CN110174818A - The nano impression preparation method and its substrate of substrate - Google Patents
The nano impression preparation method and its substrate of substrate Download PDFInfo
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- CN110174818A CN110174818A CN201910479163.5A CN201910479163A CN110174818A CN 110174818 A CN110174818 A CN 110174818A CN 201910479163 A CN201910479163 A CN 201910479163A CN 110174818 A CN110174818 A CN 110174818A
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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
- G03F7/0002—Lithographic processes using patterning methods other than those involving the exposure to radiation, e.g. by stamping
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Abstract
The invention discloses a kind of nano impression preparation methods of substrate, comprising: provides the soft template with nano impression figure；Substrate in combination is provided, the substrate in combination includes the substrate；The substrate in combination is imprinted according to the soft template, so that the substrate in combination includes nano graph, the nano graph is corresponding with the nano impression figure, and the nano graph includes groove；The first hard mask layer is formed on the top surface of the nano graph, the top surface does not surround the groove；The substrate is performed etching according to first hard mask layer, so that the substrate includes nanostructure.By the invention it is possible to significantly improve the depth-to-width ratio of primer mask, obtain high-aspect-ratio and high-precision nanostructure image substrate.
Description
Technical field
The invention belongs to the nano impression preparation method of nano graph preparation technical field more particularly to a kind of substrate and answer
With.
Background technique
The common prior art is as follows in the industry.
Nanostructure is the structure of object of the size between molecule and micro-meter scale.It is pressed with the urstoff of nanoscale
Certain aligned transfer gets up to be formed one-dimensional, two-dimentional, cubical array nano structural material, since it has nanoparticle
Feature, such as the features such as quantum size effect, small-size effect, skin effect, but exist by nanostructure combine caused by newly
Effect, such as quantum coupling effect and synergistic effect.Secondly, this nano structural material is easy to through additional electricity, magnetic, light
The control to its performance is realized in field, realizes the application of various functionalization.In next-generation figure transfer technology, electron-beam direct writing, X
X ray exposure x and nanometer embossing occupy an important position.Wherein nanometer embossing is high with yield, at low cost and technique is simple
Single advantage, is the important manufacturing technology of nanoscale electronic devices.With the development of the micro fabrications such as nanometer embossing,
Various nanostructure figures are produced out.
Nanometer embossing is to obtain one kind method at low cost and fireballing of replicated architecture in nanoscale, it can be with
The high resolution design that high-volume repeatedly prepares nano graph structure over a large area, and produced has fairly good
Uniformity and repeatability.It is suitable for nanostructure figure to send out towards large area, low cost, micro-nano size and integrated direction
Exhibition.
Using traditional nanometer embossing of direct mechanical contact hot padding mode, transfer visuals area will lead to
Domain causes figure imperfect because of impression block is not directly contacted, namely the reduction of coining quality.
Summary of the invention
In view of the problems of the existing technology, the present invention provides a kind of nano impression preparation method and applications of substrate.
The main purpose of the present invention is to provide a kind of nano impression preparation methods of substrate, comprising:
Soft template provides step, has the soft template of nano impression figure including providing；
Substrate provides step, including providing substrate and the coining glue-line on the substrate；
Imprint step, including the coining glue-line is imprinted according to the soft template, so that the coining glue-line packet
Nano graph is included, the nano graph is corresponding with the nano impression figure, and the nano graph includes running through the coining
The groove of the top surface of glue-line；
First hard mask layer forming step, including forming the first hard mask layer on the top surface of the nano graph；
Etching step, including the substrate is performed etching according to first hard mask layer, so that the substrate includes
Nanostructure.
In an embodiment of the present invention, the soft template provides step and specifically includes:
Step a, including by photoetching process, hard template is made, so that the hard template includes transfer coining pattern；
Step b, including the soft template is imprinted according to the hard template, so that the soft template includes described receives
Rice coining pattern, wherein the hardness of the soft template is lower than the hard template.
In an embodiment of the present invention, the first etch layer and the second etching are equipped between the substrate and the coining glue-line
Layer, wherein second etch layer is located at the side close to the coining glue of first etch layer, the imprint step tool
Body includes:
Step (1), including the coining glue-line is imprinted using the soft template, so that the coining glue-line includes
The nano graph, the nano graph is corresponding with the nano impression figure, and the nano graph includes the groove；
Step (2), including forming first hard mask layer on the top surface of the nano graph of the coining glue-line；
Step (3), including by etching technics, using first hard mask layer as etch mask, etch the second etch layer；
Step (4), including pass through etching technics, first hard mask layer obtained with step (3), the coining glue-line
It is etch mask with second etch layer, etches first etch layer, wherein the etch rate of first etch layer is big
In the etch rate of second etch layer；
Step (5), including pass through etching technics, first hard mask layer obtained with step (4), the coining glue
Layer, second etch layer and first etch layer are etch mask, etch the substrate, so that the substrate includes described
Nanostructure；
Step (6), first hard mask layer in structure, the coining glue-line, institute obtained including removal step (5)
State the second etch layer and first etch layer.
In an embodiment of the present invention, between the step (2) and the step (5), the method also includes:
Step (2a), including the coining glue-line is etched using the first hard mask layer as etch mask by etching technics.
In an embodiment of the present invention, the soft template is polymethyl methacrylate or polydimethyl siloxane material
It is made；Second etch layer includes silica, silicon nitride, metallic aluminium, crome metal or amorphous carbon material；And described
The material of one etch layer is STU-2 or STU-8 material；The material of first hard mask layer is silica, silicon nitride, gold
Belong to aluminium, crome metal or amorphous carbon film, thickness is in 10nm-100nm.
Another object of the present invention is to provide a kind of height prepared by the nano impression preparation method using the substrate
Depth-to-width ratio nanostructure substrate.
Another object of the present invention is to provide a kind of photonic crystals, including the use of the nano impression preparation side of the substrate
The substrate of method preparation.
Another object of the present invention is to provide a kind of semiconductor devices, prepare including the use of the nano impression of the substrate
The substrate of method preparation.
Another object of the present invention is to provide a kind of display panels, prepare including the use of the nano impression of the substrate
The substrate of method preparation.
Another object of the present invention is to provide a kind of display devices, prepare including the use of the nano impression of the substrate
The substrate of method preparation.
In conclusion advantages of the present invention and good effect are as follows:
The advantage of present invention combination nano-imprinting method is etched residual in coining glue mask layer by dry etch process
Glue, smooth and etch resistant hard mask layer can guarantee that the residue glue for imprinting glue mask layer different-thickness is removed clean, while right
Multiple etching operation between glue exposure mask and hard exposure mask with different etching rate is realized under the conditions of hard mask layer etch resistant
To the higher etch rate of glue-line, the image fine degree of nanostructure figure can be largely improved, is obtained larger deep wide
The nanostructure figure of ratio.Controllability of the present invention is good, and repeatability operation is particularly suitable for production semiconductor nano device, light
The nano graphs structure such as sub- crystal.
Using method provided by the invention, the soft template replicated with the hard template of depth-to-width ratio 1:1, coining is obtained and template phase
With the figure of depth-to-width ratio, then passing through multiple etching mask, can produce depth-to-width ratio is the nanometer for being less than 500nm in 10, period
Figure, the depth-to-width ratio for the figure that comparison is obtained with traditional mechanical stamping usually have progress significant in 1-6 or so.
Detailed description of the invention
Fig. 1 is the production schematic diagram of soft template provided in an embodiment of the present invention；
Fig. 2 is the schematic diagram that each film layer is formed on substrate provided in an embodiment of the present invention；
Each processing step of the nano-imprinting method of Fig. 3 a- Fig. 3 f step 3a-3f provided in an embodiment of the present invention is shown
It is intended to.
In figure: 100, hard template；101, soft template；201, substrate；2001, nanostructure substrate；202, primer layer；
2002, primer mask layer；203, hard membrane layer；2003, the second hard mask layer；204, glue-line is imprinted；2004, glue mask layer is imprinted；
205, the first hard mask layer；2005, the first thinned hard mask layer.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to embodiments, to the present invention
It is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, it is not used to
Limit the present invention.
Soft mode plate technique in the prior art the problem is that: the easy curved soft template of deformation is easy in moulding process
The residue glue that depth does not wait is formed, the uniformity and large area for influencing nanostructure figure transfer.Also it be easy to cause figure curved simultaneously
Song collapses, and seriously constrains processed nano-scale pattern depth-to-width ratio, while may cause the distortion of nano graph.
In view of the above-mentioned problems, the present invention is described in detail with reference to the accompanying drawing.
Fig. 1 is please referred to, Fig. 1 is the production schematic diagram of the soft template in the nano impression preparation method of substrate of the present invention.
The nano impression preparation method of substrate of the present invention includes: that soft template provides step, substrate provides step, coining step
Suddenly, the first hard mask layer forming step and etching step.
The soft template provides step, has the soft template 101 of nano impression figure including providing.
The soft template provides step and specifically includes step a and step b.The step a, including pass through photoetching process,
Hard template 100 is made, so that the hard template 100 includes transfer coining pattern.The step b, including according to the hard template
100 pairs of soft templates 101 imprint, so that the soft template 101 includes the nano impression figure, wherein described soft
The hardness of template 101 is lower than the hard template 100.
The substrate provides step, including providing substrate 201 and the coining glue-line 204 on the substrate 201.
The imprint step, including the coining glue-line 204 is imprinted according to the soft template 101, so that described
Imprinting glue-line 204 includes nano graph, and the nano graph is corresponding with the nano impression figure, and the nano graph includes
Groove through the top surface of the coining glue-line 204.
The imprint step specifically includes step (1), step (2), step (3), step (4), step (5) and step
(6).The step (1), including the coining glue-line 204 is imprinted using the soft template 101, so that the coining glue
Layer 204 includes the nano graph, and the nano graph is corresponding with the nano impression figure, and the nano graph includes institute
State groove.The step (2), including forming the described first hard exposure mask on the top surface of the nano graph of the coining glue-line 204
Layer 205.The step (3), including be etch mask with first hard mask layer 205 by etching technics, etched for the second quarter
Lose layer.The step (4), including by etching technics, first hard mask layer 205, the coining obtained with step (3)
Glue-line and second etch layer are etch mask, etch first etch layer, wherein the etching speed of first etch layer
Rate is greater than the etch rate of second etch layer.The step (5), including by etching technics, the institute obtained with step (4)
Stating the first hard mask layer 205, the coining glue-line 204, second etch layer and first etch layer is etch mask, is carved
The substrate 201 is lost, so that the substrate 201 includes the nanostructure.The step (6), including removal step (5) obtain
Structure in first hard mask layer 205, the coining glue-line 204, second etch layer and first etch layer.
The first hard mask layer forming step, including forming the first hard mask layer 205 on the top surface of the nano graph.The erosion
Step is carved, including the substrate 201 is performed etching according to first hard mask layer 205, so that the substrate 201 includes receiving
Rice structure.
In addition, the method also includes step (2a) between the step (2) and the step (5): by etching work
Skill is etch mask with the first hard mask layer 205, etches the coining glue-line 204.
In addition, the soft template 101 is made of polymethyl methacrylate or polydimethyl siloxane material.
In addition, the second etch layer includes silica, silicon nitride, metallic aluminium, crome metal or amorphous carbon material.
In addition, the material of the first etch layer is STU-2 or STU-8 material；The material of first hard mask layer is two
Silica, silicon nitride, metallic aluminium, crome metal or amorphous carbon film, thickness is in 10nm-100nm.
In the imprint step, depth-to-width ratio is directly prepared using electron beam lithography in 1.2 hard templates below
100, be conducive to be passed to the figure in hard template 100 in soft template 101 and subsequent coining glue-line 204.Especially by control
Figure is passed to polymer surfaces by the way of hot padding and forms soft template 101, gathered by the temperature and pressure in moulding process
It closes object and is chosen as polymethyl methacrylate (Poly (methyl methacrylate)) or dimethyl silicone polymer
(Polydimethylsiloxane) etc. materials, gradually remove pressure later and are cooled to and obtain required soft template 101 at room temperature.
Next step is as shown in Fig. 2, be the schematic diagram that each film layer is formed on substrate 201.The step specifically includes following mistake
Journey:
Surface clean and dry pre-treatment are carried out to smooth substrate 201 first, substrate 201 is chosen as glass, silicon wafer, phosphorus
Change the materials such as indium sheet, gallium arsenide film；
Then, one layer of primer layer 202 of spin coating on 201 surface of substrate, the primer layer 202 is as the first etching
Layer, and the materials such as STU-2 or STU-8 are chosen as, and uv-exposure solidification is executed to it, which can be according to final required bottom
Glue mask pattern depth determines；Then one layer of hard membrane layer 203 is plated by techniques such as electron beam evaporation platings on primer layer 202,
Hard membrane layer 203 is used as the second etch layer, and is chosen as the materials such as silica, silicon nitride, metallic aluminium, crome metal or agraphitic carbon
Material.The fast primer layer 202 of etch rate and the slow hard membrane layer 203 of etch rate have been sequentially formed on 201 surface of substrate.So as to
Enough during etching processing, etching obtains the primer layer 202 of deeper mask pattern, and then covering using the high-aspect-ratio
Film pattern realizes the nanostructure figure of high-aspect-ratio；
It finally is laminated print glue-line 204 in 203 surface spin coating one of hard membrane layer, and uses hot pressing mode to solidify it, most end form
At stacked structure as shown in Figure 2.
Next step is the substep transfer step of nano graph as shown in Fig. 3 a- Fig. 3 f.First with obtained by step
Nano graph soft template 101 forms required nano graph on coining glue-line 204 by way of uv-exposure, smooth
Coining glue-line 204 is transformed into the coining glue mask layer 2004 with nanostructure, can be in coining glue mask layer after the completion of this step
Left in 2004 nanostructure part residue glue have it is to be removed；
Then pass through magnetron sputtering, plasma enhanced chemical vapor deposition (Plasma Enhanced Chemical
Vapor Deposition, PECVD) etc. technologies generation 2004 surface of coining glue mask layer deposit the first hard mask layer 205,
First hard mask layer, 205 material is chosen as silica, silicon nitride, metallic aluminium, crome metal or amorphous carbon film, and thickness is in 10-
Between 100nm.Since the particle in the technologies such as magnetron sputtering, PECVD cannot be introduced into nano-scale structure during the deposition process
It is internal and rest on its surface, so obtain the first hard mask layer 205 for being formed in coining 2004 surface of glue mask layer；
Followed by multiple dry etch step, it is first exposure mask with the first hard mask layer 205, is carved by reactive ion
Residue glue in the techniques etching coining glue mask layer 2004 such as erosion or induction plasma etching, smooth and etch resistant the first hard exposure mask
Layer 205 can guarantee that the residue glue for imprinting different-thickness in glue mask layer 2004 is removed clean, and by etching stopping in hard membrane layer
203 surfaces；
Then it is exposure mask with the first hard mask layer 205 and coining glue mask layer 2004, passes through reactive ion etching or induction
The techniques such as plasma etching etch hard membrane layer 203, and hard membrane layer 203 is transformed into the second hard mask layer 2003 with nanostructure,
Etching stopping is on 202 surface of primer layer, at the same time, will also result in the first hard mask layer 205 while etching hard membrane layer 203
Etching so as to cause the thinned of the first hard mask layer 205 and forms the first thinned hard mask layer 2005；
It then is to cover with the first thinned hard mask layer 2005, coining glue mask layer 2004 and the second hard mask layer 2003
Film etches primer layer 202 by the techniques such as reactive ion etching or induction plasma etching, and primer layer 202, which is transformed into, to be had
The primer mask layer 2002 of even nanostructure；
Then it using the structure etched before as exposure mask, is etched by the techniques such as reactive ion etching or induction plasma etching
Substrate 201, substrate 201 are transformed into equally distributed nanostructure substrate 2001.
The first thinned hard mask layer 205 in the structure that finally process above is obtained, coining glue mask layer 2004, the
Two hard mask layers 2003 and primer mask layer 2002 remove completely, nanostructure figure are formed on 201 surface of substrate, finally more
Under the slow hard exposure mask effect of layer etch rate fast softmask and etch rate, the nano junction composition of high-aspect-ratio is prepared
Shape.
Nano-imprinting method according to the invention is by layered mask etching technics, in the fast softmask of multilayer etch rate
With etch rate under the effect of slow hard exposure mask, the nanostructure figure in hard template is passed on substrate, profundity is prepared
Spend the nanostructure substrate of ratio.The nanostructure of this high-aspect-ratio in ceramic field, microelectronics, on bioengineering, light
The fields such as electrical domain, chemical field, medicine have a wide range of applications value.
Application of the invention is further described combined with specific embodiments below.
Embodiment of the present invention selects 200 nanometers of the period, and depth-to-width ratio is the photonic crystal silicon template of 1:1 on the surface of silicon wafer
Prepare 200 nanometers of period, the photonic crystal arrays that depth-to-width ratio is 10:1.
The method that first step uses hot padding, the pattern of silicon template is passed in IPS soft template, the period 200 is obtained
Nanometer, the photonic crystal IPS soft template that depth-to-width ratio is 1:1.
Next step carries out surface clean using acetone, dehydrated alcohol and deionized water on target silicon wafer and 200 degree dry
Dry processing, with a thickness of 500nm, carries out ultra-violet curing to bottom glue, then then in one layer of bottom glue STU2 of substrate surface spin coating
Pass through plasma enhanced chemical vapor deposition (Plasma Enhanced Chemical Vapor on bottom glue
Deposition, PECVD) one layer of 20 nanometers of thick silicon dioxide are plated, finally in one layer of 100 nanometer thickness of silica surface spin coating
The hot ultraviolet stamping glue of mr-NIL6000.1E.
The IPS soft template figure that first step replicates is passed to mr- by the method that next step uses hot ultraviolet stamping
The surface of the hot ultraviolet stamping glue of NIL6000.1E.
The structure of high-aspect-ratio is made by multiple induction plasma etching technics for next step.Pass through magnetron sputtering first
One layer of 10 nano metal chromium is sputtered as hard mask layer, crome metal on the surface of mr-NIL6000.1E ultraviolet stamping glue mask layer
Only nanostructure outer surface can be deposited on and cannot be introduced among cellular structure, next using the crome metal of top layer as mask
Plate removes the residue glue of coining glue mask layer using reactive ion etching, then imprints glue and crome metal with mr-NIL6000.1E
Next layer of silica is etched as mask plate, finally with crome metal, mr-NIL6000.1E coining glue and next layer of dioxy
SiClx is finally used for deep etching substrate silicon with above-mentioned all mask layers, obtains deep width as 500 nanometer thickness primer layer of mask etching
Than the photon crystal structure for 10:1.All mask layers can be removed by acetone and other organic solvent.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Made any modifications, equivalent replacements, and improvements etc., should all be included in the protection scope of the present invention within mind and principle.
Claims (10)
1. a kind of nano impression preparation method of substrate, which is characterized in that the nano impression preparation method of the substrate includes:
Soft template provides step, has the soft template of nano impression figure including providing；
Substrate provides step, including providing substrate and the coining glue-line on the substrate；
Imprint step, including the coining glue-line is imprinted according to the soft template, so that the coining glue-line includes receiving
Rice figure, the nano graph is corresponding with the nano impression figure, and the nano graph includes running through the coining glue-line
Top surface groove；
First hard mask layer forming step, including forming the first hard mask layer on the top surface of the nano graph；And
Etching step, including the substrate is performed etching according to first hard mask layer, so that the substrate includes nanometer
Structure.
2. the nano impression preparation method of substrate as described in claim 1, which is characterized in that the soft template provides step tool
Body includes:
Step a, including by photoetching process, hard template is made, so that the hard template includes transfer coining pattern；
Step b, including the soft template is imprinted according to the hard template, so that the soft template includes the nanometer pressure
Impression shape, wherein the hardness of the soft template is lower than the hard template.
3. the nano impression preparation method of substrate as described in claim 1, which is characterized in that the substrate and the coining glue
The second etch layer and the first etch layer are equipped between layer, wherein second etch layer is located at the close of first etch layer
The side of the coining glue, the imprint step specifically include:
Step (1), including the coining glue-line is imprinted using the soft template, so that the coining glue-line includes described
Nano graph, the nano graph is corresponding with the nano impression figure, and the nano graph includes the groove；
Step (2), including forming first hard mask layer on the top surface of the nano graph of the coining glue-line；
Step (3), including by etching technics, using first hard mask layer as etch mask, etch the second etch layer；
Step (4), including pass through etching technics, first hard mask layer obtained with step (3), the coining glue-line and institute
Stating the second etch layer is etch mask, etches first etch layer, wherein the etch rate of first etch layer is greater than institute
State the etch rate of the second etch layer；
Step (5), including pass through etching technics, first hard mask layer obtained with step (4), the coining glue-line, institute
Stating the second etch layer and first etch layer is etch mask, the substrate is etched, so that the substrate includes the nanometer
Structure；
Step (6), including first hard mask layer, the coining glue-line, described the in removal step (5) obtained structure
Two etch layers and first etch layer.
4. the nano impression preparation method of substrate as claimed in claim 3, which is characterized in that in the step (2) and described
Between step (5), the method also includes:
Step (2a): by etching technics, using the first hard mask layer as etch mask, the coining glue-line is etched.
5. the nano impression preparation method of substrate as claimed in claim 3, which is characterized in that the soft template is poly- methyl-prop
E pioic acid methyl ester or polydimethyl siloxane material are made；
Second etch layer includes silica, silicon nitride, metallic aluminium, crome metal or amorphous carbon material；And
The material of first etch layer is STU-2 or STU-8 material；The material of first hard mask layer is titanium dioxide
Silicon, silicon nitride, metallic aluminium, crome metal or amorphous carbon film, thickness is in 10nm-100nm.
6. a kind of substrate prepared by the nano impression preparation method using substrate described in claim 1.
7. a kind of photonic crystal is prepared including the use of the nano impression preparation method of any one of the claim 1-5 substrate
Substrate.
8. a kind of semiconductor devices is prepared including the use of the nano impression preparation method of any one of the claim 1-5 substrate
Substrate.
9. a kind of display panel is prepared including the use of the nano impression preparation method of the described in any item substrates of claim 1-5
Substrate.
10. a kind of display device is prepared including the use of the nano impression preparation method of the described in any item substrates of claim 1-5
Substrate.
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| US11619766B2 (en) * | 2019-04-17 | 2023-04-04 | No.59 Institute Of China Ordnance Industry | Micro- and nano-hot embossing method for optical glass lens arrays |
| CN111606300A (en) * | 2020-05-26 | 2020-09-01 | 杭州欧光芯科技有限公司 | Method for manufacturing high aspect ratio nano grating |
| CN112462468A (en) * | 2020-10-27 | 2021-03-09 | 中国科学院微电子研究所 | Method for manufacturing photonic crystal by utilizing graph inversion and photonic crystal |
| CN112723305A (en) * | 2020-12-25 | 2021-04-30 | 杭州欧光芯科技有限公司 | Super surface manufacturing method |
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