CN102362224A - Method for forming resist pattern, and device - Google Patents
Method for forming resist pattern, and device Download PDFInfo
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- CN102362224A CN102362224A CN2010800127958A CN201080012795A CN102362224A CN 102362224 A CN102362224 A CN 102362224A CN 2010800127958 A CN2010800127958 A CN 2010800127958A CN 201080012795 A CN201080012795 A CN 201080012795A CN 102362224 A CN102362224 A CN 102362224A
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- Prior art keywords
- resist
- resist layer
- photomask
- developer solution
- substrate
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F1/00—Originals for photomechanical production of textured or patterned surfaces, e.g., masks, photo-masks, reticles; Mask blanks or pellicles therefor; Containers specially adapted therefor; Preparation thereof
- G03F1/38—Masks having auxiliary features, e.g. special coatings or marks for alignment or testing; Preparation thereof
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F1/00—Originals for photomechanical production of textured or patterned surfaces, e.g., masks, photo-masks, reticles; Mask blanks or pellicles therefor; Containers specially adapted therefor; Preparation thereof
- G03F1/68—Preparation processes not covered by groups G03F1/20 - G03F1/50
Abstract
Disclosed is a method for forming a resist pattern, wherein the uniformity of development is improved by increasing the wettability of the surface of a resist layer when the resist pattern is formed on a device such as a photoresist. Specifically, a resist layer (93) is formed by applying a photosensitive resist over a substrate (91) (resist application step). Then, the resist layer (93) is partially irradiated with light (light exposure step). After that, a process gas for lyophilization is brought into contact with the resist layer (93) by being expelled through a discharge space (23) at near atmospheric pressure (atmospheric-pressure remote plasma lyophilization step). Then, a developer liquid (5) is brought into contact with the resist layer (93) (development step).
Description
Technical field
The equipment that the present invention relates to form the resist method of patterning and make through this method particularly is suitable for making photomask or the color filter formation method as the resist pattern of the said equipment.
Background technology
Photomask is the employed equipment of electronic component such as manufacturing integrated circuit.Because the pattern of photomask is copied on the electronic component, so whether pattern is good has very big related with the quality of electronic component.
An example to the manufacturing process of photomask describes.
The photomask (photomask forms operation) of filming on the whole on the abundant surface of washed glass substrate and to form by chromium etc.On this photomask, apply (slit coat) through spin coating (spin coat) or slit and apply photosensitive resist (resist working procedure of coating).Resist can be divided into positivity and negativity.The resist that applied is carried out preliminary drying (initial baking) afterwards, along the pattern of hope make public (exposure process).In positive corrosion-resisting agent, exposed portion decomposes and becomes solubility.In negative resist, exposed portion is polymerized to insoluble.After the exposure, according to circumstances toast once more.Afterwards, developer solution is contacted with resist, develop pattern (developing procedure).Under the situation of positive corrosion-resisting agent, use the developer solution of dissolving exposed portion.Under the situation of negative resist, use the developer solution of the resist beyond the dissolving exposed portion.Thus, the exposed portion of positive corrosion-resisting agent is removed, and the exposed portion of negative resist is by residual.Clean with washing fluid after developing, after fully removing moisture, carry out the back and dry by the fire (last baking).So far operation is called as photoetching process.After this, the photomask to the part of uncoated resist carries out etching (etching work procedure).Then, dissolving is coated with the resist of residual photomask etc. in organic solvent, to remove (resist removal operation).
Above-mentioned photoetching process also is applicable to the manufacturing of the color filter of LCD.
For equipment such as the photomask of making quality better or color filters, need the exposed portion and the non-exposed portion of clear and definite resist, to form resist pattern according to design.Therefore, exposure process and developing procedure are regarded as and are even more important.
Exposure process adopts the mode that electron beam is directly drawn pattern to the resist irradiation, or at the upside configuration pattern mask of resist, and the mode of making public from the upside irradiation ultraviolet radiation of this pattern mask.
Developing procedure is general through flooding (dip), shower (shower), revolving and cover in these three kinds of visualization way of submergence (paddle) any and carry out.
Immersion development is with being developed the visualization way that substrate is immersed in the developer solution and it is shaken.Be applicable to development operation based on the handwork at volume production initial stage more.Generally be many to be developed to be installed in after substrate gathers on the special-purpose suspension utensil carry out.
It is constantly to blow out developer solution from ejiction opening with the shower shape on one side that shower is developed, will be developed substrate and carry the visualization way of taking advantage of in roller conveyer on mode with the shower of crosscut developer solution move on one side.It in the device that carries out the robotization line production prevailing method.One then one new developer solution contacted with the resist on the surface that is developed substrate post.Therefore, developing powder is the fastest in three kinds of visualization way.In addition, the developer solution after the spraying is reclaimed, and come cycling and reutilization, thereby can reduce the consumption that each is developed the developer solution of substrate through filtration unit.
Revolving and covering dip-type developing is to be developed film that forms developer solution on the surface of substrate and the method for developing.The film of developer solution be through from the peristome of slit-shaped to the surface that the is developed substrate developer solution that drips, or form through spray vaporificly with sprayer.Revolve and cover dip-type developing, the homogeneity of just developing is best among three kinds of visualization way in this point, and the processing of the development spot during shower is developed is effective.
In patent documentation 1, record: near under the atmospheric situation oxygen containing gas is carried out plasma at pressure, and photoresist is carried out ashing (ashing).
In patent documentation 2, record; Make the gas of fluoride carry out atmosphere pressure discharging, and resist is carried out ashing.
(technical literature formerly)
(patent documentation)
Patent documentation 1:JP spy opens the 2003-163207 communique
Patent documentation 2:JP speciallys permit communique No. 2768760
(summary of invention)
(inventing technical matters to be solved)
In above-mentioned three kinds of visualization way in the developing procedure, the problem below existing respectively.
In immersion development, in developer solution, shake and be developed substrate, though to be the carrying out that develops in order promoting, to develop with shower and compare, be developed developer solution mobile poor of substrate surface.
In shower was developed, it is inhomogeneous that the shower of developer solution becomes easily, is easy to generate the development spot.Prevent owing to the configuration of the ejiction opening of shower or move situation that (head-swinging type etc.) run into developer solution to be developed substrate surface to occur biasedly though spent the time, the development spot is difficult to eliminate.
Cover in the dip-type developing revolving, developer solution can rest on the same position on the surface that is developed substrate.Therefore, resist is static with contacting of developer solution, and almost only the antistress through chemistry develops.Therefore, developing powder is slower than other visualization way.In addition and since developer solution be developed on the substrate static, therefore, the developer solution variation of finishing using and development power is reduced.The mixed volume of impurity is also a lot.Therefore, be difficult to the developer solution cycling and reutilization, need constantly use new developer solution.Therefore, each to open the consumption of the developer solution be developed substrate also many than other visualization way.Particularly if the surface of resist is concavo-convex, then need increase the thickness of developer solution, the consumption of developer solution can more increase.
Summary of the invention
(means of technical solution problem)
In order to solve above-mentioned problem, the formation method of resist pattern of the present invention is carried out successively:
The resist working procedure of coating applies photosensitive resist and forms resist layer on the substrate of equipment;
Exposure process is to said resist layer irradiates light partly;
Atmospheric pressure remote plasma lyophily chemical industry preface makes the lyophily use body of regulating the flow of vital energy spray near atmospheric discharge space through pressure and contact said resist layer; With
Developing procedure makes said resist layer contact developer solution.
Through atmospheric pressure remote plasma lyophily chemical industry preface, can carry out lyophilyization to the surface of resist layer, thereby can improve wettability.Therefore, in developing procedure after this, the developer solution of can filming equably on the surface of resist layer can develop equably.Because wettability is good, even in shower is developed, also can fully guarantee the homogeneity of developing.In immersion development,, also can fully guarantee the homogeneity of developing even be developed some variation that flows of the developer solution of substrate surface.Therefore, good resist pattern can be formed, the product of better quality can be made.In addition, because wettability is good, can reduce the consumption of developer solution.Cover in the dip-type developing revolving especially, concavo-convex even the surface of resist layer is, also need not to increase especially the thickness of developer solution, thereby can reduce the consumption of developer solution more reliably.
The said lyophily use body of regulating the flow of vital energy, the mixed gas of nitrogen or nitrogen and oxygen.The regulate the flow of vital energy oxygen amount of body of lyophily use, preferred 0～20 volume %, more preferably 0～5 volume %, further preferred 0.01～1 volume %.
Atmospheric pressure remote plasma lyophily chemical industry preface is under pressure comprises the approaching atmospheric situation of atmospheric pressure, to carry out.So-called pressure is meant 1.013 * 10 near atmospheric pressure
4Pa～50.663 * 10
4The scope of Pa is if consider the facilitation of pressure adjustment or the easy of apparatus structure, then preferred 1.333 * 10
4Pa～10.664 * 10
4Pa, more preferably 9.331 * 10
4Pa～10.397 * 10
4Pa.
And as lyophilyization (give surface moist, improve surface energy) disposal route, the ultraviolet treatment with irradiation or the electric crown that are known under oxygen (air) atmosphere are handled.But,, therefore can not be suitable for ultraviolet treatment with irradiation because resist is photosensitive.In addition, in electric crown is handled,, then can produce local arc discharge, have damage to be processed the danger of substrate metal film if being processed the metal film of filming on the substrate.
Though can consider under vacuum, to give wettability in the oxygen plasma through being exposed to; But will be processed substrate and put into vacuum plant; After plasma treatment, take out and get into next operation, can cause that operation increases, equipment cost increases and the processing time increases.
Even be the processing of atmos plasma lyophily; Also the internal configurations at the approaching atmospheric discharge space of pressure is processed substrate; Thereby under the situation that is processed the direct plasma of the isoionic atmospheric pressure of substrate direct irradiation lyophilyization; Owing to, and be difficult to adopt to photonasty resist irradiation plasma light.In addition, if being processed the metal film of filming on the substrate, then can produce discharge to this metal film, being processed substrate has the danger that is damaged.
With respect to this, the processing of atmospheric pressure remote plasma lyophily is to dispose with atmospheric discharge space to be processed substrate with being separated, and is ejected in discharge space by the processing gas of plasma to being processed substrate.Therefore; Through the position relation of adjusting discharge space with the ejiction opening of handling gas; Perhaps between discharge space and ejiction opening or at ejiction opening and be processed light-blocking member is set between the substrate; Can easily avoid running into being processed substrate, thereby the resist that can prevent to be caused by plasma light is rotten at the plasma light that discharge space produces.In addition; Even be processed the metal film of having filmed on the substrate; Also can be through regulating electrode and the distance that is processed substrate, perhaps make by the electric field shielding parts that constituted by electrical ground electric conductor between electrode and be processed between the substrate, and prevent that easily being processed substrate is damaged.
Preferably after said resist working procedure of coating and before the said exposure process; Carry out atmospheric pressure remote plasma lyophily chemical industry preface; This atmospheric pressure remote plasma ashing operation makes the ashing use body of regulating the flow of vital energy spray near atmospheric other discharge space through pressure, and contacts with said resist layer.
Atmospheric pressure remote plasma ashing operation is to comprise under the approaching atmospheric situation of atmospheric pressure at pressure, and the top layer part of resist layer is carried out light ashing (slight ashing).Time through regulating ashing or handle gas condition etc., make the layer segment that more leans on downside than the top layer of resist layer by residual.In the remote plasma ashing, the bossing of handled object is easier to contact with active podzolic gas than sunk part, and ashing speed is faster.Thus, thickness that can the homogenising resist layer, thus can make the flattening surface of resist layer.Therefore, after exposure process in, the resist part that can make public equably and should make public makes it rotten equably, thus can clearly distinguish the rotten resist part of this quilt with not by the resist part that goes bad.Therefore, in developing procedure, can clearly distinguish resist part and the residual resist part removed through developer solution.Consequently, can form better resist pattern.And, can further reduce the consumption that each is processed the developer solution of substrate.Cover in the dip-type developing revolving especially, the thickness of the developer solution that can more reduce to launch on the resist layer can reduce the consumption of developer solution reliably.
The said ashing use body of regulating the flow of vital energy, the mixed gas of nitrogen or nitrogen and oxygen.The regulate the flow of vital energy oxygen amount of body of ashing use, preferred 0～20 volume %, more preferably 0～10 volume %, further preferred 0.01～5 volume %.
And it is difficult through vacuum plasma resist being carried out light ashing.This is because if the resist of preliminary drying state is dropped into vacuum plant, and vacuumizes, the solvent evaporates in the resist then, and the composition of resist can go bad.
Because resist is photosensitive, therefore can not carry out light ashing through ultraviolet asher.So-called ultraviolet asher is indoor in the ashing that has imported gases such as ozone, under ultraviolet irradiation, utilizes the chemical reaction of gas and resist to peel off the light stimulus cineration device of resist.
Even be the atmos plasma ashing treatment; Also the internal configurations at the approaching atmospheric discharge space of pressure is processed substrate; Thereby under the situation that is processed the direct plasma ashing of the isoionic atmospheric pressure of substrate direct irradiation; Owing to, and be difficult to adopt to photonasty resist irradiation plasma light.In addition, if being processed the metal film of filming on the substrate, then can produce discharge to this metal film, being processed substrate has the danger that is damaged.
With respect to this, atmospheric pressure remote plasma ashing treatment is to dispose near atmospheric discharge space with pressure to be processed substrate with being separated, and is ejected in discharge space by the processing gas of plasma to being processed substrate.Therefore; Through the position relation of adjusting discharge space with the ejiction opening of handling gas; Perhaps between discharge space and ejiction opening or at ejiction opening and be processed light-blocking member is set between the substrate; Can easily avoid running into being processed substrate, thereby the resist that can prevent to be caused by plasma light is rotten at the plasma light that discharge space produces.In addition; Even be processed the metal film of filming on the substrate; Also can be through regulating electrode and be processed the distance of substrate, or make by the electric field shielding parts that constituted by electrical ground electric conductor between electrode and be processed between the substrate, easily prevent to be processed substrate and be damaged.
Equipment of the present invention is to utilize the formation method of above-mentioned resist pattern to make.As equipment, for example, can enumerate photoresist or color filter.Through the formation method of resist pattern of the present invention being applied to the manufacturing of photoresist, can access photoresist with good copying pattern.Through using this photoresist, can make the electronic element products of fine quality.Through the formation method of resist pattern of the present invention being applied to the manufacturing of color filter, can access the color filter that has good matrix pattern and then have good RGB pattern.
According to the present invention, can improve wettability to the surperficial lyophilyization of resist layer.Can also developer solution be filmed on the surface of resist layer equably on this basis through developing, can develop equably.Thus, can form the resist pattern of fine quality.In addition, can reduce the consumption of developer solution.
Description of drawings
Fig. 1 representes the manufacturing process of the photomask (equipment) of an embodiment of the present invention, after resist working procedure of coating and preliminary drying operation, and the cut-open view of the photomask negative before the atmospheric pressure remote plasma ashing operation.
Fig. 2 is the front section view that illustrative is represented the atmospheric pressure remote plasma ashing operation in the manufacturing process of above-mentioned photomask.
Fig. 3 is the front section view that illustrative is represented the exposure process in the manufacturing process of above-mentioned photomask.
Fig. 4 is the front property cut-open view that illustrative is represented the atmospheric pressure remote plasma lyophily chemical industry preface in the manufacturing process of above-mentioned photomask.
Fig. 5 is the front section view that illustrative is represented the developing procedure in the manufacturing process of above-mentioned photomask.
Fig. 6 is the front section view that illustrative is represented the photomask etching work procedure in the manufacturing process of above-mentioned photomask.
Fig. 7 is the cut-open view of above-mentioned photomask.
Embodiment
Below, an embodiment of the present invention is described.
As shown in Figure 7, the equipment that becomes manufacturing object in this embodiment is photomask 9.Photomask 9 has glass substrate 91.Surface coating at glass substrate 91 has photomask 92.On photomask 92, be formed with the pattern 92a of regulation.
Manufacturing approach to photomask 9 describes.
[cleaning operation]
At first, clean the surface of glass substrate 91, wash the organism or the lipid on the surface of substrate 91 off.Thus, can guarantee the tack of photomask 92 or resist 93.
[photomask formation operation]
Then, as shown in Figure 1, the photomask 92 of on whole of glass substrate 91, filming forms photomask negative 90.The composition of photomask 92 for example is metals such as chromium.As coating method, for example be suitable for the splash method.
[resist working procedure of coating]
Then, on photomask 92, apply the resist that forms by aqueous photoresist, and form resist layer 93.In this embodiment, though used positive corrosion-resisting agent, also can use negative resist.The thickness of resist layer 93 is about number μ m～100 μ m.As coating machine, can use spin coating, also can use the slit to apply.If apply resist through spin coating, then the thickness of the peripheral part of photomask negative 90 is compared with the thickness of the resist of the inside portion of photomask negative 90, easily thickening.If apply through the slit, the thickness that then applies the resist of beginning part is compared with other part, easily thickening.Therefore, like expression turgidly in Fig. 1, the surface of resist layer 93 (upper surface) becomes concavo-convex easily.
[preliminary drying operation]
Then, baking photomask negative 90 solidifies resist layer 93.
[atmospheric pressure remote plasma ashing operation]
Then, as shown in Figure 2, photomask negative 90 is imported atmospheric pressure remote plasma cineration device 1.Atmospheric pressure remote plasma cineration device 1 has handles 10.Be provided with pair of electrodes 11,11 opposed to each other handling in 10.Opposed faces at each electrode 11 is formed with solid dielectric layer (omitting diagram).An electrode 11 is connected with power supply 12.Another electrode 11 electrical ground.Voltage through from power supply 12 is supplied with, and the space that electrode is 11,11 becomes pressure near atmospheric discharge space 13.The waveform of the service voltage of power supply 12 can be that pulsating wave also can be a continuous wave.
The ashing use body supply source 14 of regulating the flow of vital energy links to each other with the upper reaches end of discharge space 13.As the ashing use of supply source 14 body of regulating the flow of vital energy, the pure gas of nitrogen or the mixed gas of nitrogen and oxygen have been adopted.Handle preferred 0～20 volume % of oxygen concentration in the gas, more preferably 0～10 volume %, further preferred 0.01～5 volume %.
With this ashing use body (N that regulates the flow of vital energy
2+ O
2) import discharge space 13 and carry out plasma.From ejiction opening 15 ejections of handling a bottom of 10 by the processing gas of plasma.Handle 10 below dispose photomask negative 90 with being separated.To this photomask negative 90, it is above-mentioned by the ashing use of the plasma body of regulating the flow of vital energy to jet.Thus, shown in the dummy line of Fig. 2, the top layer part 93e of resist layer 93 is carried out light ashing.Time through regulating ashing or handle gas condition etc., thus make the resist layer 93 that more leans on downside than top layer part 93e by residual.Usually, in remote plasma irradiation, the bossing of handled object is compared with the concave portion of this handled object, more near handling 10, can contact with more highly active podzolic gas, and ashing speed can be faster.Therefore, the protruding part on the surface of resist layer 93 is removed by ashing earlier than the recessed part on the surface of this resist layer 93.Thus, can make the thickness of resist layer 93 even, surface that can planarization resist layer 93.Therefore, in above-mentioned resist working procedure of coating, do not need strictly to require the homogeneity that applies.
With the ashing use regulate the flow of vital energy body winding-up concurrently, through travel mechanism 17 photomask negative about 90 is come and gone and moves.Also can stationary photomask negative 90, make and handle 10 and come and go and move.The speed and the number of times that come and go to move according to the kind of resist and want the thickness of ashing suitably to set, preferably are set at resist the degree of light ashing.Particularly, the preferred 0.2～10m/min of translational speed, more preferably 0.5～2m/min.Mobile number of times be with the one way of going Cheng Fangxiang or backhaul direction as once, preferred about 5～50 times.
And, can heat photomask negative 90 with suitable temperature through heating part 18.
Owing to photomask negative 90 is arranged, therefore, can be easy to prevent that photomask 92 from being shone by plasma and be damaged in the exterior arrangement of discharge space 13.In addition; Through regulating the configuration relation of discharge space 13 and ejiction opening 15; Perhaps through between discharge space 13 and the ejiction opening 15 or between ejiction opening 15 and photomask negative 90 light-blocking member (not shown) being set, the plasma light that can be easy to avoid in discharge space 13, producing is run into photomask negative 90.Thus, can prevent that resist layer 93 from being gone bad by what plasma light caused.
Preferably electric field shielding parts 16 are set in a bottom of handling 10.Electric field shielding parts 16 are to be made up of metal, and electrical ground.The electric field that electric field shielding parts 16 shield from the electrode 11 that is connected with power supply 12, and then prevent to fall arc discharge from electrode 11 to photomask 92.Thus, can prevent that photomask negative 90 from receiving electric field and damaging.
Handle 10 with photomask negative 90 between distance W D, though more little effective more, occur at photomask negative 90 under the situation of bending etc., also be set at not the size of the degree that contacts with processing 10.Usually, distance W D preferably is made as WD=0.3～10mm, more preferably is made as 0.5～3mm.
[exposure process]
Then, as shown in Figure 4, by 3 pairs of photomask negatives of electron beam illuminating device, 90 irradiating electron beam 3a, and the point of irradiation of electron beam 3a is relatively moved with respect to photomask negative 90 with the mode of describing desirable pattern.Thus, can carry out partial exposure to resist layer 93.Because the surface of resist layer 93 is by abundant planarization, therefore, the resist part 93a that should make public among the resist layer 93 that can make public equably, thus rotten equably.Therefore, can clearly distinguish through this exposure and rotten resist part 93a and unexposed unmetamorphosed resist part 93b.
Also can replace directly describing pattern at the upside configuration pattern mask of photomask negative 90 through electron beam 3a, and ultraviolet through the pattern hole of pattern mask 3 to resist layer 93 local irradiations.As ultraviolet ray, mainly adopt the g line of 436nm or the i line of 365nm.Kind according to resist can be selected any ultraviolet ray.The ultraviolet time shutter is normally about several seconds～30 second.
[PEB (Post Exposure Bake: operation post exposure bake)]
Photomask negative 90 to after the exposure toasts.This operation most cases can be omitted.
[atmospheric pressure remote plasma lyophily chemical industry preface]
Then, as shown in Figure 4, photomask negative 90 is imported the makeup of atmospheric pressure remote plasma lyophily put 2.Atmospheric pressure remote plasma lyophily makeup is put 2 and is had and handle 20.Be provided with pair of electrodes 21,21 opposed to each other handling in 20.On the opposed faces of each electrode 21, be formed with solid dielectric layer (omitting diagram).An electrode 21 is connected with power supply 22.Another electrode 21 electrical ground.Voltage through from power supply 22 is supplied with, and electrode 21, the space between 21 become pressure near atmospheric second discharge space 23.The waveform of the service voltage of power supply 22 both can be a pulsating wave, also can be continuous wave.
The lyophily use body supply source 24 of regulating the flow of vital energy links to each other with the upper reaches end of discharge space 23.As the lyophily use of supply source 24 body of regulating the flow of vital energy, the pure gas of nitrogen or the mixed gas of oxygen and nitrogen have been adopted.Handle the oxygen concentration in the gas, preferred 0～20 volume %, more preferably 0～5 volume %, further preferred 0.01～1 volume %.
With this ashing use body (N that regulates the flow of vital energy
2+ O
2) import discharge space 23 and carry out plasma.From ejiction opening 25 ejections of handling a bottom of 20 by the processing gas of plasma.Handle 20 below dispose photomask negative 90 with being separated.Above-mentioned to these photomask negative 90 winding-ups by the processing gas of plasma.Thus, the surface energy of resist layer 93 is improved, can carry out lyophilyization to the surface of resist layer 93, thereby increase wettability for developer solution.
Handle gas concurrently with winding-up, photomask negative 90 is moved up at right and left through travel mechanism 27.Also can stationary photomask negative 90, make and handle 20 and move.The speed and the number of times that move though can suitably set, move on the one way direction usually and once get final product.
Owing to photomask negative 90 is arranged, therefore, can be easy to prevent that photomask 92 from being shone by plasma and be damaged in the exterior arrangement of discharge space 23.In addition; Through regulating the configuration relation of discharge space 23 and ejiction opening 25; Perhaps through between discharge space 23 and the ejiction opening 25 or between ejiction opening 25 and photomask negative 90 light-blocking member (not shown) being set, the plasma light that can be easy to avoid in discharge space 23, producing is run into photomask negative 90.Thus, can prevent that resist layer 93 from causing rotten by plasma light.
Preferably electric field shielding parts 26 are set in a bottom of handling 20.Electric field shielding parts 26 are to be made up of metal, and electrical ground.The electric field that electric field shielding parts 26 shield from the electrode 21 that is connected with power supply 22, and then prevent to fall arc discharge from electrode 21 to photomask 92.Thus, can prevent that photomask negative 90 from receiving electric field and damaging.
[developing procedure]
Then, as shown in Figure 5, developer solution 5 is contacted with photomask negative 90.Because the atmospheric pressure remote plasma through preceding operation is handled, therefore the surface that makes resist layer 93, can be made developer solution 5 contact the surface of resist layer 93 fast and equably by hydrophiling.Thus, positive type resist layer 93 by light-struck rotten part 93a dissolved removal in developer solution 5, only residual down not by light-struck non-rotten part 93b.And, when using negative resist, be not removed by light-struck non-rotten part, and residual down by light-struck rotten part.Owing to clearly distinguish rotten part 93a and non-rotten part 93b, therefore can access desirable resist pattern.
Visualization way can be an immersion development, can be that shower is developed, and also can be to revolve to cover dip-type developing.Because the screening characteristics of developer solution 5 is good, therefore not only cover in the dip-type developing revolving, even in shower is developed, also can prevent the spot that develops, develop full and uniformly.In immersion development, even, also can fully guarantee the homogeneity of developing in how many variation that flow of the developer solution on the surface of photomask negative 90.And, made the flattening surface of resist layer 93 through the atmospheric pressure remote plasma ashing operation before making public, therefore, can make developer solution 5 reliably contact the surfaces of resist layer 93 equably, can further improve the homogeneity of development.And, can reduce the consumption of the developer solution 5 that is equivalent to a photomask negative 90.Cover in the dip-type developing revolving especially, can reduce to be covered in the thickness of the developer solution 5 on the resist layer 93, thereby can reduce the consumption of developer solution.And, even the surface of resist layer 93 hypothesis is concavo-convex, also can be owing to wettability is good, and cover the thickness that need not to increase especially developer solution 5 in the dip-type developing revolving, thus can reduce the consumption of developer solution reliably.
[rinsing process]
Clean with rinsing liquid after developing.Rinsing liquid can be a pure water.
[back baking operation]
Then, on the basis of having removed the moisture that in developing procedure and rinsing process, adheres to fully, also carry out final back baking, residual resist is solidified.
From cleaning the operation of operation, be called as photoetching process to the back baking.
[photomask etching work procedure]
Then, as shown in Figure 6, the photomask 92 of the part that does not cover resist layer 93 is carried out etching.Residual by the photomask 92 of the part of resist layer 93 coverings.
[resist removal operation]
Then, as shown in Figure 7, dissolve resist layer 93 grades that covered residual photomask 92 and remove with organic solvent.Thus, photomask 92 is made public.Owing in developing procedure, obtained the resist pattern of hoping,, also can access desirable pattern 92a to photomask 92.Thus, can form the photomask 9 of better quality.
The present invention is not limited to above-mentioned embodiment, in the scope of its aim, can adopt variety of way.
For example, also can an atmospheric pressure remote plasma treating apparatus also be also used as the makeup of atmospheric pressure remote plasma cineration device 1 and atmospheric pressure remote plasma lyophily and put 2.
The concrete steps of each operation can suitably change, and clean operation, roasting procedure etc. and can suitably omit.
The present invention is not limited to the manufacturing of photomask, also can be applicable to the manufacturing based on photolithographic miscellaneous equipment of color filter etc.
(embodiment 1)
Embodiment is described.Self-evident, the present invention is not limited to this embodiment.
On whole of glass substrate 91, apply positive corrosion-resisting agent through the slit, and carry out preliminary drying.The size of glass substrate is 510mm * 610mm.The initial average thickness of resist layer 93 is 500nm.As resist, adopted the ZEP520 of Japanese ゼ オ Application commercial firm system.The temperature of preliminary drying is made as 150 ℃.
Use and Fig. 2 or atmospheric pressure remote plasma treating apparatus 1,2 shown in Figure 4 be the device of same configuration in fact, above-mentioned sample has been implemented the atmospheric pressure remote plasma handled.As handling gas, adopted the mixed gas of nitrogen 600L/min and oxygen 0.15L/min.Be made as 3kW from the input power of 12 pairs of electrodes 11 of power supply.Transmission speed based on travel mechanism 17 is made as 1.2m/min.Move number of times (number of processes), move as once being made as 20 times with one way, handle 10 and the distance of sample be made as WD=1mm.Treatment temperature is made as room temperature, heats.
Afterwards, carry out developing procedure, rinsing process and back baking operation successively.The visualization way of developing procedure is made as immersion development.Use ZED-50N (Japanese ゼ オ Application commercial firm system) as developer solution.The dip time of developer solution is made as 90sec.Use the rinsing liquid of pure water as rinsing process.The temperature of back baking is made as 150 ℃.
Then, measure the thickness of resist layer 93, the reduction (initial average thickness-mensuration thickness) of thickness is estimated.Mensuration be with the Width of the transmission direction quadrature on the surface of resist layer 93 on 60mm at interval, and in transmission direction 65mm at interval, amount to that 99 places carry out.In addition, measured behind the preliminary drying resist layer 93 after (atmospheric pressure remote plasma handle before) and atmospheric pressure remote plasma are handled the surface to water contact angle.
As comparative example, except omitting the atmospheric pressure remote plasma handles,, and implement 1 and carried out the reduction evaluation of resist thickness and identically the mensuration of water contact angle to the sample of under the condition identical, having implemented the same treatment operation with embodiment 1.
Below table 1 and table 2 ecbatic
[table 1]
The film reduction
| Maximal value | Minimum value | Mean value | Maximum-minimum | Standard deviation | |
| Embodiment 1 | 399.3nm | 319.7nm | 374.0nm | 79.6nm | 20.2 |
| Comparative example | 271.3nm | 56.8nm | 215.1nm | 214.5nm | 34.8 |
[table 2]
To water contact angle
Visible from table 1, confirm: handle through carrying out the atmospheric pressure remote plasma, can make the flattening surface of resist layer.
Visible from table 2, handle through carrying out the atmospheric pressure remote plasma, can significantly improve the water wettability of resist layer.Therefore, confirm: in developing procedure after this, can make developer solution contact the surface of resist layer fast and equably, can develop equably.
(utilizability on the industry)
The present invention for example can be applied to the manufacturing of photomask.
The explanation of symbol:
1-atmospheric pressure remote plasma cineration device,
10-handles head,
The 11-electrode,
The 12-power supply,
Other discharge space of 13-,
The 14-ashing use body supply source of regulating the flow of vital energy,
The 15-ejiction opening,
16-electric field shielding parts,
17-travel mechanism,
The 18-heating part,
The makeup of 2-atmospheric pressure remote plasma lyophily is put,
20-handles head,
The 21-electrode,
The 22-power supply,
The 23-discharge space,
The 24-lyophily use body supply source of regulating the flow of vital energy,
The 25-ejiction opening,
26-electric field shielding parts,
27-travel mechanism,
3-electron beam irradiating machine,
The 3a-electron beam,
The 5-developer solution,
9-photomask (equipment),
90-photomask negative (object being treated),
The 91-glass substrate,
The 92-photomask,
The 92a-pattern,
The 93-resist,
The 93a-part that goes bad,
The non-rotten part of 93b-,
93e-ashing removal portion.
Claims (3)
1. the formation method of a resist pattern is characterized in that, carries out successively:
The resist working procedure of coating applies photosensitive resist and forms resist layer on the substrate of equipment;
Exposure process is to said resist layer irradiates light partly;
Atmospheric pressure remote plasma lyophily chemical industry preface makes the lyophily use body of regulating the flow of vital energy spray near atmospheric discharge space through pressure and contact said resist layer; With
Developing procedure makes said resist layer contact developer solution.
2. the formation method of resist pattern according to claim 1 is characterized in that,
The said lyophily use body of regulating the flow of vital energy is the mixed gas of nitrogen or oxygen and nitrogen, and the oxygen amount is 0～20 volume %.
3. an equipment is characterized in that,
Be to utilize the formation method of claim 1 or 2 described resist patterns to make.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2009-094297 | 2009-04-08 | ||
| JP2009094297A JP4681662B2 (en) | 2009-04-08 | 2009-04-08 | Method for forming resist pattern |
| PCT/JP2010/002139 WO2010116647A1 (en) | 2009-04-08 | 2010-03-25 | Method for forming resist pattern, and device |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102362224A true CN102362224A (en) | 2012-02-22 |
Family
ID=42935948
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010800127958A Pending CN102362224A (en) | 2009-04-08 | 2010-03-25 | Method for forming resist pattern, and device |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP4681662B2 (en) |
| CN (1) | CN102362224A (en) |
| WO (1) | WO2010116647A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104199256A (en) * | 2014-09-25 | 2014-12-10 | 上海和辉光电有限公司 | Method, device and preliminary drying device for producing photoresist patterns |
| CN104570626A (en) * | 2013-10-28 | 2015-04-29 | 中芯国际集成电路制造(上海)有限公司 | Method for improving uniformity of critical sizes and defect rate of pinholes |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6089667B2 (en) * | 2012-12-13 | 2017-03-08 | 大日本印刷株式会社 | Photomask blanks manufacturing method with resist, and photomask manufacturing method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09246166A (en) * | 1996-03-13 | 1997-09-19 | Nittetsu Semiconductor Kk | Developing method for photoresist |
| JPH10153867A (en) * | 1996-11-25 | 1998-06-09 | Hitachi Ltd | Pattern forming method and device, production of semiconductor integrated circuit and production of photomask |
| JP2003163207A (en) * | 2001-11-29 | 2003-06-06 | Sekisui Chem Co Ltd | Removing treatment method for remaining photo-resist |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2768760B2 (en) * | 1989-10-19 | 1998-06-25 | 株式会社東芝 | Resist ashing device |
| JP2007027187A (en) * | 2005-07-12 | 2007-02-01 | Sharp Corp | Plasma treatment apparatus and plasma treatment method using the same |
-
2009
- 2009-04-08 JP JP2009094297A patent/JP4681662B2/en not_active Expired - Fee Related
-
2010
- 2010-03-25 CN CN2010800127958A patent/CN102362224A/en active Pending
- 2010-03-25 WO PCT/JP2010/002139 patent/WO2010116647A1/en active Application Filing
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09246166A (en) * | 1996-03-13 | 1997-09-19 | Nittetsu Semiconductor Kk | Developing method for photoresist |
| JPH10153867A (en) * | 1996-11-25 | 1998-06-09 | Hitachi Ltd | Pattern forming method and device, production of semiconductor integrated circuit and production of photomask |
| JP2003163207A (en) * | 2001-11-29 | 2003-06-06 | Sekisui Chem Co Ltd | Removing treatment method for remaining photo-resist |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104570626A (en) * | 2013-10-28 | 2015-04-29 | 中芯国际集成电路制造(上海)有限公司 | Method for improving uniformity of critical sizes and defect rate of pinholes |
| CN104199256A (en) * | 2014-09-25 | 2014-12-10 | 上海和辉光电有限公司 | Method, device and preliminary drying device for producing photoresist patterns |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2010243918A (en) | 2010-10-28 |
| JP4681662B2 (en) | 2011-05-11 |
| WO2010116647A1 (en) | 2010-10-14 |
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Application publication date: 20120222 |