CN102591142B - Nano imprinting device and method for imaging sapphire substrate - Google Patents

Nano imprinting device and method for imaging sapphire substrate Download PDF

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CN102591142B
CN102591142B CN 201210049910 CN201210049910A CN102591142B CN 102591142 B CN102591142 B CN 102591142B CN 201210049910 CN201210049910 CN 201210049910 CN 201210049910 A CN201210049910 A CN 201210049910A CN 102591142 B CN102591142 B CN 102591142B
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sapphire substrate
resist
nano
mould
imprint
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CN102591142A (en
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兰红波
丁玉成
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Qingdao University of Technology
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Qingdao University of Technology
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Abstract

The invention discloses a nano imprinting device and method for imaging a sapphire substrate. The nano imprinting device comprises a nano imprinting mould, an ultraviolet nano imprinting resist, the sapphire substrate and an exposure ultraviolet light source, wherein the ultraviolet nano imprinting resist is spread on the sapphire substrate, the exposure ultraviolet light source is arranged below the sapphire substrate, and a characteristic cavity is arranged on the nano imprinting mould to form a characteristic image on the mould. By using a modified fluorocarbon resin-based hard polymer mould which has lowest surface energy and the advantages of a soft mould and a hard mould and better mechanical and physical performances and by combining the sapphire substrate which has better light transmission property relative to ultraviolet rays, the above-4 inch large-size wafer level nano imaged sapphire substrate is manufactured in a low-cost, high-productivity and large-scale manner. The invention can also be used for imaging other transparent substrates (such as a ZnO substrate).

Description

Be used for the patterned nano-imprinting device of Sapphire Substrate and method
Technical field
The present invention relates to a kind of manufacture method of graphical sapphire substrate, relate in particular to and a kind ofly be used for the patterned nano-imprinting device of Sapphire Substrate and method based on fluorocarbon modified resin-based hard polymer mould, realize volume production large scale wafer level nano-patterned sapphire substrate, belong to minute manufacturing and optoelectronic device manufacturing technology field.
Background technology
Sapphire Substrate is to make at present the topmost substrates of GaN base LED such as blue light, green glow and white light, (such as silit, silicon, GaN, ZnO etc.) compare with other substrate, have that manufacturing technology maturation, monolithic cost are low, chemistry and temperature stability is good, good mechanical property, do not absorb the advantages such as visible light, be the most widely used substrate of present LED industry.But, main flow substrate as the LED industry, Sapphire Substrate has a significant deficiency: have larger lattice mismatch and thermal stress mismatch with GaN homepitaxy material, this will cause epitaxial wafer to produce a large amount of defective (namely because the Lattice Matching degree is low, causing Interfacial Dislocations density height).This has had a strong impact on the internal quantum efficiency of LED, the Performance and quality of led chip.For example, the two grating constant of GaN and saphire substrate material differs and reaches 16%, and this causes GaN epitaxial loayer defect concentration larger, and spreads to active layer InGaN, and defect concentration reaches 10 9~10 11Cm -2The order of magnitude.These line defects are understood absorption portion Injection Currents, have reduced the generation rate of charge carrier, cause injection efficiency to descend.Simultaneously, it is compound that charge carrier in defect level non-radiation type occurs easily, and the luminous energy of charge carrier radiativity composition generation is also absorbed generation heat energy easily by defective.This is the inherent shortcoming of saphire substrate material, and the key technical problem that the defects reflection causes in actual applications is exactly " Droop effect ", and namely along with the increase of current density, interior conversion quantum efficiency constantly descends." Droop effect " reduced light output intensity on the one hand, increased on the other hand the heat energy of production capacity in the course of work, and heat radiation is had higher requirement.One of maximum technological challenge problem of present LED industry, in the urgent need to being solved.
Graphical sapphire substrate (Patterned Sapphire Substrate, PSS) is to produce micron order or nano level pattern with microstructure ad hoc rules in Sapphire Substrate, makes GaN homepitaxy material become horizontal extension by vertical extension.Can effectively reduce on the one hand the dislocation desity of GaN epitaxial material, improve crystal mass, thereby reduce the non-radiative compound of active area, reduce reverse leakage current, improve the life-span of LED; On the other hand, the light that active area sends through GaN and graphical sapphire substrate interface Multiple Scattering, has changed the emergence angle (escape light cone) of total reflection light, thereby has increased the probability of light from the chip internal outgoing, has improved and has got optical efficiency.The reason of comprehensive this two aspect makes the light extraction efficiency of the LED that grows at PSS, output power greatly improve than traditional LED, and the life-span of LED has also obtained prolongation.Therefore, the PSS method is so that Sapphire Substrate LED promotes on internal quantum efficiency and light extraction efficiency to some extent, and the Performance and quality of LED has had very large improvement, is for take sapphire effectively improving one's methods as the substrate GaN-based LED defective.Graphical sapphire substrate is becoming the main flow substrate of semiconductor lighting, is an important support technology that realizes high-brightness LED.
But, the graphical sapphire substrate that present LED industrial community provides mostly is greatly micron order graphical sapphire substrate (Micro-scale Patterned Sapphire Substrate, PSS), for example, present usage comparison is the similar taper shape of a kind of pattern or hemispheric figure generally, diameter is 3-5 μ m, and the figure cycle is about 3-6 μ m, highly is about 1-3 μ m.Compare with common micron order patterned substrate, existing result of study confirms (Applied Physics Letters. 2010,96,201106; Materials Science and Engineering B. 2009,164,76 – 79; Journal of Crystal Growth. 2011,322,15-22; Phys. Status Solidi C 2010,7,7 – 8,1784 – 1786), nano patterned Sapphire Substrate (Nano-Patterned Sapphire Substrate, NPSS) show better performance: the stress of (1) more effective relaxation heterojunction boundary growth course, further reduce the dislocation desity of epitaxial loayer, improve the quality of crystal.Existing achievement in research shows: GaN is not having patterned Sapphire Substrate (flat substrate), PSS and NPSS growth respectively, and its dislocation desity is respectively: 1 * 10 9~ 1 * 10 10Cm 2~1 * 10 8Cm 2Be lower than 1 * 10 7Cm 2(2) higher light extraction efficiency (Better Light Extraction) for PSS, only has the light beam of larger incident angle just can be reflected and is coupled in the escape light cone, also has some light to radiate, and through Multi reflection, finally is absorbed.And for NPSS, almost the angled light of institute's incident all can be scattered, and great majority can be coupled in the escape light cone, radiate (figure of small-feature-size has more increased the probability of light scattering, in other words conj.or perhaps again reflectivity).(3) better agglomeration effect (Better Coalescence), the line dislocation density of inhibition longitudinal direction.(4) less reverse leakage current improves the LED life-span.In addition, if the micro-nano structure characteristic dimension less than the wavelength of light wave, the refractive index of this layer nanostructured is between sapphire and GaN; When the degree of depth of micro-nano structure greater than λ/4n, light beam in boundary surface by interreflection and propagation.Therefore, output power can effectively be improved.So nano patterned Sapphire Substrate especially large scale NPSS has become present raising LED brightness, performance and life-span and has had one of technology of commercial applications prospect most.
For traditional PSS(PSS), usually adopt the method for photoetching and etching to make micron-sized figure, contact or proximity lithographic equipment are generally adopted in photoetching, and etching adopts dry etching or wet etching.But for NPSS, adopt existing contact or proximity lithographic equipment can't satisfy the requirement that nano graph is made, adopt step-by-step movement projection lithography (Stepper) although can realize the NPSS manufacturing, but the Stepper that semicon industry uses seems too expensive in the LED industry, increased the manufacturing cost of LED, and LED is very responsive for cost.In addition, adopt beamwriter lithography also can satisfy the requirement that nano graph is made, but cost is high, throughput rate is low, is difficult to realize the manufacturing of large tracts of land, scale.Although other has also attempted being applied to the manufacturing of NPSS such as nanometer manufacture methods such as nanosphere pearly-lustre quarter, anodic oxidation aluminium formwork (AAO), laser interference lithographies; but all in the deficiency that exists aspect certain; such as cost, throughput rate, consistance, yield and scale manufacturing etc., can't satisfy the LED industry for the harshness requirement (LED is very strict for the requirement of cost, consistance and yield) of high rate/low cost production, high yield.Realizing that with adopting above nano-fabrication technique NPSS compares, use nano-imprint lithography to make NPSS, is a kind of ideal solution.Nano-imprint lithography (Nanoimprint Lithography, NIL) be a kind of new nanostructured and the manufacture method of figure, it has high resolution, the characteristics such as Ultra Low Cost (NIL of the equal production technique of internal authority organization evaluation is than the low at least order of magnitude of traditional optical projection lithography) and high productivity, and its most significant advantage is the ability (especially for soft UV-NIL) that large tracts of land and complex three-dimensional micro-nano structure are made, especially single step Integral wafer nano-imprinting technique has the manufacturing capacity that realizes large scale wafer scale micro-nano graph and structure.In addition, NIL realizes that by the stress deformation of resist it is graphical, does not relate to the use of various high energy beams, and is little for the damage of substrate.At present, nano impression has become nano-patterned sapphire substrate, photonic crystal LED is made one of optimal technical method.
Repeating nano-imprint process with stepping compares, adopt Integral wafer nano-imprinting to make NPSS and have that cost is low, the significant advantage of high productivity, but existing large scale Integral wafer nano-imprinting technique faces following challenge technical barrier: (1) demoulding difficulty.Increase along with the contact area of mould and substrate, comprising mould micro-nano structure feature on the one hand increases greatly, mould and resist sticking problem become and become increasingly conspicuous on the other hand, what cause need to very large knockout press could realizing mould and wafer separates the easy mold damage of large knockout press and the figure that copies; In addition, if knockout press is excessive, then the particle that solidifies resist may be sticked to die surface, and may cause the destruction of die surface micro-nano structure, namely cause " pollution " of impressing mould; (2) no matter apply hard mold or the soft mold of release layer mould limited serviceable life, and its serviceable life is limited, is difficult to satisfy the requirement of industrial applications; (3) be difficult to realize the manufacturing of high graphics.In order to realize contacting fully of mould and full wafer wafer uniformity, quick, the complete micro-nano cavity body structure of filling mould of liquid resist, repeating nano-imprint process with stepping compares with the small size imprint process, the force of impression that large scale full wafer wafer impression need to more arrive, large force of impression will cause mould to produce distortion, particularly serious for its distortion of soft mold, this will cause the replica precision reduction, have defective, even graph copying failure; (4) bubble is eliminated.Eliminate bubble is the very stubborn problem that nano-imprint process faces always, and there is defective in the figure that the existence of bubble will cause copying, has a strong impact on the quality of making figure.Seal very easily produces bubble in the large scale Integral wafer nano-imprinting process, but is very difficult to solve yet eliminate bubble; (5) large tracts of land applies the force of impression of uniformity.The force of impression skewness causes mould can't contact fully fully with substrate on the one hand, affects replica precision and quality, even causes figure to shift unsuccessfully, and for template or the substrate of hard brittle material, the inhomogeneous of force of impression very easily causes it cracked on the other hand.Sapphire Substrate is from early stage 2inch and 4inch, and at present forward 6inch and 8inch development along with the increase of substrate dimension, means that the cost of manufacture of per unit area reduces, the lifting of overall production capacity.But along with the continuous increase of substrate (wafer) size, in full wafer substrate graph process, how obtain the more difficult that the force of impression of uniformity becomes at large-area substrate.Requirement for stamp work platform and eindruckwerk performance is also more and more higher; (6) whole imprinting area obtains uniformity and thin residual layer.Figure on the resist need to be transferred on the wafer (substrate), at imprinting area acquisition uniformity and the thin residual layer of full wafer wafer, for realizing that high-quality figure shifts the conclusive effect of playing.
Especially for large scale Integral wafer nano-imprinting technique, good demoulding ability has determined quality and the mold use life-span of coining pattern, the hard mold that existing nano impression uses, must carry out surface treatment such as silicon, quartz etc., apply one deck release agent, but thinner release agent in use is easy to come off, and causes die life limited.Soft mold, such as PDMS, although have lower surface energy, demolding performace is better, in the use procedure, easily produce distortion, and its serviceable life is limited.Need often to change, affect production efficiency, be difficult to satisfy the production requirement that the commercial Application large-scale is made.
Select preferably high molecular polymer of physics and chemical combination property, and by suitable physics or chemical modification, make it have following characteristic: higher elasticity modulus, low-down surface energy, solvent resistance are strong, machinery and good physical performance etc., satisfy nano impression for the various functional requirements of mould, such mould is called the hard polymer mould.Be different from traditional hard mold (silicon, quartz etc.) or soft mold (PDMS etc.), the elastic modulus of hard polymer mould arrives between several lucky handkerchiefs in the hundreds of MPa, stronger opposing external pressure is arranged and keep the ability of self shape, remarkable advantage with hard mold is conducive to realize the manufacturing of high precision figure.In addition, it have again soft template preferably with the conformal engagement capacity of substrate, be fit to have warpage, the nano impression of the figure of flexural property substrate; A characteristic that is even more important is that for the fluorocarbon resin base hard polymer mould after the modification, it namely has extremely low surface energy (17.98 mJm -2), well chemical solvent resistance and ultra-violet resistance, have again higher elastic modulus, toughness preferably, be particularly suitable as the mould that large tracts of land, non-smooth substrate nano impression are used.For the nano-imprint process of non-flat substrate, large tracts of land full wafer wafer provides a kind of desirable solution.
Summary of the invention
The object of the invention is to stripping feature and superior mechanical and the physical property of utilizing fluorocarbon resin base hard polymer mould good; and in conjunction with the Sapphire Substrate good light permeability (from ultraviolet to infrared good transmitance arranged all) characteristics; provide a kind of based on fluorocarbon modified resin-based hard polymer mould be used for the patterned nano-imprinting device of Sapphire Substrate and method, realize macro nanometer level graphic sapphire high rate/low cost production and scale manufacturing more than 4 inches.
To achieve these goals, the present invention takes following technical solution take the matrix material of fluorocarbon modified resin as the hard polymer mould, adopts die casting technique to make the template (mould) of nano impression; Exposure places with ultraviolet source under the Sapphire Substrate, utilizes the good saturating ultraviolet light characteristic of sapphire, exposes from Sapphire Substrate one side, and the resist after the complex is cured.Particularly, apparatus structure of the present invention is:
A kind of large scale wafer level nano-patterned sapphire substrate imprinting device, it comprises: be followed successively by from top to bottom: metallic mold for nano-imprint, the ultraviolet nanometer impression is used resist, Sapphire Substrate, the ultraviolet source of exposure usefulness.Wherein, resist is coated with and is laid on the Sapphire Substrate, and exposure places under the Sapphire Substrate with ultraviolet source, and metallic mold for nano-imprint is provided with the feature die cavity, thereby consists of the feature pattern on the mould.
Described nano impression module adopts fluorocarbon modified resin-based hard polymer material, and it is mixed according to mass ratio 1:0.27:0.07 by FEVE (vinyl chloride-ethylene base ether) type fluorocarbon resin, hardening agent, polyacrylic acid modified organic siliconresin; Its method for making adopts the die casting manufacturing process.
Described ultraviolet source adopts ultraviolet LED lamp module, places a side of Sapphire Substrate, under Sapphire Substrate.
Described moulding process carries out under the low-voltage vacuum environment.Eliminate the air bubble problem that Integral wafer nano-imprinting causes on the one hand, in addition, realize resist to the Fast Filling of impressing mould feature die cavity, its step is:
(1) is coated with the shop resist;
The resist of spin coating ultraviolet nanometer impression usefulness on Sapphire Substrate (resistance erosion glue, a kind of liquid organic polymer).
(2) moulding process;
After aligning, metallic mold for nano-imprint (fluorocarbon modified resin-based hard polymer mould) and Sapphire Substrate press down, the feature die cavity of the complete filling metallic mold for nano-imprint of resist, and residual layer is thinned to the film thickness that stays of setting.
(3) solidification process;
Open ultraviolet source, ultraviolet light sees through sapphire, and exposure is cured the resist after the complex.
(4) knockout course;
Metallic mold for nano-imprint separates with resist after the complex, realizes that feature pattern is to the transfer of resist figure on the metallic mold for nano-imprint.
The preparation method of described graphical sapphire substrate is:
(1) resist in shop that Sapphire Substrate is coated with produces the nanofeature figure;
(2) remove residual layer;
(3) adopt etching technics that the upper nanofeature figure of resist is transferred on the Sapphire Substrate;
(4) remove resist;
(5) Sapphire Substrate after cleaning graphically.
The descriptive geometry of described graphical sapphire substrate is shaped as: clavate, semisphere, column, circle hole shape, hexagon hole shape, U-shaped, pyramid, hexagon, V-shape is carinate or photon crystal structure.
Described resist is the uv-curing type resist, and is good for the elching resistant of fluorine class and chlorine class gas, and the etching selectivity of the Sapphire Substrate that LED is used is higher than 0.5.
The etching technics that relates in the described nano-patterned sapphire substrate manufacture method is wet etching, reactive ion etching or plasma etching.
The invention has the beneficial effects as follows:
1) in conjunction with the advantage of fluorocarbon modified resin-based hard polymer metallic mold for nano-imprint and Sapphire Substrate, be that fluorocarbon modified resin-based hard polymer metallic mold for nano-imprint has low-down surface energy (being fit to the large tracts of land demoulding), have advantage (the complex precision is high, die life is long, be fit to non-flat substrate impression) soft, hard mold concurrently; Sapphire Substrate is for the good light transmission of ultraviolet light.The fluorocarbon resin base hard polymer mould of function admirable is applied to the ultraviolet nanometer impression, is macro nanometer level graphic sapphire high rate/low cost production and scale manufacturing more than 4 inches, and a kind of application solution of technical grade is provided.
2) be easy to the demoulding.The material that metallic mold for nano-imprint uses is fluorocarbon modified resin-based hard polymer, has low-down surface energy (17.98 mJm -2), be easy to the demoulding of large tracts of land full wafer wafer impression, solved the maximum technical barrier of large-area nano impression.
3) metallic mold for nano-imprint long service life.Hard mold such as quartz molds that tradition ultraviolet nanometer impression uses in order to be easy to the demoulding, need to be carried out surface treatment, apply one deck release agent, but thinner release agent are easy in use come off, and causes metallic mold for nano-imprint limited serviceable life; The PDMS mould that soft UV-NIL uses, although have lower surface energy, demolding performace is better, serviceable life is limited, and easily produces distortion, needs often to change, and is difficult to satisfy the production requirement that the commercial Application large-scale is made.It namely has extremely low surface energy (17.98 mJm the hard metallic mold for nano-imprint of fluorocarbon modified resin-based hard polymer that the present invention uses -2), well chemical solvent resistance and ultra-violet resistance, have again higher elastic modulus, toughness preferably, compare with the PDMS soft mold with the hard mold of existing coating release agent, have long serviceable life, satisfy the demand of industrial scale applications.
4) the complex precision is high.The elastic modulus of hard polymer metallic mold for nano-imprint arrives between several lucky handkerchiefs in the hundreds of MPa, stronger opposing external pressure is arranged and keep the ability of self shape, in addition, the demoulding is easy, be conducive to realize high-resolution nanostructured in the imprint process process or the manufacturing of figure, satisfy NPSS for the requirement of figure manufacturing accuracy.
5) impression of suitable non-flat (warpage, bending etc.) substrate.Compare with traditional hard mold, the fluorocarbon modified resin-based hard polymer nano-imprint stamp that the present invention uses, it has preferably toughness, have good and conformal engagement capacity substrate, impression at the bottom of the non-flat integral basis such as suitable warpage, bending satisfies the patterned technological requirement of large tracts of land Sapphire Substrate.
6) the present invention can realize high rate/low cost production and the scale manufacturing of non-flat (warpage, bending etc.) substrate S ub-50nm feature pattern.
7) the present invention exposes for resist from Sapphire Substrate one side, make resist and Sapphire Substrate fully solidify the two interface and have good binding characteristic, the defective of resist and substrate separation after avoiding the large tracts of land demoulding to solidify, in addition, it is too tight to avoid resist to be combined with mold cured, and the demoulding produces the defective that adheres to.In addition, simplified the design of eindruckwerk.
Description of drawings
Fig. 1 is the structural representation of wafer level nano-patterned sapphire substrate imprinting device of the present invention.
Fig. 2 is wafer level nano-patterned sapphire substrate manufacturing technology steps figure of the present invention.
Fig. 3 A-Fig. 3 G is wafer level nano-patterned sapphire substrate schematic diagram of fabrication technology of the present invention.
Fig. 4 A-Fig. 4 H is the present invention's wafer level nano-patterned sapphire substrate schematic diagram of fabrication technology when using hard mask layer.
Among the figure, 1. nano-imprint stamp, 101. the feature pattern on the mould, 102. feature die cavity, 2. resists, 201. the feature pattern on the resist, 202. the residual layer on the resist, 3. Sapphire Substrate, the feature pattern that shifts on 301. Sapphire Substrate, 4. ultraviolet source, 501. hard mask layers.
Embodiment
The present invention is described in further detail according to embodiment that technical scheme of the present invention provides below in conjunction with accompanying drawing and inventor.
Among Fig. 1, Fig. 2, Fig. 3 A-Fig. 3 G and Fig. 4 A-Fig. 4 H, take 4 English inch (about 100 millimeters) nano-patterned sapphire substrate 3 as embodiment, describe the ultraviolet nanometer imprint process that adopts based on fluorocarbon modified resin-based hard polymer mould in detail, realize imprinting apparatus and the manufacture method thereof of wafer level nano-patterned sapphire substrate.
Among Fig. 1, a kind of wafer level nano-patterned sapphire substrate imprinting device, it comprises: be followed successively by from top to bottom: modified Nano impressing mould 1, ultraviolet nanometer impression resist 2, Sapphire Substrate 3, the ultraviolet source 4 of exposure usefulness.Wherein, resist 2 is coated with and is laid on the Sapphire Substrate 3, and exposure places under the Sapphire Substrate 3 with ultraviolet source 4, is provided with feature die cavity 102 at metallic mold for nano-imprint 1, thereby consists of the feature pattern 101 on the mould.
Described metallic mold for nano-imprint 1 adopts fluorocarbon modified resin-based hard polymer material, and it is mixed according to mass ratio 1:0.27:0.07 by FEVE (vinyl chloride-ethylene base ether) type fluorocarbon resin, hardening agent, polyacrylic acid modified organic siliconresin.FEVE type fluorocarbon resin is matrix (main body) material of metallic mold for nano-imprint 1, improve its curing performance, further reduce surface energy, raising mechanical property and physical characteristics by adding hardening agent and polyacrylic acid modified organic siliconresin, satisfy the requirement of large tracts of land ultraviolet nanometer imprint process.Hydroxyl on the FEVE type fluorocarbon resin side chain (OH) can with the hardening agent of isocyanates in the NCO radical reaction and film-forming, other resinoid that in fluorocarbon resin, adds the low-surface-energy that contains hydroxy functional group, this resin can solidify with the NCO radical reaction in the hardening agent of isocyanates on the one hand, can reduce again on the other hand the surface energy of whole system.Follow-on fluorocarbon resin not only self has very low surface energy, and higher intensity, toughness are preferably arranged again, also has good chemical solvent resistance and ultra-violet resistance.Have the advantage of dura mater tool and soft mold material concurrently.
The method for making of metallic mold for nano-imprint 1 is as follows: at first, adopt the electron-beam lithography system exposure to be formed at the positive glue ZEP520A of electron beam figure on the silicon chip as motherboard; Then, the FEVE type fluorocarbon resin of will be take mass ratio as 1:0.27:0.07 mixed fluorocarbon resin GK-570(Daikin company), hardening agent Z4470(Beyer Co., Ltd) and polyacrylic acid modified organic siliconresin Protect 5001(Tego company) water and cast from the motherboard, then be evacuated to 10Pa, curing made template forming in 24 hours under 80 ° of C; At last, stripping silicon chip obtains metallic mold for nano-imprint 1.
Among Fig. 2, adopt wafer level nano-patterned sapphire substrate imprinting device of the present invention to carry out method for stamping, its step is:
(1) is coated with shop resist 2;
The resist of spin coating ultraviolet nanometer impression usefulness on Sapphire Substrate 3 (resistance erosion glue) 2.Such as Fig. 3 A.
(2) moulding process;
Metallic mold for nano-imprint 1 presses down after aligning with Sapphire Substrate 3, the feature die cavity 102 of resist 2 complete filling metallic mold for nano-imprint 1, and further press down, the residual layer 202 on the resist is thinned to the film thickness that stays of setting.Such as Fig. 3 B.
(3) solidification process;
Open ultraviolet source 4, ultraviolet light sees through Sapphire Substrate 3, and exposure is cured the resist 2 after the replica.Such as Fig. 3 C.
(4) knockout course;
Metallic mold for nano-imprint 1 separates with resist 2 after the complex, realizes the transfer of the feature pattern 201 of feature pattern 101 to the resist on the mould.Such as Fig. 3 D.
The preparation method of described graphical sapphire substrate 3 is:
(1) produces feature pattern 201 on the resist at the resist 2 of full wafer Sapphire Substrate 3;
(2) residual layer 202 on the removal resist is such as Fig. 3 E;
(3) adopt etching technics that the feature pattern 201 on the resist is transferred on the Sapphire Substrate 3, copy the feature pattern 301 that Sapphire Substrate shifts in Sapphire Substrate 3, such as Fig. 3 F;
(4) remove resist 2, such as Fig. 3 G;
(5) Sapphire Substrate 3 after cleaning graphically.
The descriptive geometry of described graphical sapphire substrate 3 is shaped as: clavate, semisphere, column, circle hole shape, hexagon hole shape, U-shaped, pyramid, hexagon, V-shape is carinate or photon crystal structure.
The etching technics that relates in described nano-patterned sapphire substrate 3 manufacture methods is wet etching, reactive ion etching or plasma etching.
The parameter of Sapphire Substrate arranges as follows among the embodiment of an actual fabrication of the present invention: 4 English inch sapphires, make nano graph hole pattern array thereon, and the geometric parameter in figure hole is: the diameter 200nm of circular hole, cycle 400nm, the degree of depth in hole is 100nm.
Employing the present invention is based on device and the technique of the ultraviolet nanometer impression of fluorocarbon modified resin-based hard polymer mould, and the method for wafer level nano-patterned sapphire substrate, the concrete manufacturing technology steps of present embodiment:
1) adopts imprint process of the present invention and device, produce feature pattern 201 on the resist at resist 2;
Resist is carried out patterned concrete technology step:
(a) spin coating ultraviolet nanometer impression resist 2
Spin coating 250nm ultraviolet nanometer impression resist 2 on Sapphire Substrate 3.Such as Fig. 3 A.
(b) moulding process
Metallic mold for nano-imprint 1 presses down after aligning with Sapphire Substrate 3, and the feature die cavity 102 of resist 2 complete filling metallic mold for nano-imprint 1, and further pressing down is thinned to the film thickness that stays of setting with the residual layer 202 on the resist, and staying film thickness is 80nm.Such as Fig. 3 B.
(c) solidification process;
Open ultraviolet source 4, ultraviolet light sees through Sapphire Substrate 3, and exposure is cured the resist 2 after the replica, set time 15s.Such as Fig. 3 C.
(d) knockout course;
Metallic mold for nano-imprint 1 separates with resist 2 after the complex, realizes the transfer of the feature pattern 201 of feature pattern 101 to the resist on the mould.Such as Fig. 3 D.
2) remove residual layer 202
Employing reactive ion etching etching technics removes the residual layer 202 on the resist.Such as Fig. 3 E.
3) figure shifts
Feature pattern 201 on the resist uses BCl as mask 3/ Cl 2Be etching gas, using plasma etching (ICP) technique is transferred to the feature pattern 201 on the resist on the Sapphire Substrate 3, copies the feature pattern 301 that Sapphire Substrate shifts in Sapphire Substrate; Such as Fig. 3 F.
4) remove resist 2
Remove resist 2, such as Fig. 3 G.
5) Sapphire Substrate 3 after cleaning graphically
Ultraviolet nanometer impression can be selected the nano impression resin of the kind petro-chemical corporation of Japanese ball with resist, and this nano impression resin is high to the elching resistant of fluorine class and chlorine class gas, and the etching selection ratio of the Sapphire Substrate of LED use is reached 0.7~0.8.Etching selection ratio numerical value is higher, the resin bed of just more can attenuate substrate microfabrication using.Resin bed is thinner, easier metallic mold for nano-imprint 1 is stripped down from resist 2, and can significantly improve production efficiency.
In addition, also can use transparent hard mask layer 501(such as silicon dioxide SiO 2, Cr, ITO etc.), reduce the requirement (elching resistant to fluorine class and chlorine class gas is high) for the shop characteristic of resist 2, and realize making the more ability of high aspect ratio figure.At first, at the hard mask layer 501 of Sapphire Substrate deposition layer of transparent, on hard mask layer 501, be coated with again and spread one deck resist 2; Secondly, adopt apparatus and method of the present invention that resist is carried out graphically; Then, adopt etching technics that the feature pattern 201 on the resist is transferred to hard mask layer 501, further adopt etching technics that the figure on the hard mask layer 501 is transferred on the Sapphire Substrate 3; At last, remove resist 2 and hard mask layer 501, the Sapphire Substrate 3 after cleaning is graphical.
Fig. 4 A-Fig. 4 H is that the present invention adopts hard mask layer wafer level nano-patterned sapphire substrate schematic diagram of fabrication technology.Concrete manufacturing technology steps:
1) the deposited hard mask layer 501
The silicon dioxide of sputter on sapphire (magnetron sputtering or plasma reinforced chemical vapour deposition PECVD) deposition 120nm (silicon dioxide is saturating ultraviolet light not only, but also also has anti-reflection effect for Sapphire Substrate) is as hard mask layer 501.Such as Fig. 4 A.
2) adopt imprint process of the present invention and device, produce nano graph at resist 2
Resist 2 is carried out patterned concrete technology step:
(a) spin coating ultraviolet nanometer impression resist 2
Spin coating 250nm ultraviolet nanometer impression resist 2 above the hard mask layer 501 on Sapphire Substrate 3.Such as Fig. 4 A.
(b) moulding process
Metallic mold for nano-imprint 1 presses down after aligning with Sapphire Substrate 3, and the feature die cavity 102 of resist 2 complete filling metallic mold for nano-imprint 1, and further pressing down is thinned to the film thickness that stays of setting with the residual layer 202 on the resist, and staying film thickness is 80nm.Such as Fig. 4 B.
(c) solidification process;
Open ultraviolet source 4, ultraviolet light sees through Sapphire Substrate 3 and printing opacity hard mask layer 501, and exposure is cured the resist 2 after the replica, set time 18s.Such as Fig. 4 C.
(d) knockout course;
Metallic mold for nano-imprint 1 separates with resist 2 after the complex, realizes the transfer of feature pattern 101 feature pattern 201 to the resist 2 on the mould.Such as Fig. 4 D.
3) residual layer 202 on the removal resist
Adopt the residual layer 202 on the reactive ion etching etching technics removal resist.Such as Fig. 4 E.
4) feature pattern on the resist 201 is transferred to hard mask layer 501
Take ultraviolet nanometer impression resist 2 as mask, the using plasma etching technics is transferred to the feature pattern 201 on the resist on the hard mask layer (silicon dioxide) 501.Such as Fig. 4 F.
5) figure on the hard mask layer 501 is transferred to Sapphire Substrate 3
Take hard mask layer (silicon dioxide) 501 as mask, use BCl 3/ Cl 2Be etching gas, using plasma etching (ICP) technique is transferred to the feature pattern on the hard mask layer 501 on the Sapphire Substrate 3, copies the feature pattern 301 that Sapphire Substrate shifts in Sapphire Substrate 3; Such as Fig. 4 G.
6) remove resist 2 and hard mask layer 501
Utilize diluted hydrofluoric acid (HF) that hard mask layer 501 is eroded.Remove resist 2 and hard mask layer 501, such as Fig. 4 H.
7) Sapphire Substrate 3 after cleaning graphically
If use hard mask layer 501, can use the used ultraviolet nanometer impression resist of common ultraviolet nanometer impression.Reduction is for the high requirement of elching resistant to fluorine class and chlorine class gas of resist.
The present invention also can be used for the graphical of other transparent substrates (such as the ZnO substrate).
In addition, those skilled in the art also can do other variation in spirit of the present invention.Certainly, the variation that these are done according to spirit of the present invention all should be included in the present invention's scope required for protection.

Claims (8)

1. one kind is used for the patterned nano-imprinting device of Sapphire Substrate, it is characterized in that, it comprises: be followed successively by from top to bottom: metallic mold for nano-imprint, the ultraviolet nanometer impression is used resist, Sapphire Substrate, the ultraviolet source of exposure usefulness, wherein, resist is coated with and is laid on the Sapphire Substrate, is provided with the feature die cavity at metallic mold for nano-imprint, thereby consists of the feature pattern on the mould; Described metallic mold for nano-imprint adopts fluorocarbon modified resin-based hard polymer material, and it is mixed according to mass ratio 1:0.27:0.07 by FEVE vinyl chloride-ethylene base ether type fluorocarbon resin, hardening agent, polyacrylic acid modified organic siliconresin; Its method for making adopts the die casting manufacturing process.
2. as claimed in claim 1ly it is characterized in that for the patterned nano-imprinting device of Sapphire Substrate described ultraviolet source places a side of Sapphire Substrate, under Sapphire Substrate.
3. one kind is adopted the method for stamping for the patterned nano-imprinting device of Sapphire Substrate claimed in claim 1, it is characterized in that described moulding process carries out under the low-voltage vacuum environment, and its step is:
(1) is coated with the shop resist;
The resist of spin coating ultraviolet nanometer impression usefulness on Sapphire Substrate;
(2) moulding process;
After aligning, metallic mold for nano-imprint and Sapphire Substrate press down, the feature die cavity of the complete filling mould of resist, and residual layer is thinned to the film thickness that stays of setting;
(3) solidification process;
Open ultraviolet source, ultraviolet light sees through sapphire, and exposure is cured the resist after the replica;
(4) knockout course;
The mould of impression separates with the resist after the complex, realizes that feature pattern is to the transfer of resist figure on the mould.
4. method for stamping as claimed in claim 3 is characterized in that, the manufacture method of described graphical sapphire substrate is:
(1) resist in the full wafer Sapphire Substrate produces the nanofeature figure;
(2) remove residual layer;
(3) adopt etching technics that the upper nanofeature figure of resist is transferred on the Sapphire Substrate;
(4) remove resist;
(5) Sapphire Substrate after cleaning graphically.
5. Method for stamping as claimed in claim 4 is characterized in that, described resist is the uv-curing type resist, and is good for the elching resistant of fluorine class and chlorine class gas, and the etching selectivity of the Sapphire Substrate that LED is used is higher than 0.5.
6. method for stamping as claimed in claim 5, it is characterized in that the descriptive geometry of described graphical sapphire substrate is shaped as: clavate, semisphere, column, circle hole shape, hexagon hole shape, U-shaped, pyramid, hexagon, V-shape is carinate or photon crystal structure.
7. method for stamping as claimed in claim 5 is characterized in that, the etching technics that relates in the described nano-patterned sapphire substrate manufacture method is wet etching, reactive ion etching or plasma etching.
8. method for stamping as claimed in claim 5 is characterized in that, if use transparent hard mask layer, the preparation method of described graphical sapphire substrate is:
(1) deposition layer of transparent hard mask layer on Sapphire Substrate;
(2) resist on transparent hard mask layer produces the nanofeature figure;
(3) remove residual layer;
(4) adopt etching technics that the upper figure of resist is transferred to hard mask layer;
(5) adopt etching technics that the nanofeature figure on the hard mask layer is transferred on the Sapphire Substrate;
(6) remove resist and hard mask layer;
(7) Sapphire Substrate after cleaning graphically.
CN 201210049910 2012-02-29 2012-02-29 Nano imprinting device and method for imaging sapphire substrate Expired - Fee Related CN102591142B (en)

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