CN109283787A - Functional configuration manufacturing method and photoresist processing unit - Google Patents
Functional configuration manufacturing method and photoresist processing unit Download PDFInfo
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- CN109283787A CN109283787A CN201810734880.3A CN201810734880A CN109283787A CN 109283787 A CN109283787 A CN 109283787A CN 201810734880 A CN201810734880 A CN 201810734880A CN 109283787 A CN109283787 A CN 109283787A
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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
- G03F7/0035—Multiple processes, e.g. applying a further resist layer on an already in a previously step, processed pattern or textured surface
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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
- G03F7/16—Coating processes; Apparatus therefor
- G03F7/168—Finishing the coated layer, e.g. drying, baking, soaking
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- General Physics & Mathematics (AREA)
- Photosensitive Polymer And Photoresist Processing (AREA)
- Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)
- Exposure Of Semiconductors, Excluding Electron Or Ion Beam Exposure (AREA)
Abstract
A kind of functional configuration manufacturing method and photoresist processing unit are provided, the heat resistance of photoresist pattern is improved by hardening but the combination for substrate is not made to become securely, to be easily peeled off and be difficult to generate residue.Include to 1 irradiating ultraviolet light of photoresist pattern formed on the substrate 3 come after making the cured hardening process of photoresist pattern 1, to the film deposition procedures of the site deposition functional layer film 20 not covered by photoresist pattern 1 on substrate 3；And the stripping process for removing the functional layer film 20 of photoresist pattern 1 and mounting thereon.Hardening process is the process that ultraviolet light is irradiated in the mode more than the accumulative light quantity of the light of the accumulative light amount ratio exposed photosensitive wave-length coverage of the wavelength ultraviolet light shorter than the exposed photosensitive wave-length coverage of photoresist.
Description
Technical field
Present invention is related to the manufacture of various functional configuration bodies.
Background technique
Photoetching is widely used in the manufacture for the various functional configuration bodies for needing to refine small construction.Functional configuration body is
Utilize the general name of the product of the specific function of small constitution realization.
In photoetching, photoresist is the main material that the purification of shape is carried out using its photonasty, it is known to eurymeric
And minus.Eurymeric is to become solvable for developer solution by high molecular combination and formed to carry out pattern because photosensitive cut-off.
In the case where minus, monomeric photosensitive and generate cross-linking reaction, due to being polymerized as insoluble in developer solution.Figure is carried out as a result,
Case is formed.In recent years, lacking in order to compensate for luminous energy when exposing, also gradually more use chain change for generating acid due to exposure
Learn the photoresist of scale-up version.
In manufacturing process of the representativeness as photoetching using the semiconductor integrated circuit of example, to being formed on conductive layer
Photoresist layer irradiation circuit pattern light, expose photoresist layer, and make the shape of circuit pattern using development
It is made in photoresist layer.Also, the pattern of photoresist layer is passed through by Conductive Layer Etch, to form the figure of conductive layer
Case (circuit pattern).In addition, the photoresist layer of shape as defined in being patterned as below is referred to as photoresist pattern.
Other than the utilization of the photoresist pattern of mask when as being etched to such substrate layer, also have
Photoresist pattern is deposited as mask and using film the technique to form functional configuration body by Shi Caiyong.The technique will be due to that will sink
Redundance in long-pending film removes together with photoresist and is referred to as stripping method.
Fig. 9 is the skeleton diagram for showing previous common stripping method.As shown in figure 9, being applied on the substrate 3 in stripping method
Photoresist is covered to form photoresist layer 10 ((1) of Fig. 9).Then, across the light L of the defined pattern of mask M
((2) of Fig. 9) are exposed to photoresist layer 10.Defined pattern refers to corresponding with the shape of the functional layer in rear formation
Pattern.Then, by developing after exposure to photoresist layer 10, to obtain 1 (Fig. 9 of photoresist pattern
(3)).It is how much mobile to the direction parallel with the surface of substrate 3 since development is the wet process based on developer solution.Therefore, as schemed
Shown in 9 (3), becomes in the bottom of the opening sidewalls of photoresist pattern 1 and slightly dig deep section shape.
Film 20 by such photoresist pattern 1 as masked-deposition functional layer.It is deposited about film, sputtering is such
PVD (physical deposition) the case where it is more.The opening that film 20 passes through photoresist pattern 1 is deposited on the exposed division of substrate 3, removes
Also the upper surface of photoresist pattern 1 is deposited on other than this.
Next, being removed with stripper as N-Methyl pyrrolidone (NMP) to photoresist pattern 1
(liftoff).At this point, the deposition film 20 for being placed in the upper surface of photoresist pattern 1 is also removed together.As a result,
Functional layer 2 is formed on substrate 3, can get functional configuration body.
Such stripping method is for example often used in the formation of the electrode pattern in display apparatus or lighting apparatus.
Stripping method due to do not need etching therefore functional configuration body material freedom degree it is higher, and due to without etching therefore from
This reduces the consideration of the viewpoints such as environmental pressure with superior type.
Patent document 1: Japanese Unexamined Patent Publication 2000-331910 bulletin
In stripping method as described above, the heat resistance of photoresist becomes project.Hereinafter, 0 pair of click-through referring to Fig.1
Row explanation.Figure 10 is figure the problem of showing the heat resistance of the photoresist pattern in stripping method.
In above-mentioned previous stripping method, in the deposition procedures of the film of functional layer, preferably by substrate-placing in heating
Plate etc. carries out the deposition of film to substrate while heating.The reason is that because the deposition velocity (film forming speed) of film is usual
With temperature dependency, film forming speed becomes faster if further increasing temperature.
However, according to the research of inventor, if it is more than that such as 100 DEG C of temperature carries out film deposition that substrate, which is heated to,
The shape essence in the presence of the film of deposition has been distinguished in the deformation for then generating such photoresist pattern 1 shown in (A) of Figure 10, (B)
The problem of degree reduces.Therefore, in the previous method, there are the upper limits for temperature when depositing for film, cannot be formed a film by improving
Speed improves productivity.
On the other hand, using the formation process of the minute shape of photoetching using LSI as the semiconductor integrated circuit of representative
It is carried out extensively in manufacture.This technique utilizes photoetching shape after the whole face of substrate is pre-formed the film of functional layer on it
At photoresist pattern.Then, it is etched to obtain using photoresist pattern as film of the mask to functional layer
The functional layer of defined pattern.
In the photoetching (hereinafter referred to as etching method) for including such etching work procedure, due to the photoresist in etching
Pattern leaks in high temperature cruelly, and the heat resistance of photoresist pattern becomes problem.Therefore, it in etching method, is improved sometimes
The post-processing of the heat resistance of photoresist pattern.
Post-processing is to irradiate ultraviolet light to photoresist pattern, promotes polymerization to improve heat resistance using cross-linking reaction
Processing, the process especially relatively mostly used using the photoresist of eurymeric.The processing is also claimed sometimes
It hardens, sometimes referred to as curing process.Hereinafter, in this specification, being generally called with the term of " hardening ".
According to the research of inventor, the degree of polymerization of photoresist increases if being hardened, therefore heat resistance improves, i.e.,
Make the processing after carrying out with higher temperature, also can inhibit the deformation of photoresist pattern.In above-mentioned stripping method, although
When being contemplated that and use such hardening, but having distinguished in stripping method according to the research of inventor using hardening, photic resist is generated
The problem of losing the residue of agent.
If being hardened, although the heat resistance of photoresist pattern improves, since cross-linking reaction is to whole progress, because
The combination of this and substrate layer is also easy secured.Such as it in the case where forming wiring pattern with etching method, makes and leads on substrate
Electrolemma is formed on photoresist pattern and is etched to conductive film.After etching, removing photoresist is carried out
The processing of agent pattern.Photoresist pattern in most cases, is removed using oxygen plasma etc. by being ashed.Carry out
In the case where cure process, due to being got higher for the adhesive strength of the conductive film as substrate, it is therefore desirable to higher energy
Amount carries out for a long time to be ashed or be needed.
On the other hand, in stripping method, method as Oxygen plasma ashing brings damage to the functional layer being made, and leads to
It is not often used, but uses the method removed as described above by stripper.However, according to the research of inventor, due to
The combination of photoresist pattern and substrate after cure process is reinforced, therefore cannot be sufficiently carried out stripping by stripper
From being easy to produce residue.If the case where generating residue, affecting to the performance of functional layer is more, easily becomes product and lack
Sunken reason.
Summary of the invention
Present invention is made into order to solve the above problems, it is therefore intended that improves photoresist pattern by hardening
Heat resistance but so that the combination for substrate is become securely to provide a kind of removing easy and be not likely to produce the excellent system of residue
Make technology.
In order to solve the above problems, the invention that the technical solution 1 of this application is recorded is that manufacture includes the function after patterning
The functional configuration manufacturing method of the functional configuration body of layer, comprising: the photoresist of photoresist pattern is formed on substrate
Agent pattern formation process；After photoresist pattern formation process, photoresist pattern irradiating ultraviolet light is made photic
Resist pattern solidifies the hardening process improved；After hardening process, on substrate not by photoresist pattern cover
The film deposition procedures of the film of site deposition functional layer；And after film deposition procedures, photoresist pattern and mounting are removed
In the stripping process of the film of the functional layer in photoresist pattern, hardening process is the exposure with wavelength than photoresist
Mode more than the accumulative light quantity of the light of the accumulative light amount ratio exposed photosensitive wave-length coverage of the short ultraviolet light of photosensitive wavelength range is irradiated
The process of the ultraviolet light.
In addition, in order to solve the above problems, the invention that technical solution 2 is recorded is described in the composition of the technical solution 1
Hardening process is compared with the light of wavelength ratio 330nm long with the process of high illumination irradiation 330nm ultraviolet light below.
In addition, in order to solve the above problems, composition of the invention that technical solution 3 is recorded in the technical solution 1 or 2
In, the absorptivity of the photoresist ultraviolet light shorter than the exposed photosensitive wave-length coverage to wavelength is greater than to the exposure
The absorptivity of the light of photosensitive wavelength range.
In addition, in order to solve the above problems, the invention that technical solution 4 is recorded is in any one of the technical solution 1 to 3
In composition, the photoresist is eurymeric.
In addition, in order to solve the above problems, the invention that technical solution 5 is recorded is in any one of the technical solution 1 to 4
In composition, the photoresist includes the polymerization initiator of 0.1 weight percent or more.
In addition, in order to solve the above problems, the invention that technical solution 6 is recorded is in any one of the technical solution 1 to 5
In composition, the temperature of the substrate is set as 100 DEG C or less in the hardening process.
In addition, in order to solve the above problems, the invention that technical solution 7 is recorded is in any one of the technical solution 1 to 4
In composition, the temperature of the substrate is set as 30 DEG C or less in the hardening process.
In addition, in order to solve the above problems, the invention that technical solution 8 is recorded is in any one of the technical solution 1 to 5
In composition, the substrate is not added in the hardening process in addition to irradiating progress heating using the ultraviolet light
Heat.
In addition, in order to solve the above problems, the invention that technical solution 9 is recorded is in any one of the technical solution 1 to 8
In composition, the ultraviolet light is irradiated while cooling down the substrate in the hardening process.
In addition, in order to solve the above problems, the invention that technical solution 10 is recorded has: illumination unit, including generate ultraviolet
The light source of line；And workbench, mounting are formed with the substrate of photoresist pattern, illumination unit is so that wavelength ratio forms light
The ultraviolet light for causing the exposed photosensitive wave-length coverage of the photoresist of resist pattern short becomes than exposed photosensitive wave-length coverage
The mode of accumulative light quantity more than light, the unit of the ultraviolet light is irradiated to substrate.
In addition, in order to solve the above problems, the invention that technical solution 11 is recorded is in the composition of the technical solution 10, institute
It states illumination unit to have compared with the transmissivity of the light of the exposed photosensitive wave-length coverage, wavelength is than the exposed photosensitive wavelength model
Enclose the high filter of short transmission of ultraviolet rays.
Invention effect
As described below, the dress recorded according to method or technical solution 10 that the technical solution of this application 1 is recorded
It sets, due to improving the heat resistance of photoresist pattern, the heavy of the film of functional layer can be carried out with higher temperature
Product.Therefore, productivity is got higher.On the other hand, since the residue of the photoresist after removing tails off, reduce photic anti-
The problem of residue of erosion agent brings a negative impact the performance of product.
In addition, according to the invention that technical solution 3 is recorded, in addition to said effect, due to the exposure to wavelength than photoresist
The absorptivity of the ultraviolet light of light sensation light wave length is greater than the absorptivity to the light of exposed photosensitive wave-length coverage, therefore easily reduces light
Cause the residue of resist.
In addition, according to the invention that technical solution 4 is recorded, in addition to said effect, since photoresist is eurymeric, by
The significant effect that the heat resistance that hardening is realized improves, the meaning of invention are preferably played.
In addition, according to the invention that technical solution 5 is recorded, in addition to the temperature of said effect, substrate when due to hardening is set as
Therefore 100 DEG C hereinafter, can shorten the time needed for hardening.
In addition, according to the invention that technical solution 6 is recorded, in addition to the temperature of said effect, substrate when due to hardening is set as
Therefore 30 DEG C hereinafter, can further shorten the time needed for hardening.
In addition, according to the invention that technical solution 7 is recorded, due in hardening process, substrate in addition to by ultraviolet light irradiate into
Capable heating is not heated, therefore the management for the processing time hardened is easy, and is thus easier to reduce photoresist
Residue.
In addition, since in hardening, substrate is cooled, being hardened at that point according to the invention that technical solution 8 is recorded
Time management become to be more easier, it is easier to reduce the residue of photoresist.
In addition, according to the device that technical solution 11 is recorded, in addition to said effect, due to carrying out wavelength control using filter
System, therefore it is easy to get the result of optimal resist processing.
Detailed description of the invention
Fig. 1 is the figure for showing the outline of functional configuration manufacturing method of embodiment.
Fig. 2 is to show certain photoresist to the figure of the spectral-transmission favtor of ultraviolet light.
Fig. 3 is the knot for showing the experiment carried out to investigate the optimal conditions of the hardening process of photoresist pattern
The figure of fruit.
Fig. 4 is the skeleton diagram for indicating the wavelength control being shown in FIG. 3 in the experiment of result.
Fig. 5 is the skeleton diagram for showing the mechanism of the hardening in the method for embodiment.
Fig. 6 is that will compare the figure shown with embodiment in the past for the condition of hardening.
Fig. 7 is the front skeleton diagram of the photoresist processing unit of embodiment.
Fig. 8 is the skeleton diagram for being shown as the luminescent spectrum of the Excimer lamp of an example of light source.
Fig. 9 is to show the previous skeleton diagram for typically stripping off method.
Figure 10 is figure the problem of showing the heat resistance of the photoresist pattern in stripping method.
Description of symbols
1 photoresist pattern
10 photoresist layers
2 functional layers
20 functional layer films
3 substrates
4 illumination units
41 light sources
42 filters
5 workbench
51 temperature control devices
Specific embodiment
Next, being illustrated to the mode (hereinafter, embodiment) for implementing the present application.
Fig. 1 is the figure for showing the outline of functional configuration manufacturing method of embodiment.The functional configuration body of embodiment
Manufacturing method uses stripping method.That is, it is photic anti-to be formed to coat photoresist on the substrate 3 as shown in (1)~(3) of Fig. 1
Oxidant layer 10 is lost, is developed after with the exposure of the light of defined pattern, to obtain photoresist pattern 1.
Next, carrying out hardening process in the method for embodiment.As shown in (4) of Fig. 1, to light in hardening process
It causes resist pattern 1 to irradiate ultraviolet light L2, generates cross-linking reaction, improve the degree of polymerization.At this point, as described later, carrying out making to come from
The wavelength control that the light of light source 41 passes through filter 42 to irradiate.Also, later, as shown in (5) of Fig. 1, functional layer use is carried out
The deposition procedures of film 20.Film deposition is more by sputtering the case where such PVD (physical vapour deposition (PVD)) is carried out, but is not excluded for making
With the CVD (chemical vapor deposition) of reactant gas.In the case that functional layer is conductive layer with the functional layer of film 20, by gold, copper
Such conductive material is formed.
As shown in (5) of Fig. 1, exposed surface of the film 20 in addition to being deposited on the substrate not covered by photoresist pattern 1, also
It is deposited on the upper surface of photoresist pattern 1.Later, stripping process is carried out, becomes as shown in (6) of Fig. 1 and eliminates
State after photoresist pattern 1.Removing is the wet process of stripper as having used NMP, photoresist pattern 1 and load
Film 20 placed on it is removed together.It forms functional layer 2 on the substrate 3 as a result, becomes the state for completing functional configuration body.
In the functional configuration manufacturing method of such embodiment, hardening process in order to solve the problems, such as conventional art and
It optimizes.That is, being changed improving the heat resistance of photoresist pattern by hardening but not generated on residue in removing
It is kind.Hereinafter, being illustrated to the point.
Inventor is for the residue after the removing that solves the problems, such as to have generated when having added hardening process, it is intended that photic anti-
Erosion agent pattern hardens but photoresist pattern is not made to become firm to the combination of substrate.As its countermeasure, it is contemplated that do not make
The deep that the effect of hardening reaches photoresist pattern may be effectively.For realizing that the technological maheup of the countermeasure has carried out with keen determination
Research, the wavelength of ultraviolet light when hardening can be studied by having distinguished.
Fig. 2 is to show certain photoresist to the figure of the spectral-transmission favtor of ultraviolet light.The example of Fig. 2 be novolaks system just
The spectral-transmission favtor of type photoresist.This photoresist changes with characteristic after exposure before exposure.Therefore, it shows
The spectral-transmission favtor after spectral-transmission favtor and exposure before exposure.
The photoresist that spectral-transmission favtor is shown in FIG. 2 is assumed to be exposed by i line (365nm).That is, exposed photosensitive wavelength
For 365nm.Therefore, as shown in Fig. 2, photoresist has enough transmissivities at 365nm.Also, the wave shorter than 365nm
The transmissivity of strong point is lower than the transmissivity at 365nm.
In the case where eurymeric, photoresist pattern is in the remaining state of unexposed portion, but includes as polymerization
The ingredient that initiator functions.For example, the crosslinking that emulsion as two nitrine of naphthoquinones can generate novolac resin is anti-
It answers.Therefore, if the photoresist pattern to unexposed portion irradiates ultraviolet light, cross-linking reaction is generated, the degree of polymerization is got higher, light
The heat resistance of resist pattern is caused to improve.
In the method for embodiment, when the hardening, biggish wavelength is absorbed by photoresist by more irradiation
Thus ultraviolet light inhibits cross-linking reaction to reaching deep.As being illustrated Fig. 2, it is designed to photoresist for exposed photosensitive
The light of wavelength has biggish transmissivity, smaller for the transmissivity of the light of the wavelength shorter than its.Transmissivity is smaller to be meaned to inhale
It receives larger.It, can if being hardened using the short ultraviolet range of the light than exposed photosensitive wave-length coverage according to the research of inventor
It improves the heat resistance of photoresist and can be realized the excellent process of the residue after no removing.
The transmissivity and photoresist after exposure that exposed photosensitive wave-length coverage refers to the photoresist before exposure
The wave-length coverage that transmissivity has differences.In the feelings of the resist being made of novolaks system resin for example as shown in Figure 2
Under condition, the wave-length coverage of 300nm~480nm is referred to as exposed photosensitive wave-length coverage.
Fig. 3 is the knot for showing the experiment carried out to investigate the optimal conditions of the hardening process of photoresist pattern
The figure of fruit.Fig. 3 is also the embodiment for showing the present application and the figure of its comparative example.
In this experiment, in order to form photoresist pattern on substrate, and the resistance to of the photoresist pattern is investigated
It is hot, it heats the substrate on hot plate and to whether producing the deformation of photoresist pattern and confirmed.In heating plate
The heating test of upper progress uses 100 DEG C, 120 DEG C, 140 DEG C of these three conditions, and heating time is set as 5 minutes.
In addition, in this experiment, the LUMILON (note for using the JSR (company) of novolaks system to make as photoresist
Volume trade mark) LP series, photoresist pattern formation when exposure wavelength used 365nm.In addition, being used as developer solution
(2.38%, TMAHaq (temperature condition: 23 DEG C), 60 seconds).
In Fig. 3, sample A has carried out heating test after photoresist pattern is formed without hardening, and sample B is not
It carries out wavelength control and has carried out heating test after being hardened, sample C and sample D are in the reality to carry out wavelength control
Apply mode condition hardened after, carried out heating test.
Fig. 4 is the skeleton diagram for indicating the wavelength control being shown in FIG. 3 in the experiment of result.Wherein, (A) of Fig. 4 is shown
The illumination spectra in the case of wavelength control is not carried out, and (B) of Fig. 4 indicates to have carried out the illumination spectra in the case of wavelength control.?
In the embodiment, wavelength control is carried out by filter, therefore (A) of Fig. 4 is equivalent to the luminescent spectrum of the lamp as light source,
(B) of Fig. 4 is equivalent to the spectrum after transmission filter.
In this experiment, use high-pressure mercury-vapor lamp as light source.In the case where carrying out wavelength control, in light source and substrate
Between be configured with the cut-off filter blocked to the light for the wavelength for being longer than 330nm.Therefore, as shown in (B) of Fig. 4, into
In the case where row wavelength control, 330nm light below is actually only irradiated.
The outline section shape of each sample after each heating test is shown in FIG. 3 (is inserted electron micrograph
Figure forms).In addition, the residue after having the removing of no-trump photoresist pattern in each sample is shown in FIG. 3.Zero means
No residue or having be it is a small amount of, × mean more residue.
As shown in figure 3, without hardening process, although the residue after not removing, by 120 DEG C with
And 140 DEG C of heating, produce the moderate finite deformation of photoresist pattern.As a result, without hardening, meaning
Functional layer film deposition when temperature can only rise to 100 DEG C or so.
On the other hand, in the sample B~D for having carried out hardening process, become the deformation of the photoresist pattern of problem
It is not generated under all heating temperatures.It is thus identified that the heat resistance for improving photoresist pattern by hardening.
As shown in figure 3, even if hardened, but when without wavelength control, produced in 120 DEG C or more of heating test
The residue of more photoresist is given birth to.Although 100 DEG C of heating test considers the temperature this is because hardening without residue
It is compared with the past lower (previous for more than 100 DEG C or so).
On the other hand, in the case where carrying out wavelength control, the sample C that temperature when for hardening is 30 DEG C, even if producing
It has given birth to the residue of photoresist but amount is less, preferably.In addition, carrying out wavelength control in hardening and being set as 100 DEG C of temperature
In the case where sample D, more residue is produced in the case where 140 DEG C of heating test, but in 100 DEG C and 120 DEG C of heating
In the case where test, residue is less, can use in practical.
The result shown in Fig. 3 is shown, preferably with respect to the exposed photosensitive wave more irradiated than photoresist
The heating temperature of substrate when the wavelength control of the short wavelength of long range and being hardened, and more preferably hardened is only
It is high.According to the research of inventor, the heating temperature of substrate when preferably hardening is 100 DEG C hereinafter, more have choosing is 70 DEG C
Below or 50 DEG C or less.In addition, it is further preferred that the heating temperature of substrate be 30 DEG C or less (such as 20~30 DEG C) or
Person's room temperature.
Illustrate to control in such hardening process medium wavelength below and the presence or absence of the photoresist residue after removing is generated
The reason of influence.Fig. 5 is the skeleton diagram for showing the mechanism of the hardening in the method for embodiment.
As described above, hardening is that the photoresist to form photoresist pattern is made to generate cross-linking reaction to improve polymerization
The processing of degree.In this case, such photoresist pattern 1 shown in (A) for Fig. 5, if with Gao Zhao as in the past
Degree irradiation includes the light of the wavelength domain of exposed photosensitive wave-length coverage to be hardened, then as shown in (B) of Fig. 5, it is believed that scheming
Cross-linking reaction is generated in the whole region of the depth direction of case, the degree of polymerization, which is enhanced, (in Fig. 5, to be indicated to improve polymerization with 1 '
The region of the photoresist pattern 1 of degree).Thus, it is believed that photoresist pattern 1 becomes steady relative to the combination of substrate
Gu generating the residue after more removing.
On the other hand, in the hardening of embodiment, it is believed that consider the light that biggish short wavelength side is absorbed due to using,
Therefore cross-linking reaction only carries out in the shallower region on surface, deeper region, particularly with the boundary part of substrate without handing over
Connection reacts but still keeps low polymerization degree (region for indicating holding low polymerization degree with 1 " in Fig. 5).Therefore, photoresist figure
Case 1 still keeps weaker relative to the combination of substrate, it is believed that improves heat resistance and is on the other hand held in removing using stripper
Easily removed.In other words, technical idea is that affect to the thermal deformation of photoresist pattern 1 is surface part
The degree of polymerization, in contrast, what residue when to removing affected is the contact portion with substrate, therefore makes the contact with substrate
The partial degree of polymerization is lower than the degree of polymerization of surface part.
In addition, can with 3 seconds~7 seconds or so short periods according to the research of inventor about the time needed for hardening
Obtain the effect of the raising of above-mentioned heat resistance.
Next, for the condition of the hardening process in embodiment, and it was compared to be illustrated in the past.Fig. 6 is
The figure shown will be compared with an embodiment in the past for the condition of hardening.
As shown in (A) of Fig. 6, previous hardening process purple for example since the temperature of substrate is 100 DEG C or so of state
Outside line irradiation continues ultraviolet light irradiation during heating the substrate within 70 seconds to 160 DEG C or so costs.
On the other hand, as shown in (B) of Fig. 6, in the embodiment for belonging to above embodiment, only to be slightly less than 30 DEG C
Temperature irradiate ultraviolet light 10 seconds.
In this way, in the method for embodiment, due to being hardened with 100 DEG C of lower temperatures below, heating with
And the time needed for cooling shortens, therefore hardens required overall time and be shortened.Therefore, production time (through put)
It shortens, productivity improves.Also, secondly, the cross-linking reaction of photoresist pattern 1 is alleviated and makes the contact portion with substrate
The degree of polymerization lower than surface section the degree of polymerization effect it is more significant.
According to the functional configuration manufacturing method of above-mentioned embodiment, due to improving the heat-resisting of photoresist pattern
Property, therefore the deposition of the film of functional layer can be carried out with higher temperature.Therefore, productivity is got higher.On the other hand, due to stripping
The residue of photoresist from after tails off, therefore the residue for reducing photoresist brings a negative impact the performance of product
The problem of.
Carrying out hardening this point using the short wavelength of the exposed photosensitive wave-length coverage than photoresist has following meanings,
Make to be hardened in making slow progress on the thickness direction of photoresist as described above, be easy to make in photoresist pattern with
The degree of polymerization of the boundary part of substrate still keeps lower.At this point, the suction of the light for the wavelength shorter than exposed photosensitive wave-length coverage
Yield, the characteristic of this larger photoresist has following meanings compared with for the absorptivity of the light of exposed photosensitive wave-length coverage
Justice, i.e. light are difficult to reach deeper part therefore are further easy to make still to keep lower with the degree of polymerization of the boundary part of substrate.
Further, since being carried out after being hardened in exposure process, the absorption of the light of the wavelength shorter than exposed photosensitive wave-length coverage
Rate biggish relationship compared with for the absorptivity of the light of exposed photosensitive wave-length coverage, as long as in photoresist after exposure
Establishment.
In addition, photoresist is typically eurymeric, but minus can also be implemented.In the case where minus, although photic anti-
The part for improving the degree of polymerization due to exposure when the formation of agent pattern is lost, is insoluble in developer solution and remaining pattern, but
Sometimes unreacted part residual further improves the degree of polymerization by ultraviolet light irradiation.In this case, exist pair
The photoresist of minus carry out based on ultraviolet light irradiate hardening the case where, in this case, also can as embodiment that
Sample is set as still keeping the lower degree of polymerization in the boundary part with substrate.Therefore, negative type photoresist can be implemented.But
It is that, about eurymeric, the significant effect that the heat resistance of the unexposed remaining eurymeric in part realized by hardening improves plays bigger
Meaning.
In addition, according to different photoresists, be especially in the presence of even if without polymerization initiator also due to ultraviolet light shines
The photoresist of cross-linking reaction is penetrated and generated, preferably includes polymerization initiator with ratio more than 0.1 weight percent degree.
In addition, in hardening process, about substrate, preferably not to base other than being heated the substrate by ultraviolet light irradiation
Plate is heated.The point is also for by making making slow progress for cross-linking reaction, to be easy to set in the boundary part with substrate
For the viewpoint for still keeping the lower degree of polymerization.If temperature is got higher, the progress of cross-linking reaction also becomes faster, thus in order to substrate
Boundary part in be set as still keeping the lower degree of polymerization and becoming easy the removing of no residue, the time management of cure process
It is particularly important.
Next, being illustrated to the embodiment of the invention of photoresist processing unit.Fig. 7 is the light of embodiment
Cause the front skeleton diagram of resist processing unit.
Device shown in Fig. 7 is the device used in the functional configuration manufacturing method of above embodiment, and is real
Apply the device of hardening process.The device has the illumination unit 4 and workbench 5 of the light source 41 including generating ultraviolet light.
Illumination unit 4 is more photic than this in exposure when will form the photoresist pattern 1 as object to be processed
The light of the short wavelength of the exposed photosensitive wave-length coverage of resist, with illumination higher compared with the light of the exposed photosensitive wave-length coverage
The unit being irradiated.In this embodiment, illumination unit 4 is the list that such wavelength control is carried out using filter 42
Member.Specifically, using the high-pressure mercury-vapor lamp of such luminescent spectrum shown in (A) of Fig. 4 as light source 41, in light source 41 and work
Make between platform 5 configured with to the light for the wavelength for being longer than 330nm blocked by filter 42.
Workbench 5 is to be built-in with temperature control device 51 in the component of the mesa-shaped of upper surface mounting substrate 3.In hardening,
Substrate 3 is irradiated by ultraviolet light to be heated, but optimum temperature when due to hardening is room temperature~30 DEG C or so, in the embodiment party
Temperature control device 51, which becomes, in formula carries out cooling device.Suitable for using by making refrigerant circulation to pass through workbench 5
By the cooling mechanism of substrate 3.3 vacuum suction of substrate is also applicable in for the viewpoint for improving heat exchanger effectiveness in workbench 5.
In addition, in the behind of light source 41 configured with the reflecting mirror 43 for improving light illumination efficiency.Light source 41 be with paper
Longer rodlike on the vertical direction in face, reflecting mirror 43 can be the sink shape of the length direction extension along light source 41.Reflecting mirror
43 reflecting surface can be in oval circular arc or parabolical situation.
In addition to this, device, which has, moves in substrate 3 and is placed in workbench 5, and by the substrate 3 being disposed from work
The transfer robot (not shown) etc. that platform 5 is removed.
In addition, device has the control unit (not shown) for controlling each portion.Control unit also controls the processing time of hardening.
Illumination unit 4 has gate 44, and the processing time is the time that gate 44 is opened.Control unit in order to foregoing hardening when
Between manage and regulating gate 44.
In the method for above-mentioned embodiment and device, use filter 42 as relatively more irradiations than exposure
The mechanism of the light of the short wavelength of photosensitive wavelength range, but also can be by using the light source of luminescent spectrum appropriate with reactive filter
It realizes on ground.As an example, it can be considered that using Excimer lamp as light source.
Fig. 8 is the skeleton diagram for being shown as the luminescent spectrum of the Excimer lamp of an example of light source.Wherein, Fig. 8's
(1) luminescent spectrum that the Excimer lamp for using XeCl as luminous gas is shown in is shown in (2) of Fig. 8 and is made using KrCl
For the luminescent spectrum of the Excimer lamp of luminous gas.
As shown in (1) of Fig. 8, XeCl Excimer lamp is the almost unicast near 308nm with stronger luminescent spectrum
Long lamp.In addition, KrCl Excimer lamp is the lamp near 222nm with the almost Single wavelength of stronger luminescent spectrum.Therefore,
These Excimer lamps can be suitable for it is foregoing by i line (365nm) be set as exposed photosensitive wavelength by photoresist dosage form
At photoresist pattern 1 cure process in.
In addition, the filter ended to the wavelength for being longer than arbitrary wavelength is easy to get, in contrast, only passing through light
The luminescent spectrum in source realizes the composition of the light of relatively more irradiations wavelength shorter than exposed photosensitive wave-length coverage, by the type of light source
Limitation, thus it is very uneasy.That is, having using the embodiment that filter carries out wavelength control can be easy to get most preferably
Resist processing result meaning.
In the above-described embodiment, exposed photosensitive wavelength is i line (365nm), and the condition of hardening is using 330nm as side
Boundary, its long light of weakening ratio compared with the light of the wavelength shorter than its, but this is an example, it both can be using 340nm as side
Boundary, can also be using 320nm as boundary.Also, it also can be using wavelength as 300nm or 280nm as boundary.
It is exposed in addition, KrF excimer laser (wavelength 248nm) or ArF resist excimer laser (wavelength 193nm) are used as
The photoetching of light light source is also practical, in the photoresist wherein used, the present application can also be implemented.Such as
For the photoresist by KrF excimer laser exposure, the KrCl quasi-molecule that luminescent spectrum is shown in (2) of Fig. 8 is used
Lamp is hardened as embodiment described above.In addition, though the illustration is omitted, Xe2*Excimer lamp is the several of wavelength 172nm
The lamp of Single wavelength can be used in the hardening of the photoresist of ArF excimer laser exposure.In addition, for KrF standard point
The photoresist of sub- laser explosure or the photoresist of ArF excimer laser exposure, also can be using lamp and filtering
The illumination unit that device is composed also is able to use Cooper-Hewitt lamp etc. as lamp other than high-pressure mercury-vapor lamp.
In addition, as functional layer, about the formation of the electrode pattern in display apparatus above-mentioned or lighting apparatus, function
It is an example that function in layer, which is electrical function, and in addition to this, insulating effect or charge savings also may be implemented in functional layer
Effect etc., or mechanical effect as micromachine also may be implemented.Also, it also sometimes will be real as catalyst action
Now the layer of effect chemically is formed as functional layer.
[embodiment]
Next, being illustrated to embodiment.The following are the good implementations of the present application confirmed by inventor
Example.
Firstly, using the LUMILON (registered trademark of the said firm) of JSR joint-stock company as photoresist, form
Two layers of photoresist layer.Specifically, coating LUMILON LP-0101 as lower layer with 1 μm of thickness, and carry out
120 DEG C, baking in 180 seconds.LUMILON LP0500 is coated with 2 μm of thickness on it, and has carried out the baking of 110 DEG C, 180 seconds
It is roasting.
The photoresist layer is exposed with i line.Accumulative light quantity in exposure is set as 120mJ/cm2。
Developed after exposure with TMAH (tetramethyl-ammonium=hydroxide) developer solution of 2.38 weight %.Development is paddle
Formula development, is set as the condition of 23 DEG C, 60 seconds.
After development, hardening process is implemented later with the cleaning of pure water progress 60 seconds.Hardening is to carry out Fig. 4's
(B) 30 DEG C, 5 minutes in the state of wavelength control are condition.
After hardening, golden film is formed as functional layer film using the thickness of 100nm using magnetron sputtering.Investment electricity in sputtering
Power is 400W, and the flow of the argon as sputtering gas is 25sccm, and film formation time is 1600 seconds.
Later, it using NMP, is removed.It peels through and 23 DEG C of NMP liquid is implemented to impregnate for 300 seconds to carry out.
After removing, cleaning in 600 seconds is carried out with 20 DEG C of IPA (isopropanol), and carried out 30 with 23 DEG C of pure water
The cleaning of second.Substrate after cleaning is confirmed, the residue of resist is not confirmed, but has confirmed and has carried out well
The formation of functional layer.
Claims (11)
1. a kind of functional configuration manufacturing method, manufacture includes the functional configuration body for the functional layer being patterned, and feature exists
In, comprising:
The photoresist pattern formation process of photoresist pattern is formed on substrate；
After photoresist pattern formation process, consolidate photoresist pattern photoresist pattern irradiating ultraviolet light
Change the hardening process improved；
After hardening process, to not sunk by the film of the film for the site deposition functional layer that photoresist pattern covers on substrate
Product process；And
After film deposition procedures, the film of photoresist pattern and the functional layer being placed in photoresist pattern is removed
Stripping process,
Hardening process is exposed with the accumulative light amount ratio of the wavelength ultraviolet light shorter than the exposed photosensitive wave-length coverage of photoresist
The process that mode more than the accumulative light quantity of the light of photosensitive wavelength range irradiates the ultraviolet light.
2. functional configuration manufacturing method as described in claim 1, which is characterized in that
The hardening process is compared with the light of wavelength ratio 330nm long with the ultraviolet of high illumination irradiation 330nm wavelength below
The process of line.
3. functional configuration manufacturing method as claimed in claim 1 or 2, which is characterized in that
The absorptivity of the photoresist ultraviolet light shorter than the exposed photosensitive wave-length coverage to wavelength is greater than to the exposure
The absorptivity of the light of light sensation optical wavelength range.
4. functional configuration manufacturing method as claimed in claim 1 or 2, which is characterized in that
The photoresist is eurymeric.
5. functional configuration manufacturing method as claimed in claim 1 or 2, which is characterized in that
The photoresist includes the polymerization initiator of 0.1 weight percent or more.
6. functional configuration manufacturing method as claimed in claim 1 or 2, which is characterized in that
In the hardening process, the temperature of the substrate is set as 100 DEG C or less.
7. functional configuration manufacturing method as claimed in claim 1 or 2, which is characterized in that
In the hardening process, the temperature of the substrate is set as 30 DEG C or less.
8. functional configuration manufacturing method as claimed in claim 1 or 2, which is characterized in that
In the hardening process, the substrate is not heated in addition to irradiating progress heating using the ultraviolet light.
9. functional configuration manufacturing method as claimed in claim 1 or 2, which is characterized in that
In the hardening process, the ultraviolet light is irradiated while cooling down the substrate.
10. a kind of photoresist processing unit, which is characterized in that have:
Illumination unit, the light source including generating ultraviolet light；And
Workbench, mounting are formed with the substrate of photoresist pattern,
Illumination unit is so that the exposed photosensitive wave-length coverage of photoresist of the wavelength than forming photoresist pattern is short
Ultraviolet light becomes the mode of the accumulative light quantity more than the light of exposed photosensitive wave-length coverage, and the unit of the ultraviolet light is irradiated to substrate.
11. photoresist processing unit as claimed in claim 10, which is characterized in that
The illumination unit has compared with the transmissivity of the light of the exposed photosensitive wave-length coverage, and wavelength is than the exposed photosensitive
The high filter of the short transmission of ultraviolet rays of wave-length coverage.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
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| JP2017139686A JP2019021794A (en) | 2017-07-19 | 2017-07-19 | Functional structure manufacturing method and photoresist processing apparatus |
| JP2017-139686 | 2017-07-19 |
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| CN109283787A true CN109283787A (en) | 2019-01-29 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112015059A (en) * | 2019-05-31 | 2020-12-01 | 夏普株式会社 | Method for removing organic resin film and method for manufacturing semiconductor device |
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| CN110379707B (en) * | 2019-08-21 | 2024-05-28 | 无锡英菲感知技术有限公司 | Metal patterned stripping structure and manufacturing method thereof |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63133628A (en) * | 1986-11-26 | 1988-06-06 | Alps Electric Co Ltd | Treatment of positive-type photoresist |
| JP3030102B2 (en) * | 1991-02-08 | 2000-04-10 | 関西ペイント株式会社 | Coating method |
| JPH06214402A (en) * | 1992-10-30 | 1994-08-05 | Matsushita Electric Ind Co Ltd | Formation of fine pattern |
| JP3330214B2 (en) * | 1993-12-14 | 2002-09-30 | 三菱電機株式会社 | Method of forming multilayer resist pattern and method of manufacturing semiconductor device |
| JPH10333340A (en) * | 1997-05-27 | 1998-12-18 | Sharp Corp | Forming method of resist pattern |
| US7229745B2 (en) * | 2004-06-14 | 2007-06-12 | Bae Systems Information And Electronic Systems Integration Inc. | Lithographic semiconductor manufacturing using a multi-layered process |
| US7960097B2 (en) * | 2007-10-30 | 2011-06-14 | Triquint Semiconductor, Inc. | Methods of minimizing etch undercut and providing clean metal liftoff |
| KR101353012B1 (en) * | 2009-11-17 | 2014-01-22 | 가부시키가이샤 히다치 하이테크놀로지즈 | Sample treatment device, sample treatment system, and method for treating a sample |
| JP2015057633A (en) * | 2013-08-16 | 2015-03-26 | 東京応化工業株式会社 | Method for forming resist pattern |
| JP6520673B2 (en) * | 2015-12-07 | 2019-05-29 | 豊田合成株式会社 | Semiconductor device manufacturing method |
-
2017
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| CN112015059A (en) * | 2019-05-31 | 2020-12-01 | 夏普株式会社 | Method for removing organic resin film and method for manufacturing semiconductor device |
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Application publication date: 20190129 |