CN104698745B - A kind of controllable nanometer blocks production method of size - Google Patents
A kind of controllable nanometer blocks production method of size Download PDFInfo
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- CN104698745B CN104698745B CN201510076382.0A CN201510076382A CN104698745B CN 104698745 B CN104698745 B CN 104698745B CN 201510076382 A CN201510076382 A CN 201510076382A CN 104698745 B CN104698745 B CN 104698745B
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Abstract
The invention discloses a kind of controllable nanometer blocks production methods of size, this method comprises: a photoresist layer is arranged in the upper surface of substrate；First time exposure is carried out to the substrate, to record one-dimensional grating figure on photoresist layer；Substrate after exposing to first time is developed, to manifest one-dimensional photoresist grating pattern；Second of exposure and imaging is carried out to the substrate after development, so that one-dimensional photoresist grating pattern is become photoresist nanometer block array；After being performed etching to the substrate with photoresist nanometer block array, photoresist is removed, to realize the production of nanometer blocks.Method of the invention has the advantages that nanometer block size equipment that is controllable, at low cost, being not required to complexity and can be used for large-area manufacturing.It the composite can be widely applied in the field of nanometer blocks production.
Description
Technical field
The present invention relates to the manufacture craft of nanometer blocks more particularly to a kind of controllable nanometer blocks production methods of size.
Background technique
Nanometer block array is in the one-dimentional structures array such as magnetic storage, opto-electronic device, biosensor and nano wire, nanotube
Preparation field in have significant application value.By the scientific research of more than ten years, there are many sides of production nanometer block array
Method.However, come with some shortcomings in existing nanometer blocks production method at present, such as: electron beam or focused ion beam exposure
Method, used equipment is expensive, and has production efficiency low, and is unfavorable for the disadvantages of large area produces, and this method is logical
Often it is only used for use when making in laboratory a small amount of sample；Film deposition or Chemical self-assembly method, although its simple process, also preferably
It is produced in large area, it can be difficult to obtaining that size distribution is relatively narrow and the more perfect nanometer block array of latticed form；Nano impression
Method is this several years faster technologies of development, it can realize the preparation of large area even block, but used by it
Impression block is difficult to make, and is often also required to combine above-mentioned electron beam exposure method when making template.Thus, one
Kind of low cost, be easily achieved and the controllable nanometer blocks production method of size be at present technical problem in the urgent need to address it
One.
Summary of the invention
In order to solve the above-mentioned technical problem, the object of the present invention is to provide it is a kind of it is at low cost, be easily achieved and size is controllable
The nanometer blocks production method of system.
The technical scheme adopted by the invention is that: a kind of controllable nanometer blocks production method of size, this method comprises:
S1, one photoresist layer is set in the upper surface of substrate；
S2, first time exposure is carried out to the substrate, to record one-dimensional grating figure on photoresist layer；
S3, develop to the substrate after first time exposure, to manifest one-dimensional photoresist grating pattern；
S4, second of exposure and imaging is carried out to the substrate after developing in step S3, thus by one-dimensional photoresist grating figure
Case becomes photoresist nanometer block array；
S5, after being performed etching to the substrate with photoresist nanometer block array, photoresist is removed, to realize nanometer blocks
Production.
Further, the step S4, specifically:
By the edge exposure technology based on mask plate, exposed to carry out second to the substrate after developing in step S3
Light, the substrate after then exposing to second is developed, so that one-dimensional photoresist grating pattern is become photoresist nanometer blocks
Array.
Further, the step S4 includes:
S41, the mask plate with grating pattern is placed in the substrate after developing in the step S3, on the mask plate
Grating lines direction it is vertical with the grating lines direction in the substrate；
S42, substrate described in step S41 is carried out to expose for second, the substrate after then exposing second carries out
Development, so that one-dimensional photoresist grating pattern is become photoresist nanometer block array.
Further, the step S2, specifically:
By way of holographic lithography or the mode of mask plate edge exposure carries out first time exposure to the substrate, from
And one-dimensional grating figure is recorded on photoresist layer.
Further, the mode of the holographic lithography, specifically: using laser as light source, pass through spatial filter
The laser issued to laser carries out after expanding filtering, so that laser is formed interference fringe using Laue mirror optical path.
Further, the step for substrate after exposing described in the step S3 to first time is developed, specifically:
Substrate after first time is exposed, which is placed in the KOH solution that mass percent concentration is 0.5%, develops.
Further, step S0, the step S0 are as follows: pre-process to substrate are additionally provided with before the step S1.
Further, the step S0 specifically:
It after substrate clear water and acetone are cleaned, is placed in baking oven, 10 minutes removing steam and remnants is toasted at 130 DEG C
Acetone carries out oxygen gas plasma processing after baking.
Further, vacuum degree used by the oxygen gas plasma is handled is 25 Pa, and power is 60 W, bombardment time
It is 90 seconds.
Further, the substrate is silicon wafer or glass.
The beneficial effects of the present invention are: method of the invention is to complete photoresist nanometer blocks by double exposing and developing
Then the production of array performs etching the substrate with photoresist nanometer block array, due to photoresist nanometer block array conduct
Therefore the pattern of nanometer block array after performing etching, can be transferred in substrate by protective layer, then, by the photoresist in substrate
Just the production of nanometer blocks is completed after removing.Thus, passing through control technique ginseng for the production method of nanometer blocks of the present invention
Number, such as exposure dose and/or interference angle, to can control the size of nanometer blocks, production flexibility is high, Er Qieben
The method of invention also have many advantages, such as not need complicated equipment, it is at low cost, can be used for large-area manufacturing.
Detailed description of the invention
Specific embodiments of the present invention will be further explained with reference to the accompanying drawing:
Fig. 1 is a kind of step flow chart of the controllable nanometer blocks production method of size of the present invention；
Fig. 2 is the technique of holographic exposure in a kind of controllable one specific embodiment of nanometer blocks production method of size of the present invention
Step schematic diagram；
Fig. 3 is in a kind of controllable one specific embodiment of nanometer blocks production method of size of the present invention based on PDMS mask plate
The processing step schematic diagram of edge exposure；
Fig. 4 is the system of PDMS mask plate in a kind of controllable one specific embodiment of nanometer blocks production method of size of the present invention
Make technique step schematic diagram.
Specific embodiment
As shown in Figure 1, a kind of controllable nanometer blocks production method of size, this method comprises:
S1, one photoresist layer is set in the upper surface of substrate；
S2, first time exposure is carried out to the substrate, to record one-dimensional grating figure on photoresist layer；
S3, develop to the substrate after first time exposure, to manifest one-dimensional photoresist grating pattern；
S4, second of exposure and imaging is carried out to the substrate after developing in step S3, thus by one-dimensional photoresist grating figure
Case becomes photoresist nanometer block array；
S5, after being performed etching to the substrate with photoresist nanometer block array, photoresist is removed, to realize nanometer blocks
Production.
It is further used as preferred embodiment, the step S4, specifically:
By the edge exposure technology based on mask plate, exposed to carry out second to the substrate after developing in step S3
Light, the substrate after then exposing to second is developed, so that one-dimensional photoresist grating pattern is become photoresist nanometer blocks
Array.Preferably, the edge exposure technology based on mask plate is the edge exposure technology based on PDMS mask plate.
It is further used as preferred embodiment, the step S4 includes:
S41, the mask plate with grating pattern is placed in the substrate after developing in the step S3, on the mask plate
Grating lines direction it is vertical with the grating lines direction in the substrate；
S42, substrate described in step S41 is carried out to expose for second, the substrate after then exposing second carries out
Development, so that one-dimensional photoresist grating pattern is become photoresist nanometer block array.When the edge based on mask plate of use exposes
When light technology is the edge exposure technology based on PDMS mask plate, the mask plate is then PDMS mask plate.
It is further used as preferred embodiment, the step S2, specifically:
By way of holographic lithography or the mode of mask plate edge exposure carries out first time exposure to the substrate, from
And one-dimensional grating figure is recorded on photoresist layer.When by the way of holographic lithography expose for the first time to substrate,
By changing two interfering beams in the angle on photoresist layer surface, then the one-dimensional grating figure of different interval just can be made, and
It is then by selecting different exposure doses when by the way of mask plate edge exposure expose for the first time to substrate
To make the one-dimensional grating figure of different interval.
It is further used as preferred embodiment, the mode of the holographic lithography, specifically: using laser as light
Source, carries out after expanding filtering the laser that laser issues by spatial filter, forms laser using Laue mirror optical path dry
Relate to striped.
It is further used as preferred embodiment, the substrate after exposing described in the step S3 to first time is developed
The step for, specifically:
Substrate after first time is exposed, which is placed in the KOH solution that mass percent concentration is 0.5%, develops.
Similarly, when the substrate after exposing to second is developed, the substrate after can also exposing second is placed in
Develop in the KOH solution that mass percent concentration is 0.5%.
It is further used as preferred embodiment, step S0, the step S0 are as follows: right are additionally provided with before the step S1
Substrate is pre-processed.
Preferably, the step S0 specifically:
It after substrate clear water and acetone are cleaned, is placed in baking oven, 10 minutes removing steam and remnants is toasted at 130 DEG C
Acetone carries out oxygen gas plasma processing after baking.It is handled preferably for the oxygen gas plasma, used by
Vacuum degree is 25 Pa, and power is 60 W, and bombardment time is 90 seconds.
It is further used as preferred embodiment, the substrate is silicon wafer or glass.The photoresist layer is positivity
Photoresist layer or negative photo glue-line.
One specific embodiment of the method for the present invention
A kind of controllable nanometer blocks production method of size, it is shown that specific step is as follows.
Holographic exposure technique is carried out first, as shown in Fig. 2, the specific steps of the technique of the holographic exposure include:
Step 1: pre-processing to substrate 1, the substrate 1 can be a silicon wafer or a glass；
For described the step for being pre-processed to substrate 1, specifically, after the clear water of substrate 1 and acetone are cleaned,
It is placed in baking oven, 10 minutes removing steam and residual acetone is toasted at 130 DEG C, oxygen gas plasma processing is carried out after baking,
Increase substrate 1 surface can, vacuum degree used by the oxygen gas plasma is handled is 25 Pa, and power is 60 W, when bombardment
Between be 90 seconds.
Step 2: photoresist to be spun on to the upper surface of pretreated substrate 1, i.e., it is arranged one in the upper surface of substrate 1
Photoresist layer 2, the thickness of the photoresist layer 2 dry the substrate 1 with photoresist layer 2 at 90 DEG C in 1 microns
It is 5 minutes roasting.
Step 3: exposure 3 for the first time is carried out to the substrate 1 after toasting in step 2 by way of holographic lithography, thus
One-dimensional grating figure is recorded on photoresist layer 2.Time and dosage for exposure should be according to the thickness and light of the photoresist layer 2
It is strong to determine.
For the mode of the holographic lithography, specifically: using the laser of certain wavelength as light source, pass through space
Filter carries out after expanding filtering the laser that laser issues, and so that laser is formed interference fringe using Laue mirror optical path.Work as labor
When the angle of reflecting mirror and photoresist layer 2 in angstrom mirror optical path is 90o, the period of interference fringe is d=λ/(2sin θ),
Wherein, λ is optical maser wavelength, and θ is angle of two interfering beams on photoresist layer surface, i.e. interference angle.Therefore, using described
The mode of holographic lithography to carry out single exposure to substrate 1, and what the photoresist layer 2 was recorded is one-dimensional lines figure
Shape, i.e. one-dimensional grating figure.Thus, different θ can produce the one-dimensional photoresist grating pattern of different interval.
Step 4: the substrate 1 after exposing first time is placed in the KOH that mass percent concentration is 0.5% after the completion of exposure
Develop in solution, after development, then can manifest one-dimensional photoresist grating pattern 4.A is the schematic top plan view of substrate in Fig. 2.
Then edge exposure technique is carried out, as shown in figure 3, the technique specific steps of the edge exposure include:
Step 5: the PDMS mask plate 5 with grating pattern is placed in the substrate 1 after developing for the first time, it is described to have
The grid stroke of one-dimensional photoresist grating pattern 4 on grating lines direction and the substrate 1 on the PDMS mask plate 5 of grating pattern
Direction is vertical, i.e. one-dimensional photoresist on grating lines direction on the PDMS mask plate 5 with grating pattern and the substrate 1
The grating lines direction placement in 90 ° of grating pattern 4.
For the above-mentioned PDMS mask plate 5 with grating pattern, be by way of duplication made from, step as scheme
Shown in 4, configured PDMS viscous fluid 12 is toppled and is shakeout on grating mother matrix 11, the grating mother matrix 11 can be by covering
The modes such as diaphragm plate exposure or holographic exposure make.After grating mother matrix 11 is completely covered in PDMS viscous fluid 12, toasted with 60 DEG C
Solidify PDMS within 30 minutes, then remove cured PDMS layer from grating mother matrix 11, to obtain with grating pattern
PDMS mask plate 5.Wherein, PDMS viscous fluid 12 is by PDMS performed polymer (184 elastomer of Sylgard) and curing agent
(184 curing agent of Sylgard) is mixed according to volume ratio 10:1 and is obtained.
Step 6: after the covering of PDMS mask plate 5 with grating pattern places on the base 1, in ultraviolet light
Under be exposed 6, i.e., second is carried out to the substrate 1 and exposed.Due to the edge exposure effect of the PDMS mask plate, root
Different exposure effects can be obtained according to different exposure doses, for example, exposure dose can obtain wider lines 7a when smaller, exposed
Light dosage can obtain relatively narrow lines 7b when larger.
It is shown Step 7: the substrate 1 after second is exposed is placed in the KOH solution that mass percent concentration is 0.5%
Shadow.Due to the exposure of vertical direction twice, after second development, original one-dimensional photoresist grating pattern 4 then be will become
Photoresist nanometer block array 8.At this point, the schematic top plan view of substrate 1 is as shown in b and c in Fig. 3.
According to the PDMS mask plate edge exposure of above-mentioned steps six it is found that its exposure when exposure dose selection difference, can
So that nanometer blocks it is of different size (wider lines 7a can be obtained when exposure dose is smaller, can be obtained when exposure dose is larger compared with
Narrow lines 7b), thus, by the difference of exposure dose when selection exposure, thus can be to the width of the nanometer blocks of production
Degree size is controlled.
Step 8: the substrate 1 with photoresist nanometer block array 8 is placed in reactive ion etching machine after developing in step 7
Inside perform etching.Due to the protective effect of remaining photoresist, only the part of photoresist is not etched away, the part etched away
As shown in the signified part of label 9 in Fig. 3.
Step 9: finally removing remaining photoresist in substrate 1 with acetone, so that the production of nanometer blocks is completed, in Fig. 3
Shown in label 10, d and e.And for manufactured nanometer blocks, the mother matrix that can be used as nano impression uses.
It can be seen from the above, method of the invention is that photoresist nanometer block array is made by double exposing and developing,
Then, since the photoresist nanometer block array can be used as protective layer, the substrate with photoresist nanometer block array is passed through
After ion etching technology performs etching, just nanometer blocks pattern is transferred in substrate, to complete the production of nanometer blocks.Thus may be used
, compared to previous nanometer blocks production method, method of the invention is had at least the following advantages:
1, this method does not need complicated equipment, at low cost, can be used for the production in big face.
2, the nanometer block size made can be controlled by technological parameter difference.When holographic exposure, that is, pass through holographic optical
The mode at quarter can make different interval by changing two interfering beams in the angle on photoresist layer surface come when being exposed
One-dimensional grating.And when edge exposure, then it can change nanometer blocks width size by different exposure doses.
3, photoresist nanometer block array is transferred in substrate by the method etched.The manufactured nanometer blocks, Ke Yiyong
Do the mother matrix of nano impression.
It is to be illustrated to preferable implementation of the invention, but the invention is not limited to the implementation above
Example, those skilled in the art can also make various equivalent variations on the premise of without prejudice to spirit of the invention or replace
It changes, these equivalent deformations or replacement are all included in the scope defined by the claims of the present application.
Claims (8)
1. a kind of controllable nanometer blocks production method of size, it is characterised in that: this method comprises:
S1, one photoresist layer is set in the upper surface of substrate；
S2, first time exposure is carried out to the substrate, to record one-dimensional grating figure on photoresist layer；
S3, develop to the substrate after first time exposure, to manifest one-dimensional photoresist grating pattern；
S4, second of exposure and imaging is carried out to the substrate after developing in step S3, so that one-dimensional photoresist grating pattern be become
For photoresist nanometer block array；
S5, after being performed etching to the substrate with photoresist nanometer block array, photoresist is removed, to realize the system of nanometer blocks
Make；
The step S4 includes:
S41, the mask plate with grating pattern is placed in the substrate after developing in the step S3, the light on the mask plate
Grid line orientations are vertical with the grating lines direction in the substrate；
S42, substrate described in step S41 being carried out to expose for second, the substrate after then exposing to second is developed,
To which one-dimensional photoresist grating pattern is become photoresist nanometer block array.
2. the controllable nanometer blocks production method of a kind of size according to claim 1, it is characterised in that: the step
S2, specifically:
By way of holographic lithography or the mode of mask plate edge exposure carries out first time exposure to the substrate, thus
One-dimensional grating figure is recorded on photoresist layer.
3. the controllable nanometer blocks production method of a kind of size according to claim 2, it is characterised in that: the holographic lithography
Mode, specifically: using laser as light source, the laser that laser issues is carried out expanding filter by spatial filter
After wave, laser is set to form interference fringe using Laue mirror optical path.
4. the controllable nanometer blocks production method of a kind of size according to claim 3, it is characterised in that: in the step S3
The step for substrate after the exposure to first time is developed, specifically:
Substrate after first time is exposed, which is placed in the KOH solution that mass percent concentration is 0.5%, develops.
5. the controllable nanometer blocks production method of a kind of size according to claim 1, it is characterised in that: the step S1 it
Before be additionally provided with step S0, the step S0 are as follows: pre-process to substrate.
6. the controllable nanometer blocks production method of a kind of size according to claim 5, it is characterised in that: the step S0 tool
Body are as follows:
It after substrate clear water and acetone are cleaned, is placed in baking oven, 10 minutes removing steam and remnants third is toasted at 130 DEG C
Ketone carries out oxygen gas plasma processing after baking.
7. the controllable nanometer blocks production method of a kind of size according to claim 6, it is characterised in that: described oxygen etc. from
Vacuum degree used by daughter is handled is 25Pa, and power 60W, bombardment time is 90 seconds.
8. the controllable nanometer blocks production method of a kind of size according to claim 4, it is characterised in that: the substrate is
Silicon wafer or glass.
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108873134A (en) * | 2018-07-06 | 2018-11-23 | 福建中科晶创光电科技有限公司 | A kind of more godmothers version preparing grating method based on glue curing |
| CN109270046B (en) * | 2018-08-30 | 2020-11-17 | 东南大学 | Construction method and application of controllable micro-nano array based on gold-silver nano bricks |
| CN110902647B (en) * | 2019-12-05 | 2023-07-04 | 深圳先进技术研究院 | Manufacturing method of nano channel with gradually changed size |
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| CN103226215A (en) * | 2013-04-19 | 2013-07-31 | 中国科学院半导体研究所 | Preparation method of holographic grating provided with surface with periodically graded width |
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| KR20120032024A (en) * | 2007-05-23 | 2012-04-04 | 제이에스알 가부시끼가이샤 | Radiation-sensitive resin composition |
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| CN101126900A (en) * | 2007-08-31 | 2008-02-20 | 中国科学院光电技术研究所 | Photolithography method based on metal local effect |
| CN102859441A (en) * | 2010-01-12 | 2013-01-02 | 罗利诗公司 | Nanopatterning method and apparatus |
| CN102096335A (en) * | 2010-12-31 | 2011-06-15 | 上海集成电路研发中心有限公司 | Double-exposure method |
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