CN101738854A - Pattern forming method - Google Patents
Pattern forming method Download PDFInfo
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- CN101738854A CN101738854A CN200910209666A CN200910209666A CN101738854A CN 101738854 A CN101738854 A CN 101738854A CN 200910209666 A CN200910209666 A CN 200910209666A CN 200910209666 A CN200910209666 A CN 200910209666A CN 101738854 A CN101738854 A CN 101738854A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
- H01L21/0271—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers
- H01L21/0272—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers for lift-off processes
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
- G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
- G03F7/095—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having more than one photosensitive layer
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- Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)
Abstract
The present invention relates to a pattern forming method for a display element, which is used for forming an undercut shape profile applicable to a lift-off process. The present invention increases the speed of light sensing by using a polymeric compound having a specific structure, and can easily form an undercut shape profile when forming a multi-layered photoresist layer, thereby being easily applicable to a lift-off process. In addition, a pattern with a large thickness can be formed, and an etching process in the process can be omitted, so that the process can be simplified.
Description
Technical field
The present invention relates to a kind of pattern formation method that is used for element, particularly a kind of pattern formation method that can realize that operation is oversimplified.Described method is after forming the different multilevel resist of film speed, utilize the film speed difference to form undercutting shape profile, and then remove multilevel resist by peeling off (lift-off) operation, even thereby still can form fine pattern under the big situation of thickness, and do not need to carry out etching work procedure and only just can carry out the metal evaporation process by the wet developing operation.
Background technology
Utilize in the existing method of multilayer polymeric and disclose following scheme: ground floor is used as special macromolecule layer, polymethylmethacrylate (PMMA) layer for example, and the second layer used as general photoresist layer.Yet, because the macromolecule layer of ground floor does not have exposure characteristics in the described method, therefore if there is the difficulty that need come adjustment profile by developer solution kind, concentration and development time in this method of use.
And, because described ground floor does not have reaction to light, and only form pattern, so this point can become the factors of instability by developer solution.
And, usually the novolac resin (novolak resin) that comprises about 15-30 weight % in the photoetching compositions, in the organic solvent that the macromolecule that is comprised in existing first photoresist layer can be dissolved into wherein to be comprised, thereby cause the internal mix of first photoresist layer and second photoresist layer when forming second photoresist layer.Owing to this reason, the film speed of the film speed of first photoresist layer and second photoresist layer can be mixed mutually, so each photoresist layer can not have separately film speed and physical property.Therefore, first photoresist layer can disappear or the obvious attenuation of its thickness meeting, thereby can not obtain desirable film speed, can not stably obtain desirable pattern contour thus.
Thereby in order to address this is that, existing method forms dielectric film or metal film etc. usually between the photoresist layer of the ground floor and the second layer when forming multilayer polymeric.Form described dielectric film or metal film etc. between the photoresist layer, this is because when coating second photoresist layer, in the organic solvents that first photoresist layer can be dissolved in second photoresist to be contained etc., therefore first photoresist layer can disappear or attenuation, can not give full play to its effect.Yet, with regard to this method, owing to need to increase the forming process of dielectric film or metal film, more complicated thereby operation can become.
And, also disclose the profile that forms the back taper shape in the prior art and afterwards it has been peeled away, form the pattern formation method of pattern with this.
For example, form the photoresist method of patterning of back taper by figure counter-rotating technology with the eurymeric photoresist.Yet, described figure counter-rotating technological operation complexity, temperature allowed range is little, thereby is difficult to obtain good photoresist pattern.
In addition, also disclose a kind of use negative photoresist composition in the prior art and formed the back taper method of patterning.Though use the negative photoresist composition can form the back taper pattern that is suitable for stripping process, there is the shortcoming of thermotolerance, elching resistant difference in it.
Korean Patent discloses 2005-0083314 number and discloses the photoetching compositions that is used to form eurymeric back taper pattern.Though described method can form suitable back taper pattern, and is applicable to stripping process, this method exists exposure must reach 1.5 times the shortcoming of Eop (forming the required optimum exposure of pattern under single exposure).
Technology contents
In view of above-mentioned problems of the prior art, the invention provides a kind of eurymeric photoetching compositions that utilizes the scalable film speed, can stably form the pattern formation method of the undercutting shape profile that is suitable for special procedures such as stripping process.
For achieving the above object, pattern formation method provided by the invention may further comprise the steps:
(a) on substrate, form first photoresist layer;
(b) on described first photoresist layer, form second photoresist layer; And
(c) described first photoresist layer and second photoresist layer are exposed, develop, thereby form the photoresist pattern of undercutting shape,
Described first photoresist layer is by being formed by the represented compound of following Chemical formula 1, and the film speed of described second photoresist layer is slower than the film speed of first photoresist layer,
[Chemical formula 1]
In the described Chemical formula 1, R
1To R
3Represent independently that respectively hydrogen or carbon number are 1 to 10 alkyl, n represents 10 to 1000 integer.
And after step (c) finished, described pattern formation method can also may further comprise the steps: (d) evaporation metal on described photoresist pattern; And (f) from the photoresist pattern of the described metal of evaporation, peel off first photoresist layer and second photoresist layer by stripping process.
Describe the present invention below in detail.
The present invention makes the film speed of first photoresist layer and the film speed of second photoresist layer that certain difference be arranged, thereby can form the pattern of undercutting (undercut) shape when utilizing the multilevel resist layer to form pattern.That is, the present invention is different from the film speed of second photoresist layer for the film speed that makes first photoresist layer, and the component of employed photoetching compositions cooperates differently when forming each layer.Therefore, the film speed of second photoresist layer is slower than the film speed of first photoresist layer, thereby by described two layers are exposed, develop, makes the photoresist pattern become the profile of undercutting shape.And the present invention removes two-layer photoresist layer by stripping process from the pattern of undercutting shape, thereby can form the display device pattern easily.
, the invention is characterized in for this reason, when forming multiple layer polymer in the employed photoetching compositions, at first be formed at the compound that first photoresist layer on the substrate uses following particular chemical formula 1.
[Chemical formula 1]
In the described Chemical formula 1, R
1To R
3Represent independently that respectively hydrogen or carbon number are 1 to 10 alkyl, n represents 10 to 1000 integer.
The weight-average molecular weight of the compound of described Chemical formula 1 preferably 8,000 to 15,000.
With regard to the compound of described Chemical formula 1, the position of hydrogen is replaced by specific phenolic group in the general phenolic structure, thereby has structurally improved thermotolerance, solvent resistance.Therefore, when applying second photoresist layer, at the solvent that is contained in second photoresist layer, this compound has certain patience, thereby can not be dissolved in the solvent.
The present invention is owing to used compound shown in the described Chemical formula 1, so when on first photoresist layer, applying second photoresist layer, first photoresist layer can not be dissolved in the solvent of second photoresist layer, even it is dissolved, dissolve also seldom, just can carry out subsequent step thereby need not to increase in addition other operation.And first photoresist layer is different with existing photoresist layer, has exposure characteristics, thereby can form stable pattern.Therefore, the present invention does not need as prior art, forms general dielectric film or metal film etc. between first photoresist layer and second photoresist layer, and has omitted this section operation, thereby can realize the simplification of operation.
At this moment, described " stripping process " is meant following method: in order to form certain pattern, on whole surface, form the material layer that comprises the photoresist pattern that forms as the etching mask use, remove described photoresist pattern from substrate then, at this moment, the material layer that forms on the top of described photoresist pattern can be removed in the lump, forms predetermined pattern with this.
Below, the preferred embodiment of pattern formation method that present invention will be described in detail with reference to the accompanying.
Pattern formation method of the present invention may further comprise the steps: (a) form first photoresist layer by compound shown in the described Chemical formula 1 on substrate; (b) on described first photoresist layer, form second photoresist layer; And (c) described first photoresist layer and second photoresist layer are exposed, develop, thereby form the photoresist pattern of undercutting shape.
And, owing to carry out stripping process in LCD and the semiconducter engineering, therefore preferably include stripping process, form the back deposited metal film at the photoresist pattern, and then stripping photoresist.Therefore, pattern formation method of the present invention can also may further comprise the steps after the described step of end (c): (d) evaporation metal on described photoresist pattern; And (f) there is the photoresist pattern of described metal to peel off first photoresist layer and second photoresist layer from evaporation by stripping process.Fig. 1 a to Fig. 1 f shows the synoptic diagram of the pattern formation method that one embodiment of the invention relate in regular turn.
As shown in Figure 1a, step (a) is to apply eurymeric first photoetching compositions and carry out precuring (Primarily Curing) on substrate 10, thereby forms the process of first photoresist layer 20.
At this moment, described eurymeric first photoetching compositions comprises compound shown in the described Chemical formula 1, compound shown in the described Chemical formula 1 has the film speed effect faster than second photoresist layer that makes first photoresist layer, and makes first photoresist layer have patience at the organic solvent of second photoresist layer.Promptly, compound is included in the composition shown in the described Chemical formula 1, so improved the patience of first photoresist layer, thereby can obtain the profile of undercutting shape the organic solvent that contained in second photoresist layer, even and thickness greatly still can form fine pattern.In addition, the present invention can form the photoresist pattern with undercutting shape, thereby does not need extra etching work procedure, only carry out after the wet type operation, at once just the metal evaporation operation can be carried out,, and the effect that reduces cost can be reached so operation becomes simply.
In sum, most important factor is in first photoresist layer, and compound not only has sensitometric characteristic shown in the described Chemical formula 1, and solvent resistance is very outstanding, thereby when forming second photoresist layer, the internal mix that is caused by the solvent that contains in described second photoresist layer can not take place.
At this moment, except compound shown in the described Chemical formula 1, described first photoetching compositions also comprises photosensitive material and the organic solvent that contains diazide class Photoactive compounds (diazide-type photosensitivecompound).
In order to reach suitable film speed and apply photoresist on substrate, the content of compound shown in the described Chemical formula 1 preferably accounts for the 10-30 weight % of whole compositions.
Described diazide class Photoactive compounds preferably accounts for the 2-10 weight % of whole compositions.If the content of described diazide class Photoactive compounds is lower than 2 weight %, then can not form stable pattern contour, if be higher than 10 weight %, then the storage stability of photoresist can descend.Described diazide class Photoactive compounds can be with polyhydroxy benzophenone (Polyhydroxybenzophenone), 1,2-naphtho-quinone diazide (1,2-naphthoquinone diazide) and 2-diazonium-1-naphthol-5-sulfonic acid compounds such as (2-diazo-1-naphthol-5-sulfonic acid) react and prepare.For example, described diazide class Photoactive compounds can be trihydroxybenzophenone (trihydroxybenzophenone) and 2-diazonium-1-naphthol-5-sulfonic acid are carried out esterification and prepare 2,3,4-trihydroxybenzophenone-1,2-naphtho-quinone diazide-5-sulfonate (2,3,4-trihydroxybenzophenone-1,2-naphthoquinone diazide-5-sulfonate); Perhaps tetrahydroxybenzophenone (tetrahidroxybenzophenone) and 2-diazonium-1-naphthol-5-sulfonic acid are carried out esterification and prepare 2,3,4,4 '-tetrahydroxybenzophenone-1,2-naphtho-quinone diazide-5-sulfonate, and they can be used alone or as a mixture.The blending ratio of described diazide class Photoactive compounds preferably, 2,3,4-trihydroxybenzophenone-1,2-naphtho-quinone diazide-5-sulfonate accounts for 40-60 weight portion, 2,3,4,4 '-tetrahydroxybenzophenone-1,2-naphtho-quinone diazide-5-sulfonate accounts for the 60-40 weight portion.
Described organic solvent preferably uses 60-80 weight % all existing with surplus in the composition.Described organic solvent can use and be selected from propylene glycol methyl ether acetate (PGMEA, propylene glycol methyl ether acetate), ethyl lactate (EL, Ethyllactate), ethylene glycol monomethyl ether acetate (MMP, 2-Methoxyethyl acetate), propylene glycol monomethyl ether (PGME, Propylene Glycol Monomethyl Ether), methyl ethyl ketone (MEK, methylethylketone), methyl isobutyl ketone (MIBK, methyl isobutyl ketone), and 1-Methyl-2-Pyrrolidone (NMP, 1-Methyl-2-pyrrolidinone) more than one compounds in.
In addition, as required, first photoetching compositions of the present invention can also improve performance by further adding adjuvant.Described adjuvant be selected from photosensitive accelerant, colorant, dyestuff, anti-scratch agent (anti-striation agent), plastifier, tackifier, and surfactant in more than one.
The film speed of this first photoetching compositions of the present invention can be in the scope of 5mJ to 100mJ.But with regard to the difference of film speed, the film speed of second photoresist layer is fast as long as the film speed of first photoresist layer compares, and can realize exactly, so its scope might not be limited in the described scope.
And according to use and technology type, the thickness range of photoresist layer can be very extensive, and the thickness of first photoresist layer is 200-1500nm preferably.
In addition, precuring can be carried out 60-120 second under 90-110 ℃ of temperature.
Described substrate can use common glass substrate or plastic base, can evaporation above it be selected from the material in silicon, aluminium, indium tin oxide (ITO), indium zinc oxide (IZO), molybdenum, silicon dioxide, doped silica, silicon nitride, tantalum, copper, polysilicon, pottery, aluminium/copper mixture and the polymerizing resin (polymerizable resin).
Then, in step (b), on first photoresist layer 20, apply second photoetching compositions, and form second photoresist layer 30 (Fig. 1 b) by precuring.
Described second photoetching compositions can comprise alkali soluble resins--novolac resin, comprise the photosensitive material and the organic solvent of diazide class Photoactive compounds.
Described novolac resin can comprise all novolac resins except that compound shown in the described Chemical formula 1, normally used.For example, by the separately synthetic novolac resin of metacresol (meta cresol), by the synthetic separately novolac resin of paracresol, use the novolac resin of resorcinol (resorcinol), salicylide (salicylic aldehyde) and benzaldehyde (benzyl aldehyde) reacted and the novolac resin for preparing etc.Described novolac resin can use the novolac resin that common phenolic compounds and aldehyde compound is carried out condensation reaction and prepare under the acid catalyst condition.The weight-average molecular weight of described novolac resin preferably 3,000 to 30,000.Described acid catalyst is sulfuric acid, hydrochloric acid, formic acid, acetic acid or malic acid etc.
The content of described novolac resin preferably accounts for 10-30 weight % in whole second photoetching compositions.
Described diazide class Photoactive compounds is all preferably accounting for 2-10 weight % in the composition.If described diazide class Photoactive compounds content is lower than 2 weight %, then can not form stable pattern, if surpass 10 weight %, the then non-constant of storage stability.Described diazide class Photoactive compounds can be identical with the composition that comprised in first photoetching compositions.
Described organic solvent preferably accounts for 60-90 weight % all can be used as the nubbin existence in the composition.Described organic solvent is the same with first photoresist layer, can use more than one the compound that is selected from propylene glycol methyl ether acetate (PGMEA), ethyl lactate (EL), ethylene glycol monomethyl ether acetate (MMP), propylene glycol monomethyl ether (PGME), methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK) and the 1-Methyl-2-Pyrrolidone (NMP).
As required, second photoetching compositions can also improve performance by further adding adjuvant.Described adjuvant be selected from photosensitive accelerant, colorant, dyestuff, anti-scratch agent, plastifier, tackifier, and surfactant in more than one.
The film speed of this second photoetching compositions that the present invention relates to is in 10mJ to 300mJ scope, and its film speed is slower than the film speed of first photoetching compositions.
At this moment, according to use and technology type, the thickness range of photoresist layer can be very extensive, and the thickness of second photoresist layer is 200-1700nm preferably.And precuring can be carried out in 90-110 ℃ temperature range 60-120 second.
In addition, in step (c), after exposing by mask 40 (Fig. 1 c), develop again with pattern.At this moment, in this operation, form undercutting section (Fig. 1 d) according to the difference of the film speed of the film speed of first photoresist layer 20 and second photoresist layer 30.That is, the step (a) by using compound shown in the described Chemical formula 1 and use the step (b) of general novolac resin on substrate, to form first photoresist layer and second photoresist layer, the difference according to film speed forms the undercutting section then.And, at film speed of the present invention, be not only fluoropolymer resin, and the kind of diazide compound, content also can play very big effect.
Above-mentioned conditions of exposure can realize that for example light particularly exposes by conventional method under ultraviolet condition, thereby forms desirable pattern.As mentioned above, the substrate that has exposed fully is impregnated in the alkaline developing solution, each photoresist layer of exposed portion is set aside to all then or major part when dissolving basically till.At this moment, described developing aqueous solution preferably uses and comprises certain density alkaline hydrated oxide or tetramethyl ammonium hydroxide (tetramethylammonium hydroxide, aqueous solution TMAH).
In addition, the pattern formation method that the present invention relates to after step (c) finishes, can also be carried out the stripping process of the photoresist layer of the metal evaporation of above-mentioned steps (d) and step (f), can finish desirable pattern by these steps.And, can also omit the metal evaporation step of described step (d) as required.
Therefore, in the process of carrying out step (d), come evaporation metal, thereby form metal level 50 (Fig. 1 e) based on the undercutting section that in described step (c), forms.
And, on second photoresist layer and the substrate that exposed, form substrate by metal evaporation.At this moment, but the metal thickness of evaporation can adjust according to the thickness of first photoresist layer.And the metal species of evaporation can be used common metal, for example aluminium, molybdenum, chromium, copper, platinum, indium tin oxide (ITO) etc.
Step (f) is after described metal evaporation step finishes, also to remove the process of first photoresist layer 20 and second photoresist layer 30 with general remover by stripping process.Through this process, only remaining metal level 50 on the substrate 10 forms pattern (Fig. 1 f) with this.That is, if carry out described stripping process, then the removed while of second photoresist layer, its metal level that forms above also is removed in the lump.
As mentioned above, the present invention can use by the pattern of described method formation and with it and be applicable on semiconductor element or the various display device, thereby can form conductive pattern.Especially, even also can form good shape under the big situation of thickness, and can provide display element with fine pattern.At this moment, display element of the present invention can comprise liquid crystal display cells, electroluminescent device, plasma display etc.
The present invention forms first photoresist layer by compound shown in the described Chemical formula 1, thereby improved patience to the organic solvent that is contained in second photoresist layer, and can obtain undercutting shape profile, and under the big situation of thickness, still can form fine pattern.In addition, the present invention does not need extra etching work procedure, and only just can carry out metal evaporation by the wet developing operation, thereby because operation becomes simply, can reach the effect that reduces cost.
Description of drawings
Fig. 1 a to Fig. 1 f is the process chart of the photoresist pattern formation method that relates to of one embodiment of the invention.
Fig. 2 a to Fig. 2 b is that the thickness of first photoresist layer that relates to of embodiment 1 is that the thickness of 1500nm, second photoresist layer is the electron micrograph of the pattern section of 500nm.
Fig. 3 a to Fig. 3 b is that the thickness of first photoresist layer that relates to of embodiment 2 is that the thickness of 800nm, second photoresist layer is the electron micrograph of the pattern section of 1700nm.
Fig. 4 is the electron micrograph of the pattern section made of the method that relates to by comparative example 1.
Embodiment:
Below be the preferred embodiments of the present invention.Yet following examples only illustrate for helping to understand the present invention, and content of the present invention is not limited at the embodiment shown in this.
Embodiment 1
Form the display device pattern according to the order shown in Fig. 1 a to Fig. 1 f.
That is, on glass substrate, apply first photoetching compositions, and under 90-110 ℃ temperature conditions 110 seconds of precuring, be first photoresist layer of 1500nm thereby form thickness.Then, coating second photoetching compositions on described first photoresist layer, and under 90-110 ℃ temperature conditions 110 seconds of precuring, be second photoresist layer of 500nm thereby form thickness.
Wherein, first photoetching compositions comprises compound shown in the following Chemical formula 1 of 20 weight %, as 2 of 4 weight % of diazide class Photoactive compounds, 3,4,4 '-tetrahydroxybenzophenone-1, the propylene glycol methyl ether acetate (PGMEA) of 2-naphtho-quinone diazide-5-sulfonate and 76 weight %.
[Chemical formula 1]
(n is 400 in the described Chemical formula 1.)
And, second photoetching compositions comprises the novolac resin of 20 weight %, as 2,3,4 of 5 weight % of diazide class Photoactive compounds, 4 '-tetrahydroxybenzophenone-1, the PGMEA of 2-naphtho-quinone diazide-5-sulfonate and 75 weight %.At this moment, the metacresol of novolac resin and the ratio of paracresol are 4: 6, and weight-average molecular weight is 6,000.
Then, using mask, first photoresist layer and second photoresist layer exposed under ultraviolet ray, use developer solution again with pattern--TMAH 2.38% (wt) develops.At this moment, the difference according to the film speed of first photoresist layer and second photoresist layer forms the undercutting section.Fig. 2 a, Fig. 2 b show the pattern section of the undercutting shape that forms by this method.
Then, AM aluminum metallization metal level on undercutting section basis.
After evaporation finished, (the U.S. willing product of generation advances in east in Korea S) removed first photoresist layer and second photoresist layer with remover, and forms the pattern that only contains metal on substrate.
Embodiment 2
The thickness that becomes 800nm, second photoresist layer except the thickness that makes first photoresist layer becomes the 1700nm, implements with the method identical with described embodiment 1.At this moment, Fig. 3 a, Fig. 3 b show the pattern section of undercutting shape.
Comparative example 1
As the fluoropolymer resin of first photoresist layer, the ratio of using metacresol and paracresol is that 6: 4, weight-average molecular weight are 15,000 conventional novolac resin, comes compound shown in the substituted chemistry formula 1 with this.Except the thickness that makes first photoresist layer and second photoresist layer becomes 800nm and 1700nm respectively, implement with the method identical with embodiment 1.
Comparative example 2
As the fluoropolymer resin of first photoresist layer, the ratio of using metacresol and paracresol is that 6: 4, weight-average molecular weight are 8,000 conventional novolac resin, comes compound shown in the substituted chemistry formula 1 with this.Except the thickness that makes first photoresist layer and second photoresist layer becomes 800nm and 1700nm respectively, implement with the method identical with embodiment 1.
Comparative example 3
As the macromolecule resin of first photoresist layer, the ratio of using metacresol and paracresol is that 4: 6, weight-average molecular weight are 6,000 conventional novolac resin, comes the compound of substituted chemistry formula 1 with this.Except the thickness that makes first photoresist layer and second photoresist layer becomes 800nm and 1700nm respectively, implement with the method identical with embodiment 1.
Experimental example
At described embodiment 1-2 and comparative example 1-3, detected thickness stability and pattern and formed tendency, and its result has been illustrated in the following table 1.At this moment, thickness detects by NANOSPEC3000 (the anti-promise of the U.S. (NANO metrics) company's product) equipment.And the evaluation criterion of thickness stability and formation pattern is as follows.
* thickness stability
◎: the expression thickness distribution is below the 30nm; Zero: the expression thickness distribution is 30-100nm; *: the expression thickness distribution is more than the 100nm.
* form pattern
◎: expression has presented the exposure characteristics of the ground floor and the second layer; △:, do not present the exposure characteristics of ground floor though expression forms pattern; *: expression thickness distribution (thicknessdistribution) is excessive, can't form pattern.
[table 1]
Show as the result of above-mentioned table 1, embodiment 1,2 form pattern and stable aspect on all have outstanding effect, but with regard to comparative example 1, its form pattern and thickness stability poorer than embodiment 1,2.And with regard to comparative example 2 and comparative example 3, when coating second photoresist layer, first photoresist layer is dissolved in the organic solvent that is contained in second photoresist layer, and integral thickness stability is serious to descend.
That is, in embodiment 1, applied after first photoresist layer and second photoresist layer, thickness is 1990-2020nm, and thickness distribution is below the 30nm.In embodiment 2, applied after first photoresist layer and second photoresist layer, thickness is 2490-2520nm, thickness distribution is below the 30nm.Therefore, because the thickness distribution of embodiment 1 and embodiment 2 all is below the 30nm, therefore form outstanding pattern easily.
Yet, in comparative example 1, having applied after first photoresist layer and second photoresist layer, thickness is 2300-2350nm, thickness distribution is 50nm.Because the part of first photoresist layer is dissolved in the organic solvent that is contained in second photoresist, so thickness reduces 200nm, and thickness distribution is increased to 50nm, and is bigger than embodiment 1, embodiment 2.
And, in comparative example 2, having applied after first photoresist layer and second photoresist layer, thickness is 1800-2000nm, thickness distribution is 200nm.The major part of first photoresist layer is dissolved in the organic solvent that is contained in second photoresist, and thickness reduces 500-700nm, and thickness distribution is increased to 200nm.
In comparative example 3, applied after first photoresist layer and second photoresist layer, thickness is 1800-2000nm, thickness distribution is 200nm.The major part of first photoresist layer is dissolved in the organic solvent that is contained in second photoresist, and thickness reduces 500-700nm, and thickness distribution is increased to 200nm.
Therefore, with regard to comparative example 2 and comparative example 3,, therefore can't form pattern because thickness distribution is too big.
And Fig. 2 a and Fig. 2 b show that the thickness of first photoresist layer that described embodiment 1 relates to is that the thickness of 1500nm, second photoresist layer is the electron micrograph of the pattern section of 500nm.Fig. 3 a and Fig. 3 b are that the thickness of first photoresist layer that relates to of embodiment 2 is that the thickness of 800nm, second photoresist layer is the electron micrograph of the pattern section of 1700nm.Fig. 1 shows the electron micrograph of the pattern section of the method making that relates to by comparative example 1.
Shown in Fig. 2 a to Fig. 3 b, in embodiment 1 and embodiment 2, form separately pattern respectively according to first photoresist layer exposure characteristics different with second photoresist layer.Yet, in comparative example shown in Figure 41, first photoresist layer and second photoresist layer are applied, so that their thickness becomes 800nm, 1700nm respectively, yet because the mixing of first photoresist layer and second photoresist layer, first photoresist layer and second photoresist layer can not have exposure characteristics separately.Therefore, the pattern of comparative example 1 is the form that first photoresist layer and second photoresist layer mix, and the thickness attenuation, thereby can't obtain desirable pattern contour.
Claims (9)
1. a pattern formation method is characterized in that, may further comprise the steps:
A) on substrate, form first photoresist layer;
B) on described first photoresist layer, form second photoresist layer; And
C) described first photoresist layer and second photoresist layer are exposed, develop, thereby form the photoresist pattern of undercutting shape,
Described first photoresist layer is by being formed by the represented compound of following Chemical formula 1, and the film speed of described second photoresist layer is slower than the film speed of first photoresist layer,
[Chemical formula 1]
In the described Chemical formula 1, R
1To R
3Represent independently that respectively hydrogen or carbon number are 1 to 10 alkyl, n represents 10 to 1000 integer.
2. pattern formation method according to claim 1 is characterized in that:
The weight-average molecular weight of the compound of described Chemical formula 1 is 8,000 to 15,000.
3. pattern formation method according to claim 1 is characterized in that:
Described first photoresist layer is by behind coating eurymeric first photoetching compositions on the substrate, carry out precuring and form, described first photoetching compositions comprises represented compound, the diazide class Photoactive compounds of 2-10 weight % and the organic solvent of surplus of Chemical formula 1 of 10-30 weight %.
4. pattern formation method according to claim 1 is characterized in that:
Described second photoresist layer is by behind coating second photoetching compositions on first photoresist layer, carry out precuring and form, described second photoetching compositions comprises the novolac resin of 10 to 30 weight %, the diazide class Photoactive compounds of 15 to 30 weight % and the organic solvent of surplus.
5. pattern formation method according to claim 4 is characterized in that:
Described novolac resin for by the separately synthetic novolac resin of metacresol, by the synthetic separately novolac resin of paracresol, use resorcinol (novolac resin or salicylide and benzaldehyde are reacted the weight-average molecular weight for preparing is 3,000 to 30,000 novolac resin.
6. pattern formation method according to claim 1 is characterized in that:
The thickness of described first photoresist layer is 200-1500nm, and the thickness of second photoresist layer is 200-1700nm.
7. pattern formation method according to claim 1 is characterized in that, and is further comprising the steps of after step c) finishes:
D) evaporation metal on described photoresist pattern; And
F) from the photoresist pattern of described evaporation metal, peel off first photoresist layer and second photoresist layer by stripping process.
8. pattern formation method according to claim 1 is characterized in that:
Described method is used to form the conductive pattern of semiconductor element or display device.
9. according to claim 3 or 4 described pattern formation methods, it is characterized in that:
Described organic solvent is selected from more than one the compound in propylene glycol methyl ether acetate, ethyl lactate, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, methyl ethyl ketone, methyl isobutyl ketone and the 1-Methyl-2-Pyrrolidone.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020080109528A KR20100050303A (en) | 2008-11-05 | 2008-11-05 | Preparation method of pattern |
| KR10-2008-0109528 | 2008-11-05 |
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| Publication Number | Publication Date |
|---|---|
| CN101738854A true CN101738854A (en) | 2010-06-16 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200910209666A Pending CN101738854A (en) | 2008-11-05 | 2009-11-04 | Pattern forming method |
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| Country | Link |
|---|---|
| JP (1) | JP2010113356A (en) |
| KR (1) | KR20100050303A (en) |
| CN (1) | CN101738854A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104425549A (en) * | 2013-08-30 | 2015-03-18 | 乐金显示有限公司 | Organic electroluminescence device and manufacturing method thereof |
| CN106409992A (en) * | 2016-10-25 | 2017-02-15 | 华灿光电（浙江）有限公司 | Preparation method of high-reliability light-emitting diode |
| CN108107673A (en) * | 2017-12-12 | 2018-06-01 | 深圳市晶特智造科技有限公司 | photoresist processing method |
| CN108389784A (en) * | 2018-02-26 | 2018-08-10 | 清华大学 | The preparation method of patterned metal layer |
| CN109216540A (en) * | 2017-06-30 | 2019-01-15 | 中电海康集团有限公司 | MTJ device and its production method |
| CN110054142A (en) * | 2019-04-29 | 2019-07-26 | 太原理工大学 | A kind of air filtration film and preparation method thereof based on MEMS technology |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101104208B1 (en) * | 2010-02-19 | 2012-01-10 | 고려대학교 산학협력단 | Selective patterning method of polyurethane and semiconductor device manufactured using the same |
| WO2012121138A1 (en) * | 2011-03-09 | 2012-09-13 | シャープ株式会社 | Method for forming resist pattern, method for forming wiring pattern, and method for manufacturing active matrix substrate |
| JP5780026B2 (en) * | 2011-07-12 | 2015-09-16 | 三菱電機株式会社 | MIM capacitor, semiconductor device |
| JP6147995B2 (en) * | 2012-11-26 | 2017-06-14 | 東京応化工業株式会社 | Forming method of plating model |
| KR102351958B1 (en) | 2015-01-13 | 2022-01-17 | 삼성디스플레이 주식회사 | Method for pattern of thin film |
-
2008
- 2008-11-05 KR KR1020080109528A patent/KR20100050303A/en not_active Application Discontinuation
-
2009
- 2009-11-04 JP JP2009253372A patent/JP2010113356A/en not_active Withdrawn
- 2009-11-04 CN CN200910209666A patent/CN101738854A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104425549A (en) * | 2013-08-30 | 2015-03-18 | 乐金显示有限公司 | Organic electroluminescence device and manufacturing method thereof |
| CN104425549B (en) * | 2013-08-30 | 2017-06-23 | 乐金显示有限公司 | Organic electroluminescent device and its manufacture method |
| CN106409992A (en) * | 2016-10-25 | 2017-02-15 | 华灿光电（浙江）有限公司 | Preparation method of high-reliability light-emitting diode |
| CN109216540A (en) * | 2017-06-30 | 2019-01-15 | 中电海康集团有限公司 | MTJ device and its production method |
| CN108107673A (en) * | 2017-12-12 | 2018-06-01 | 深圳市晶特智造科技有限公司 | photoresist processing method |
| CN108389784A (en) * | 2018-02-26 | 2018-08-10 | 清华大学 | The preparation method of patterned metal layer |
| CN110054142A (en) * | 2019-04-29 | 2019-07-26 | 太原理工大学 | A kind of air filtration film and preparation method thereof based on MEMS technology |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20100050303A (en) | 2010-05-13 |
| JP2010113356A (en) | 2010-05-20 |
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Open date: 20100616 |