size density difference in the resist pattern.

For above-mentioned problem, considered that once removing resultant of reaction in the way of developing develops with fresh developer solution once more.But the method that development is divided into 2 times is a technique known, for example opens in the flat 2-46464 communique open the spy.Open in the flat 2-46464 communique after developing once with developer solution the spy, flushing is dry, develops with the dense developer solution of concentration once more.The inventor thus, removes the resist residue and the scum silica frost of the bottom of resist pattern.These residues and scum silica frost are the not dissolving parts of resist, are not the resultant of reaction that is produced by the development as the object of removing in the cleaning after the 1st time is developed.The residue of these resist bottom surfaces and scum silica frost are the distinguished point that might become defective after development, almost are helpless to the homogeneity in the face.Thereby, open unresolved problem in the past developing in the flat 2-46464 communique above-mentioned spy.In addition, though do not record and narrate especially, the washing fluid of this situation typically refers to pure water.Method shown in this point and the present embodiment differs widely.

Generally, after developing for the first time, when cleaning under the situation about cleaning in handling the 1st, be replaced into the pure water of pH7, on the resist surface, produce rapid pH variation, form alkaline difficult deliquescent layer from the high developer solution of pH with pure water.Therefore, in the second development of the pattern that resultant of reaction is totally removed, begin to utilize the dissolving of alkali equably from this difficulty deliquescent layer, last, reflection stays in the former state of the surface configuration that is replaced into the difficult deliquescent layer that forms when cleaning from the 1st beginning of developing.On the other hand, at the difficult deliquescent layer that when developer solution is replaced into detergent remover, forms, exposure deviation and the influence of focusing deviation, the developing powder deviation at development initial stage etc., usually lack of homogeneity when obviously reflection exposes.Thereby it is also poor that the dimensional homogeneity in the real estate of the resist pattern that the back of developing forms is compared with common only once development.Thereby, open in the method for flat 2-46464 communique a not only unresolved problem that in the past develop to send out produced, and the homogeneity variation in the real estate as can be known above-mentioned spy.

In the developing method shown in the present embodiment, between the 1st development treatment and the 2nd development treatment, it is characterized in that handling with the liquid of oxidisability with Ozone Water etc.When beginning to clean under the situation about then cleaning the back, handle from developer solution by contacting the surperficial difficult deliquescent layer that pure water forms, by the oxidized surface upgrading by Ozone Water with Ozone Water with pure water.Perhaps, only decompose the surface, make the indissolubleization on surface solvable alkali by only improving ozone concentration.On the other hand, when under the situation that begins to clean with Ozone Water because in developer solution on the resist surface of swelling ozone molecule enter easily and make its oxidation, so even pH reduces, also indissoluble resist surface hardly keeps solubility to alkali.In either case, develop if then carry out the 2nd, then no matter how develop for the first time, the optics profile when all verily developing for exposure forms the resist pattern.And if then with the time of development time equal length carried out in the past, then be not subjected to the influence of resultant of reaction, also unaffected on the difficult deliquescent layer in surface, phenomenon is fully carried out, so the influence of the exposure during exposure, focusing deviation etc. is relaxed, the dimensional homogeneity in the face of the resist pattern after the development is enhanced.In addition, owing to clean with the oxidation shape liquid of Ozone Water etc., thereby can decompose the resultant of reaction that between inchoate resist pattern, exists, remove neatly.And then the particle that becomes defective after development also can be removed.

In addition, the time since the 1st development to ejection the 1st detergent remover is made as about 5 seconds in the present embodiment, and it be the reasons are as follows.

Figure 17 medelling has been showed obtained the curve map of the intensity of reflected light corresponding with the time when observation is utilized the situation of dissolving of developer solution of KrF eurymeric resist film.The sine wave that the 1st stage in the curve map of Figure 17 is seen is the interference effect that is produced by film thickness that proceeds to because of development that the depth direction of thickness causes.Usually, 1st stage of resist after the beginning of developing is shown in Figure 18 A, solvable regional dissolution velocity height in the exposure portion 331 of resist film 330, be dissolved on the depth direction and carry out,, in DUV exposes with the eurymeric resist, needed for 5～10 seconds up to the bottom surface that passes through to resist.In the 2nd stage, shown in Figure 18 B, developing is not the depth direction of resist film, but carries out to the direction of dissolving resist pattern sidewalls.At this moment reflection strength changes lentamente.In the 2nd stage, dissolution velocity reduces, and for the sidewall of resist pattern is dissolved into desirable size, uses the dissolving direction to carry out on the direction of comparison level.

Being dissolved on the depth direction of resist carried out in the 1st stage like this, in the 2nd stage, on transverse direction, carry out, be because the exposure intensity that produces owing to inevitable diffraction of light in projection exposure distributes, the cause from exposure portion to the slow variation of non-exposure portion's exposure intensity.Because the distribution of this exposure intensity, exposure is strong, and promptly the pars intermedia of pattern that is fully exposed and pattern is because sink the most apace when developing, so become such development of the 1st stage of sharply advancing on depth direction.On the other hand because relatively developing powder is slow with pars intermedia near the few pattern wall of exposure, so become lentamente to transverse direction advance in such development shown in the 2nd stage.In the 1st stage, in common development, hinder the most of generation of the dissolubility product that develops.

In the present embodiment, the time that sprays the 1st detergent remover since the 1st development treatment be made as develop begin about 5 seconds after, but this is the time of switching to the 2nd stage from the 1st stage, promptly, be developed in the dissolving portion and carry out, pass through to the time of the bottom surface of resist to opposite direction.Be arranged to the reasons are as follows of such timing.

By a dissolving product that in the 1st stage, once produces, washing during from the 1st stage to the 2nd phase transformation, can prevent by hindering the alkaline density loss that the dissolving product that carries out of developing causes.If the 1st development stopped soon than it, then the dissolving product makes generation make alkaline density loss once more in following development connects, and hinders and develops.If make the 1st development stand-by time slower than it, then because the dissolving product that produces produces the alkaline density loss of locality, the developing powder that produces locality in the development in the 2nd stage descends.After this promptly use in the fresh developer solution and develop once more, also can not eliminate the spatial unevenness that begins to form.Be in the part that postpones the time in the 2nd stage by the 1st development stand-by time from the 1st phase change only, the alkaline concentration of the locality of each position is fallen much lower, and unevenness also is increased.

Because it is dissolved in the 2nd stage, near residual melted zone pattern sidewalls, dissolution velocity is slow in development, in addition, because after carrying out once cleaning in the 1st stage, in time, can change on the space with the dissolving product of the relevant alkaline concentration of developing and be removed, and produce hardly, so in the 2nd develops, can control the pattern line width fully.

By 2 above reasons, the timing stop developing for the 1st time is as the transfer point optimum in the 1st stage and the 2nd stage.

In the present embodiment, switching to the point in the 2nd stage from the 1st stage of Figure 17 was 5 seconds.This value changes according to anticorrosive additive material, developer solution, alkaline concentration, temperature etc., is not limited to the value of present embodiment.

Below the experimental result of carrying out with the inventors of reality be the effect of base description present embodiment.

Order is coated with antireflection film, the positive resist of KrF on wafer, uses to comprise by wide line of 200nm and pattern (the 200nL/S pattern of forming at interval; L: S=1: 1) and the pattern of forming by the interval of wide line of 200nm and 2000nm width (200nm isolated line: L: S=1: groove 10), carry out the reduced projection exposure by KrF exciplex laser instrument, behind heat treatment step, carry out development treatment.In the development treatment operation, as follows, made 4 kinds of samples.Condition is illustrated in the table 1.

[table 1]

	Sample A	Sample B	Sample C	With reference to using sample
					Pre-treatment	Ozone Water	Ozone Water	Ozone Water	Ozone Water
The 1st development treatment	Have	Have	Have	Have
					The 1st cleans processing	Water	Ozone Water	Pure water+Ozone Water	Do not have
The 2nd development treatment	Have	Have	Have	Do not have

Wafer for whole samples, carry out pre-treatment with Ozone Water, the developer solution amount of providing that nozzle is provided from developer solution is set to 1.5L/min, and the sweep velocity of nozzle is set to 60mm/sec, forms the developer solution thickness (the 1st development treatment) of liquid thickness 1.5mm.With reference to the 1st clean the processing and the 2nd development treatment of not carrying out with sample after this, the development liquid film forms and carries out 1 time.In sample A, after development began for 5 seconds, wash once (the 1st cleans processing), once more, the developer solution amount of providing that nozzle is provided from developer solution is set to 1.5L/min, and nozzle scan speed is set to the liquid film (the 2nd cleans processing) that 60mm/sec forms liquid film 1.5mm.

Relative therewith, in sample B, carry out the 1st and clean to handle with Ozone Water, in sample C with pure water carry out the 1st clean handle after, then clean, and then then as sample A, form the 2nd time development liquid film (the 2nd development treatment) with Ozone Water.Thereafter the 2nd clean processing and dried are all handled under the same conditions.

The size evaluation result of these samples is illustrated in the table 2.

[table 2]

	Sample A	Sample B	Sample C	With reference to using sample
					1: 1 pattern homogeneity 3 σ [nm]	12.2	6.5	5.8	6.1
1: 10 pattern homogeneity 3 σ [nm]	15.2	8.2	7.8	8.3
					Density [nm]	20	5	7.8	30

In table 2, it is poor that the difference in size of the line of 200nmL/S pattern on the same substrate and 200nm isolated line pattern is set to density.Density in table 2 is poor, is arranged to deduct from isolated patterns (1: 10 pattern) value of the size of L/S pattern (1: 1 pattern).

In the reference sample, though the inner evenness of pattern dimension is relatively good, but after the development liquid film forms, the resultant of reaction that produces because develop is almost not moving, so in the big isolated line pattern of the conversion zone of per unit area (1: 10 pattern), than the big 30nm of size of the little L/S pattern of the conversion zone of per unit area (1: 1 pattern).

Relative therewith, the density difference is eliminated in sample A.On the other hand, the homogeneity in the face worsens significantly.Consider following such situation as these reasons.At first, the reason that reduces of density difference is considered as follows.Near the amount of the resultant of reaction that exists common pattern is in part that the resist pattern is dredged and close part, because different locally, thereby the alkali ion concentration in developer solution also produces the difference of locality.But, because the developer solution of fresh concentration is provided after with developer solution of pure water displacement once more, so the difference of the alkaline concentration of this locality has not had.Thereby no matter the density of pattern how, because can promote to develop by fresh developer solution, the optical profile originally that verily develops be so the difference in size that produces because of pattern density has reduced some.

The problem of the dimensional homogeneity in the face is considered as follows.Usually at development time in the fast stage, dissolution velocity is fast.In the fast stage of development time, for example different not simultaneously because of the position on the wafer with exposure focusing in exposure, the difference of dissolution velocity occurs more significantly.Usually, carry out the fully long time because develop, thus such development can't see, but the 1st flushing of present embodiment is stopped the 1st and is developed by the fast stage ejection of development time.Thereby, be thought of as above-mentioned effect and obviously occur.In addition, at this moment since developing reaction is active cause in the adding pure water, thereby cause that rapid pH value changes, the resist composition is assembled on the interface of resist and pure water, particularly former part that should be dissolved, and for example the resist surface of the not dissolving part of pattern sidewalls etc. is difficult to dissolve.By fill with developer solution once more thereafter, though develop once more, but, original dissolving condensed owing to sprinkling water because carrying out the surface of the resist in zone, dissolubility reduces, so be not original sub-image, by contact the shape of the established difficult deliquescent layer of reflection with pure water, dissolve.Thereby, become and maintain the short time and clean the homogeneity of the time difference and develop.As mentioned above, though the influence that the development of the resultant of reaction cause that develop to produce hinders does not have, the density difference reduces, and the fuzzy etc. of exposure and focusing has the factor former state of big influence to change at the development initial stage, and big influence is arranged, and makes the inner evenness variation.

Relative therewith, in sample B and sample C, as can be known the homogeneity in wafer face with reference to identical or on it with sample.Though this is because by contacting once with pure water, the resist aggegation forms difficult deliquescent layer from the teeth outwards, but by adding Ozone Water, the difficult deliquescent layer on the resist surface of the not dissolving part of oxidation as the sidewall of pattern is kept the cause to the deliquescent state of developer solution.Thereby, if add the developer solution of fresh concentration once more, can not hinder yet and develop owing to the surperficial difficult deliquescent layer of the resist on pattern sidewalls etc., then promote to develop the dimensional homogeneity in the raising face.

In addition, by carrying out once flushing, the effect of washing away near the resultant of reaction of resist pattern is the same with above-mentioned sample A.When fresh developer solution is provided for the 2nd time, because the developer solution alkalescence density loss of the locality that causes at resultant of reaction is not the same, so it is poor to reduce the density of size greatly.

At this, in sample B and sample C homogeneity exist some be not both because, in sample B, all carry out the 1st and clean processing with Ozone Water, because of the cohesion of the resist composition of the rapid pH value when developer solution is changed into washing fluid changing is relaxed by Ozone Water, former state keeps the surperficial affine easy cause of the resist of developer solution.

And then above-mentioned the 1st development treatment, the 1st is cleaned processing, the 2nd development treatment, the 2nd is cleaned and handled, and can carry out with Figure 30 or device shown in Figure 31.Situation about handling with device shown in Figure 30 is described.During the 1st and the 2nd development treatment, provide developer solution with nozzle 121 to substrate from developing, it is mobile that nozzle 220 is scanned on substrate.The 1st cleans when handling, and provides nozzle 102a to provide Ozone Water to substrate from detergent remover, nozzle 202 is scanned on substrate move.The 2nd cleans when handling, and handles with the method that illustrates in the 1st embodiment the samely.

Situation about handling with device shown in Figure 31 is described.When the 1st and the 2nd development treatment,, nozzle 220 is scanned on substrate move from developing with nozzle 121 when substrate provides developer solution.When the 1st cleans processing, provide nozzle 202a dry air to be provided and to provide nozzle 102a to provide Ozone Water from the 1st air to substrate from detergent remover to substrate, nozzle 202 is scanned on substrate move.The 2nd cleans when handling, and handles with the method for explanation in embodiment 2 the samely.

(embodiment 4)

Figure 19 is a development treatment process flow diagram in proper order of showing the embodiment 4 of the present application.

Step S201～S203, since the same with the step S101～S103 of explanation in embodiment 3, so omit explanation.

(step S204, S205)

In step S203 after forming the development liquid film on the substrate interarea about 5 seconds, from flooding nozzle, ejection low concentration ozone water.Then, though make substrate rotating, remove most of detergent remover, do not make drying substrates, only residual a small amount of detergent remover forms the ozone moisture film.

(step 206)

Then, the developer solution of the resist film on the substrate processing is formed on the substrate of the state that is formed with the ozone moisture film.The formation method of development liquid film is the same with embodiment 3.

Step S207～S209, since the same with the step S107～S109 of explanation in embodiment 3, so omit explanation.

The developing procedure of present embodiment has the effect much the same with embodiment 3.In the present embodiment, by residual liquid or alkalescent liquid on the substrate interarea with oxidisability, when the 2nd development treatment, improve affinity to the developer solution of substrate surface, thus when developer solution is provided, be reduced in the repulsive force that acts between developer solution and the substrate surface, providing of developer solution can be provided in real estate equably, and its result has improved the inner evenness of the size after developing.

The 1st clean the 2nd development treatment of handling from developing procedure after the 1st clean the processing, does not make the substrate high-speed rotation, rotates for 10 seconds with 500rpm, then, sprays the 2nd developer solution.Except above point, the experiment that the condition of carrying out is the same with the sample C of embodiment 3.As a result, pattern homogeneity 3 σ were 6.1nm in 1: 1, and pattern homogeneity 3 σ were 7.5nm in 1: 10, and the density difference is 5nm.Comparing with sample with reference is good value.

(embodiment 5)

In the present embodiment, the order of developing procedure is because the same with embodiment 3 thereby omit its detailed description.In the present embodiment, when the 1st and the 2nd development treatment, the gas molecule of the oxidisability with oxygen etc., the gas molecule that perhaps has the reductibility of hydrogen etc. is dissolved in the developer solution.

The treating apparatus of Shi Yonging is illustrated among Figure 20 in the present embodiment.As shown in figure 20, this device possesses: storage is as the development flow container 401 of the developer solution of alkaline aqueous solution; The dissolving film 402 that is connected with development flow container 401 via pipeline; The oxidizing gas generator 403 and the reducibility gas generator 404 that are connected with dissolving film 402 via pipeline; The developer solution that is connected with dissolving film 402 via pipeline provides nozzle 304.In addition, around substrate 300, be provided with over cap.And then, on the position identical, pay identical symbol and omit explanation with developing apparatus shown in Figure 12.

In this device, make the gas dissolving that in oxidizing gas generator 403 or reducibility gas generator 404, produces in dissolving film 402, by making the developer solution that provides from development flow container 401 see through this dissolving film 402, oxidizing gas or reducibility gas are dissolved in the developer solution.This device before substrate 300 ejection developer solutions, can make oxidizing gas (reducibility gas) be dissolved in the developer solution.

In the present embodiment, as oxidizing gas, make oxygen be dissolved in developer solution and carry out the 1st and the 2nd development treatment.Other processing is because of the same with embodiment 3, so omit its detailed description.

And then, in the 1st and the 2nd development treatment,, also can use to be dissolved with the reducibility gas molecule, for example the developer solution of hydrogen molecule etc. though used the developer solution that makes oxygen molecule dissolving.In addition,, do not use the developer solution that is dissolved with the oxidizing gas molecule in the time of then need not handling, can during a side processing therein yet two of the 1st and the 2nd development treatment if effect is abundant.

In the present embodiment, except embodiment 3 described effects, as developer solution, make the liquid of oxidizing gas molecular melting by use, have the resultant of reaction that produces from the beginning back of developing because of the effect of the decomposition of the oxidation of the oxygen molecule the developer solution and the resultant of reaction that causes thus, in developer solution the resist surface oxidation, because the effect of the mitigation of the size growth that the cohesion of the resultant of reaction that produces in developer solution causes etc.

In addition, during the 1st and the 2nd development treatment, perhaps when the processing of one side, be dissolved with when use under the situation of developer solution of reducibility gas molecule, have by going back resist surfaction that primary electron causes, changing the effect of resultant of reaction that the resultant of reaction that causes causes to the promotion of the diffusion in the developer solution, by the variation of resist surface potential by the surface potential of resultant of reaction to preventing adhering to of resist surface etc.

In the 1st and the 2nd development treatment, use the developer solution be dissolved with oxidizing gas, carry out the experiment the same with embodiment 3.Experimental result, the pattern dimension homogeneity was 3.8nm under 3 σ in 1: 1, was 6.1nm in the pattern at 1: 10, had confirmed desired effect.

(embodiment 6)

Figure 21 is a process flow diagram of showing the development treatment of embodiments of the present invention 6.

Order in the pattern disposal route of present embodiment, because the same with embodiment 3, the diagram of process flow diagram omitted, and the explanation of detailed order.

In the present embodiment, during the 1st development treatment, after having formed the development liquid film, develop making under the static state of substrate.Then,, as shown in figure 22, make the rotational speed of substrate 300, developer solution 307 is flowed with regulation through after the stipulated time.After making the substrate rotating stipulated time carry out flowing of developer solution, also make substrate static, under static state, expose.

In the present embodiment, carrying out the mobile time band of developer solution determines as follows.

As explanation in the embodiment 3, develop, form by the 1st stage of carrying out on the depth direction that is developed in thickness with in the 2nd stage of carrying out of on the direction of dissolving resist pattern sidewalls, developing after the 1st stage.

The purpose of the liquid flow in developing procedure is the resultant of reaction homogenising that makes in development, and alkaline concentration is recovered.Thereby, in order to make liquid flow effectively, can comprise the 1st stage from a large amount of generation resultant of reaction, the time (below, this time is called the time of passing through) of changing the 2nd stage that produces resultant of reaction hardly into carries out.

Below, the definite method by the time is described.And then, also can determine method with the time of passing through shown in following, determine to clean the beginning handled regularly at the 1st shown in the embodiment 3.

As the 1st method, be to become irradiates light on the pattern of object, measure the time variation of reflecting the intensity of reflected light that obtains, obtain result shown in Figure 17, ask and pass through time method.At this moment, be the reflected light of single wavelength because wish the intensity of reflected light of Figure 17, thus use the narrow-band light filter that the light of incident is arranged to single wavelength, perhaps can with the reflected light beam split of measuring.By the metering of time, can before actual the development, measure in advance, also can in developing procedure, measure each substrate.

As the 2nd kind of method, be to develop as the pattern of object at a plurality of development times, observe the section configuration of the pattern after developing etc., the resist of obtaining solvable zone develops to the time method of bottom surface.Below based on 2 experimental results, the mensuration by the time is described.

The object pattern of initial experiment is assumed to be 130nmL/S (1: 1) pattern (the dissolution velocity ratio is resist faster for the antireflection film of the film thickness of 60nm, the resist of 300nm film thickness).At first, obtain intensity of reflected light in the development of object pattern shown in Figure 23.Intensity of reflected light is the result of the light time of incident 550nm wavelength.From this result, obtain by the time be 6 seconds, being worth with this is the time that benchmark is determined liquid flow.

Showed among Figure 24 and represented to develop that beginning, developer solution are flowed, the diagram of development process ends with time shaft.After developer solution is supplied with operation, carry out static development in (x-1) second., make substrate with the rotating speed (250rpm) of regulation rotate 2 seconds, developer solution is flowed thereafter.That develops stops, and beginning was carried out after 30 seconds from developing.The x of this moment is defined as the timing of liquid flow.Figure 25 shows when x was changed with 2～12 seconds, the deviation (3 σ) of 130nmL/S (1: 1) pattern.Deviation when liquid does not flow is 10.2nm, and by making liquid flow, deviation has reduced.Particularly under the situation in 6 seconds, obtained best homogeneity.In addition, homogeneity is also relatively good under 4 seconds, 8 seconds situation.That is, near the time of passing through of from the intensity of reflected light of object pattern changes, trying to achieve, carry out in (by time ± 2 seconds, that is, by time ± 33%) having obtained good homogeneous under the situation of liquid flow.

Though as can be known by experiment, by the timing of liquid flow being arranged on by near the time (resist of solubility developed to the time of bottom surface), homogeneity improves, but provide the mobile restriction that waits device of nozzle owing to developer solution, under can only being set in the liquid flow start time by the situation after the time (for example in the present embodiment, in the time of can only after 9 seconds, making substrate rotating), can carry out in the time that is exceedingly fast (for example 9 seconds).

The object pattern of the 2nd experiment is assumed to be 130nmL/S (1: 1) pattern (antireflection film of the film thickness of 60nm, the resist of 300nm film thickness, the resist that dissolution velocity is slow).At first, obtain intensity of reflected light in the development of object pattern shown in Figure 26.Be the result of the light time of incident 550nm wavelength.From this result, obtain by the time be 20 seconds, being worth with this is the time that benchmark is determined liquid flow.

Figure 24 is the diagram with the time shaft order of representation.After developer solution provides operation, carry out static development in (x-1) second., make substrate with the rotating speed (250rpm) of regulation rotate 2 seconds, developer solution is flowed thereafter.Stopping of developing carries out after 60 seconds from the beginning of developing.The x of this moment is defined as the timing of liquid flow.Figure 27 has showed when x was changed with 10～35 seconds, the deviation (3 σ) of 130nmL/S (1: 1) pattern.Deviation when liquid does not flow is 9.8nm, by making liquid flow, has reduced deviation.Particularly under the situation in 20 seconds, obtained best homogeneity.In addition, homogeneity is also relatively good under 15 seconds, 25 seconds situations.That is, near the time of passing through of from the intensity of reflected light of object pattern changes, trying to achieve, carry out in (by time ± 5 seconds, that is, by time ± 25%) having obtained good homogeneous under the situation of liquid flow.

In the present embodiment, though, showed the method that makes substrate rotating, also can be by on the surface of development liquid film, forming air-flow, the method that developer solution is flowed as the method for liquid flow; The object that produce to flow is contacted with developer solution on the substrate, make the mobile method of developer solution by object or substrate are moved; Make the substrate vibration that is provided with developer solution make the mobile method of developer solution; Heat processedly, make method that developer solution flows etc. by convection current.

In addition, in the present embodiment,, also can be isolated residual pattern, the isolated any patterns such as pattern, sectional hole patterns, column pattern that connect though the L/S pattern is made as the object pattern.Also can obtain passing through the time of pattern respectively, determine the timing of liquid flow.Ought comprise simultaneously under the situation of a plurality of patterns (for example isolated residual pattern and L/S pattern), also can carry out 2 liquid and flow, can also determine the timing of liquid flow according to the time of passing through of the pattern of precision strictness from each by the time.

Make the motion that developer solution flows have many.For example, have,, on substrate, keep forming surface flow in the development liquid film, the method (spy opens the 2001-228625 communique) that developer solution is flowed by forming the air-flow that contacts with the surface of development liquid film after providing developer solution on the substrate; Make the developer solution on the front end contact substrate of the nozzle that developer solution is provided, the method (spy opens the 2000-195773 communique) that developer solution is flowed by nozzle or substrate are moved; The method (spy opens the 2001-307994 communique) that the substrate that making provides developer solution flows developer solution with the frequency vibration of stipulating.But, no matter which kind of motion, a certain timing after all whether record should developer solution provides makes liquid flow.Its result because do not make liquid flow at suitable time band, so can not realize effective liquid flow, can not obtain sufficient dimensional homogeneity.

(embodiment 7)

In semiconductor manufacturing process, form developer solution at the substrate blade that is formed with resist film, repeat the operation that resist film is processed into desirable shape.In the past, be coated with developer solution being formed with on the substrate of resist film, carried out developing procedure.Generally, for developer solution is provided, use developer solution that nozzle is provided.Like this, using developer solution to provide in the developing method of nozzle, the leading section of the nozzle of ejection developer solution provides liquid on the position near substrate.Therefore, the developer solution that is dissolved with resist contacts with nozzle.Its result provides the solids that adheres to resist on the nozzle at developer solution.This is paying the reason that thing becomes base board defect sometimes.

As the method for head it off, adopt the nozzle of developer solution to clean and adopt the nozzle of high concentration developer solution (spy opens the 2001-319869 communique) to clean.In these methods, because developer solution is used as detergent remover, so can only remove the defective that is dissolved in the developer solution.In addition, because use developer solution, so there is the high problem of cost.

Figure 28 is the process flow diagram of processing sequence of showing the pattern method of embodiments of the present invention 7.Figure 29 is the skeleton diagram of formation of the developing apparatus of embodiments of the present invention 3.In addition, use the developing method that embodiments of the present invention 3 are described from Figure 28 to Figure 29.

(step S401)

On substrate, be coated with antireflection film, chemically amplified corrosion-resisitng agent, use KrF exciplex laser instrument, by exposure groove, the reduced projection desirable pattern that exposes.This substrate of thermal treatment with the top of conveyance aut.eq. conveyance to the substrate maintaining part, attracts to be fixed on the substrate maintaining part.

(step S402)

Then, when the Ozone Water that is produced by oxidizing gas generator 504 is offered dissolving film 503,, make ozone solution in pure water, generate ozone by providing pure water to dissolving film 503 from pure water source 502.Then, the ozone that generates is offered developer solution nozzle 304 is provided.Provide nozzle 304 ejection Ozone Water by developer solution, clean developer solution provides nozzle 304.Provide the Ozone Water of nozzle 304 ejections to receive from developer solution, in liquid accommodating portion 505, be detained Ozone Water by liquid accommodating portion 505.In the Ozone Water in being trapped in liquid accommodating portion 505, soaking developer solution provides nozzle 304, cleans the face that the developer solution relative with resist provides nozzle 304.

After developer solution provides cleaning of nozzle 304, provide nozzle 304 that developer solution is provided from development flow container 501 to developer solution, by provide nozzle 304 ejection developer solutions from developer solution, the Ozone Water in the nozzle is replaced into developer solution.

And then, providing under the situation of oxidizing gas by circuit, do not need oxidizing gas generator 504.In addition, as oxidizing gas, except ozone, can also use oxygen, carbon monoxide gas, hydrogen peroxide.

(step S403)

Then, at the development liquid film that forms the resist film on the substrate processing on the substrate.At this, provide nozzle with the developer solution of rectilinear form, while provide developer solution to scan to the other end, on substrate, form the development liquid film thus from an end of wafer.

(step S404)

Behind official hour, provide flushing liquid (for example, pure water) from the flooding nozzle that is configured in the substrate top, while being rotated, it cleans substrate.

(step S405)

And then, get rid of pure water by making the substrate high-speed rotation, make drying substrates.

In the present embodiment, though as oxidizing gas, used the Ozone Water that in pure water, is dissolved with ozone, if having effect same then the dissolved gases molecule is not limited to ozone.For example, the oxidizing gas of oxygen, CO gas, hydrogen peroxide etc. also can.In addition, in the present embodiment,, nozzle cleans though being provided before the providing of developer solution, and also can be after developer solution provides.In addition, cleaning and can each substrate not carried out, also can be every regulation sheet number, every official hour.In addition, the exchange of nozzle etc. also can be carried out after maintenance.

If the repetition development treatment, then developer solution provides nozzle, owing to contact with the developer solution that is dissolved with resist, organic granular is attached on the nozzle.This particle on the resist surface, has as the residual possibility of defective in the development treatment of thereafter substrate.

Consider that in detergent remover the ozone molecule in the liquid is and attached to the impact of particles on the nozzle, with certain probability oxidation, decompose particle.Particle after being decomposed becomes low molecule, because its quality becomes very little thereby spreads in liquid easily.Its result, particle is removed.

The actual result of experiment of carrying out of inventor below is described.

Experiment according to the process flow diagram of above-mentioned Figure 28 the order on ground carry out.In order to confirm the result, in step S402, when with the ozone concentration in the solution being 10 is that the Ozone Water of m is cleaned under the nozzle situation in 5 seconds, clean under the situation in 5 seconds with developer solution and under situation about not cleaning the metering organism adhere to number of defects.Number of defects is respectively 5,10,50, and by cleaning with Ozone Water, defective has been reduced.Can confirm from these results, adopt the developer solution of Ozone Water that cleaning of nozzle 304 is provided, be very effective.

Can easily expect other advantage and variation for those skilled in the art.Therefore, the present invention its wideer aspect, be not limited in the detail of this displaying and description and represent embodiment.Thereby, under the situation of spirit and scope of the general inventive concept that does not deviate from the definition of claims and equivalent thereof, can carry out various changes.

Claims (29)

1. the developing method of the development of the light-sensitive erosion resistance film of exposing comprises:

Above-mentioned photonasty resist film to exposure carries out the 1st development treatment;

To having carried out the photonasty resist film of the 1st development treatment, provide this resist film surface is had oxidisability, or the detergent remover of alkalescence, carry out the 1st and clean and handle;

Carry out the 2nd development treatment to having finished the 1st above-mentioned photonasty resist film of cleaning processing;

The above-mentioned photonasty resist film that has carried out the 2nd development treatment is carried out the 2nd clean processing.

2. the described developing method of claim 1 is characterized in that, as the detergent remover with oxidisability, Ozone Water, oxygen water, nitric acid, and aquae hydrogenii dioxidi at least a is provided to above-mentioned photonasty resist film.

3. the described developing method of claim 1 is characterized in that, when the 2nd clean to handle, Ozone Water, oxygen water, hydrogen water, carbonated water, alkalescent water, slightly acidic water, and pure water at least a offered above-mentioned photonasty resist film.

4. the described developing method of claim 3 is characterized in that, when the 1st cleans processing, after pure water being provided to above-mentioned photonasty resist film surface, provides above-mentioned clean water.

5. the described developing method of claim 1 is characterized in that, the developer solution that uses when at least one side's of the 1st development treatment and the 2nd development treatment processing is the alkaline aqueous solution that is dissolved with the oxidizing gas molecule.

6. the described developing method of claim 1 is characterized in that, the developer solution that uses when at least one side's of the 1st development treatment and the 2nd development treatment processing is the alkaline solution that is dissolved with the reducibility gas molecule.

7. the described developing method of claim 1, it is characterized in that, roughly reach the passing through on the time of bottom surface in the zone of the soluble above-mentioned photonasty resist film of above-mentioned relatively developer solution at developer solution, above-mentioned detergent remover is provided to above-mentioned photonasty resist film, carry out the 1st and clean and handle.

8. the described developing method of claim 7 is characterized in that,

Above-mentioned passing through the time incided on the above-mentioned photonasty resist film by the light that makes specific wavelength in development, and metering is from the catoptrical Strength Changes of above-mentioned photonasty resist film, and the point that changes the waveform of representing monotone variation from interference waveform is tried to achieve.

9. the described developing method of claim 7 is characterized in that, and is above-mentioned by the time, and by the above-mentioned photonasty resist film that develops with a plurality of development times, the pattern of estimating after developing is tried to achieve.

10. the described developing method of claim 1 is characterized in that, after the 1st clean the processing, after making the aforesaid substrate dry tack free, carries out the 2nd development treatment.

11. the described developing method of claim 1 is characterized in that, in the 2nd development treatment, is carrying out under the residual state that the detergent remover that uses in the 1st clean to handle arranged on the above-mentioned photonasty resist film.

12. the described developing method of claim 1 is characterized in that, before carrying out the 1st development treatment, carries out the liquid that above-mentioned photonasty resist film is had oxidation is provided to the pre-treatment on this resist film surface.

13. the described developing method of claim 1 is characterized in that,

When the 1st and the 2nd development treatment,

To above-mentioned photonasty resist film, in the time of from the developer solution jetting nozzle ejection developer solution of length with length direction ejiction opening longer than the diameter of aforesaid substrate,

Aforesaid substrate and above-mentioned developer solution jetting nozzle are relatively moved to the other end from substrate one end, form the development liquid film on above-mentioned photonasty resist film surface.

14. the described developing method of claim 1 is characterized in that,

The above-mentioned the 2nd cleans processing,

When the ejection zone on being set at nozzle sprays detergent remover continuously to substrate, said nozzle and aforesaid substrate are relatively moved on a direction;

Wherein, the length of above-mentioned ejection zone and a direction above-mentioned direction quadrature is at the maximum gauge of aforesaid substrate or more than the longest edge equal length;

Said nozzle blows a pair gas from blowing out the zone continuously to aforesaid substrate, blows out the length of the direction zone and an above-mentioned direction quadrature, at the maximum gauge of aforesaid substrate or more than the longest edge equal length.

15. the developing method of the development of the light-sensitive erosion resistance film of exposing comprises:

Provide developer solution to above-mentioned photonasty resist film;

Developer solution on the above-mentioned photonasty resist film is flowed;

Wherein, between the start time and concluding time of the operation that above-mentioned developer solution is flowed, comprise developer solution and reach passing through the time the bottom surface in the zone of the soluble above-mentioned photonasty resist film of above-mentioned developer solution.

16. the described developing method of claim 15 is characterized in that,

Above-mentioned passing through the time incided on the above-mentioned photonasty resist film by the light that makes specific wavelength in development, and metering is from the catoptrical Strength Changes of above-mentioned photosensitive film, and the point that changes the waveform of representing monotone variation from interference waveform is tried to achieve.

17. the described developing method of claim 15 is characterized in that, and is above-mentioned by the time, by the above-mentioned photonasty resist film that develops with a plurality of development times, the pattern of estimating after developing is tried to achieve.

18. the described developing method of claim 15 is characterized in that, flowing of above-mentioned developer solution undertaken by making the substrate rotating that provides above-mentioned developer solution.

19. the described developing method of claim 15 is characterized in that, the flowing of above-mentioned developer solution is by forming air-flow and carry out providing on the substrate of above-mentioned developer solution.

20. the developing method of the development of the light-sensitive erosion resistance film of exposing comprises:

On above-mentioned photonasty resist film, provide developer solution;

Developer solution on the above-mentioned photonasty resist film is flowed;

Wherein, the start time that above-mentioned developer solution is flowed is after developer solution reaches time of passing through of bottom surface in zone of the soluble above-mentioned photonasty resist film of above-mentioned relatively developer solution.

21. the described developing method of claim 20, it is characterized in that, above-mentioned passing through the time, incide on the above-mentioned photonasty resist film by the light that in development, makes specific wavelength, metering is from the catoptrical Strength Changes of above-mentioned photonasty resist film, and the point that changes the waveform of representing monotone variation from interference waveform is tried to achieve.

22. the described developing method of claim 20 is characterized in that, and is above-mentioned by the time, by the above-mentioned photonasty resist film that develops with a plurality of development times, the pattern of estimating after developing is tried to achieve.

23. the described developing method of claim 20 is characterized in that, flowing of above-mentioned developer solution undertaken by making the substrate rotating that provides above-mentioned developer solution.

24. the described developing method of claim 20 is characterized in that, the flowing of above-mentioned developer solution is by forming air-flow and carry out providing on the substrate of above-mentioned developer solution.

25. the manufacture method of a semiconductor device is characterized in that, uses the described developing method of claim 1, is formed on the semiconductor substrate, exposure has the development of the photonasty resist film of circuit pattern.

26. the manufacture method of a semiconductor device is characterized in that, uses the described developing method of claim 15, is formed on the semiconductor substrate, exposure has the development of the photonasty resist film of circuit pattern.

27. the manufacture method of a semiconductor device is characterized in that, uses the described developing method of claim 20, is formed on the semiconductor substrate, exposure has the development of the photonasty resist film of circuit pattern.

28. a developer solution provides the method for cleaning of nozzle, is the method for cleaning that the developer solution that uses when developing the photonasty resist film of exposure provides nozzle, comprising:

Provide nozzle that developer solution is provided to above-mentioned developer solution;

On to substrate, provide the developer solution of developer solution to provide nozzle to provide oxidizing liquid to clean.

29. the described developer solution of claim 28 provides the method for cleaning of nozzle, it is characterized in that, as above-mentioned oxidizing liquid, comprising ozone, oxygen, carbon monoxide, and at least a aqueous solution of hydrogen peroxide offers above-mentioned developer solution nozzle is provided.

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