CN105093824A - Gas-electricity cooperative large-area nano-imprinting photo-etching method - Google Patents
Gas-electricity cooperative large-area nano-imprinting photo-etching method Download PDFInfo
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Abstract
The invention discloses a gas-electricity cooperative large-area nano-imprinting photo-etching method. A flexible composite mould is adopted as an imprinting template; the flexible composite mould is divided into a plurality of sub-regions by a gas circuit. Starting from one side, one sub-region at the edge is switched from vacuum to a barometric pressure along with the gas circuit; the sub-region, under the action of externally applied electric field force, is in conformal contact with a substrate and realizes complete filling of a nanometer level structure; and the state of the gas circuit is changed in sequence, and the sub-regions are also in contact with the substrate in sequence to finally realize transfer of the nanometer structure. The gas-electricity cooperative large-area nano-imprinting photo-etching method is particularly suitable for a wafer level warping substrate; furthermore, the imprinting photo-etching machine is simple in structure, has strong adaptability to different types of imprinting glue and can satisfy manufacturing of nanometer structures with big depth-width ratios.
Description
Technical field
The invention belongs to technical field of micro-nano manufacture, be specifically related to the large-area nano imprint lithography method that a kind of pneumoelectric is collaborative.
Background technology
Large-area nano patterning structure is widely used in various fields, such as photovoltaic generation, optoelectronic device, biological micro-fluidic, food packaging safety etc.Large-area nano patterning structure depends on and is applicable to large-area micro-nano manufacturing technology and equipment.Nowadays, main nano-fabrication methods has electron-beam direct writing, laser interference lithography, nanometer bead mask lithography etc., but the manufacturing cost that these technology are respectively freed from its costliness, the graph style of being limited to and manufacturing defect are difficult to the deficiencies such as control, be difficult to the manufacture being applied to large-area nano patterned structures.Through the development of two more than ten years, no matter nanometer embossing is from output, resolution, or manufacturing cost aspect is all that a kind of nanometer having competitive power manufactures means.In numerous nanometer embossing branches and mutation, stepping repeats stamping technique and has used for reference stepping photoetching technique, be a kind of comparatively conventional large-area nano stamping technique, but its still lower manufacture efficiency limits it further to be developed.In addition, roller provides a kind of high speed nano patterning method to plane, roll-to-roll stamping technique, and only need comparatively simple plant equipment, but for the non-smooth substrate of large-area rigidity, the residual layer thickness of notable difference makes its subsequent structural shift (such as dry etching) technology difficulty to be increased greatly, nanostructured distortion even, to such an extent as to sex change was lost efficacy.
Inventor has applied in 2010 patent of invention " apparatus and method of Integral wafer nano-imprinting " (publication number: 102096315A), the method is on the basis of the transparent soft mold of three-layer composite structure, by the normal pressure that pressurized air provides, wafer substrate is contacted uniformly gradually to direction, both sides from mold center position, realize force of impression to be uniformly distributed, to eliminate air blister defect, and realize copying of figure.Knockout course " opens " soft mold continuously from wafer two side direction center, under the acting in conjunction of pull of vacuum and horizontal force, adopts small knockout press to realize the large area demoulding.Due to the flexibility of composite die entirety, make the method can well be fitted with the wafer of certain angularity, realize non-smooth substrate nano patterning.On the basis of the method, inventor has applied for patent of invention " full wafer nano impression three-layer composite structure transparent flexible mold original position manufacture method " (application number: 201410120253 in 2014, in substantive examination), it manufactures thinking is first manufacture master mold, and carries out processing anti-stick company; Then on master mold, apply liquid feature structure layer, then apply elasticity liquid support layer on precuring feature structure layer; Further combined rigidity limiting layer and liquid support layer, then carry out the primary solidification demoulding, finally solidify completely.The wafer scale nano-imprinting method that this gas is auxiliary, the metastatic capacity of nanostructured is mainly derived from capillary force.The project organization of the size of capillary force and selected liquid impression glue material and marking press is in close relations, therefore marking press structural design is limited to the glue material selected, greatly limit the versatility of stamping and photoetching machine, change different impression glue, often mean new stamping and photoetching machine structural design.Further, marking press structure needs the normal pressure high transmission rate air drain that yardstick is little, structure is close usually, the wide 2.5mm spacing of such as 1mm, and this proposes harsh requirement to the manufacture of high-flatness gas tank plate.In addition, faint capillary force, to the manufacture of the column structure of certain depth-to-width ratio, exists and drives hypodynamic problem, be not especially suitable for the manufacture of large area columnar arrays.
Summary of the invention
In order to overcome the shortcoming of above-mentioned prior art, the object of the present invention is to provide the large-area nano imprint lithography method that a kind of pneumoelectric is collaborative, for variety classes impression glue strong adaptability, the manufacture of large depth-to-width ratio nanostructured can be met simultaneously.
To achieve these goals, the present invention adopts following technical scheme:
The large-area nano imprint lithography method that pneumoelectric is collaborative, adopt imprint lithography apparatus, this equipment comprises gas circuit distribution plate 2, plummer 4 and flexible compound mould 1, and the method comprises the following steps:
1) flexible compound mould is installed: the air drain 5 on gas circuit distribution plate 2 is switched to vacuum state, and flexible compound mould 1 non-working surface adsorbs under vacuum and is fixed on gas circuit distribution plate 2;
2) sample to be processed is installed: be installed on sample plummer 4 by the sample 3 of coating impression glue, remain the interval of a 50 ~ 300um between sample 3 and flexible compound mould 1; Flexible compound mould 1 and sample 3 constitute one group contact right, and by the air drain 5 on gas circuit distribution plate 2 by contact to being divided into respective sub-areas;
3) outer field voltage loads: the voltage 7 applying 100 ~ 500V between flexible compound mould 1 and sample 3 surface, defines the sandwich capacity plate antenna structure of flexible compound mould-clearance and liquid impression glue-sample substrate;
4) wing region starts: from one end of flexible compound mould 1, road air drain 5 negative pressure of gas circuit distribution plate 2 is switched to atmospheric pressure state; The flexible compound mould 1 of this air drain 5 correspondence is released, and gradually near also contacting the sample 3 being coated with liquid impression glue under the effect of electrostatic attraction;
5) wing regional structure has shifted: under the effect of electrostatic force, and flexible compound mould 1 and sample 3 contact surface area increase gradually; The direction that osculatory is expanded is parallel with air drain 5 direction; In the region that flexible compound mould 1 contacts with sample 3, under the acting in conjunction of electrostatic attraction and electric capillary force, the nanostructured of flexible compound mould 1, completely fill by liquid state impression glue;
6) Zone Full structure has shifted: air drain 5 contiguous on gas circuit distribution plate 2 is switched to atmospheric pressure state from vacuum successively, and under electrostatic forcing, flexible compound mould 1 and sample 3 surface be complete conform gradually; And achieve the graphical of whole sample 3 surface liquid impression glue;
7) solidify: the adhesive curing of liquid impression, and close impressed voltage 7;
8) demoulding: a road air drain 5 of gas circuit distribution plate 2 one end is switched to vacuum state from atmospheric pressure, under the effect of vacuum power, makes corresponding region flexible compound mould 1 depart from the impression glue of solidification;
9) impressed: gas circuit distribution plate 2 Shang Ge road air drain 5 is switched to vacuum state from atmospheric pressure successively, realized the impression demoulding, complete the nano-imprint lithography process of whole sample.
Described flexible compound mould 1 comprises back sheet 1-1, transparency conducting layer 1-2 and functional structure layer 1-3, and have flexibility, conduction, transparent feature, its manufacturing step is as follows simultaneously:
1) utilize electron-beam direct writing method to manufacture wafer scale master mold 6, in nanostructured face, deposition fluorine octafluorocyclobutane reduces its surface energy;
2) magnetron sputtering transparency conducting layer 1-2 on back sheet 1-1;
3) the liquid functional layer material of spin coating spin coating in 1000 turns/2 minutes on wafer scale master mold 6;
4) utilize oxygen gas plasma process transparency conducting layer, bonding transparency conducting layer 1-2 and liquid functional layer material, and solidify completely;
5) from the demoulding wafer scale master mold 6, flexible compound mould 1 has manufactured.
Described gas circuit distribution plate 2 manufactured materials is organic glass (PMMA), or optical glass (Glass).
On described gas circuit distribution plate 2 quantity of air drain 5 per sample 3 warpages increase and increase, per sample 3 warpages reduce and reduce.
The vacuum negative pressure size that on described gas circuit distribution plate 2, air drain 5 applies, the knockout press required for different sample 3 object increases and increases, and reduces and reduce according to required knockout press.
The described voltage 7 applied with sample 3 surface at flexible compound mould 1, the size according to different air drains 5 number, impression glue specific inductive capacity changes, and specific inductive capacity is high, then required voltage is lower, and specific inductive capacity is low, then required voltage is higher.
Described wafer scale master mold 6 take silicon as master mold base material, according to semicon industry standard process flows, adopts optical lithography, electron-beam direct writing or laser interference lithography micro-nano graph method, and makes master mold in conjunction with etching technics.
Described transparency conducting layer 1-2 adopts tin indium oxide (ITO), mixes the transparent conductive material of the tin ash (FTO) of fluorine.
The present invention is except the series of advantages that Conventional nano stamping technique has, and remarkable advantage also comprises:
1) gas-electric coordinated drive nano-imprinting method, except smooth substrate, is suitable for too the non-smooth substrate that there is certain warpage, significantly improves the scope of application of nanometer embossing;
2) gas-electric coordinated drive nano-imprinting method is a kind of full wafer stamping technique, significantly improves the efficiency that nanostructured large area manufactures;
3) under the effect of electric field driven power, gas-electric coordinated drive nano-imprinting method can be applicable to manufacture large depth-to-width ratio nanostructured, significantly improves the manufacturing capacity of nanometer embossing;
4) gas-electric coordinated drive nano-imprinting method can change extra electric field size neatly, realize the modulation of electric field-assisted power size, adapts to the manufacture demand of different structure feature nanostructured.
Accompanying drawing explanation
Fig. 1 is the present embodiment schematic flow sheet, and wherein Fig. 1 (a) is preparatory stage schematic diagram; Fig. 1 (b) places for initial sample and schemes; Fig. 1 (c) is flexible compound mould 1 and sample room on-load voltage schematic diagram; Fig. 1 (d) works in coordination with wing for pneumoelectric and starts imprint lithography schematic diagram; Fig. 1 (e) works in coordination with imprint lithography for pneumoelectric and completes schematic diagram; Figure (1f) is for removing electricity and solidifying schematic diagram; Fig. 1 (g) is impression demoulding schematic diagram; Fig. 1 (h) completes schematic diagram for imprint process.
Fig. 2 is embodiment nanostructured pictorial diagram.
Fig. 3 is that flexible compound mould 1 manufactures schematic diagram, and wherein Fig. 3 (a) is the master mold schematic diagram after low-surface-energy process; Fig. 3 (b) is sputtering ITO schematic diagram on back sheet; Fig. 3 (c) is master mold schematic diagram after choosing figure hPDMS; Fig. 3 (d) is ITO and hPDMS bonding schematic diagram; Fig. 3 (e) is flexible compound mould schematic diagram.
Embodiment
Below in conjunction with drawings and Examples, the present invention is described in detail.
With reference to Fig. 1, the large-area nano imprint lithography method that a kind of pneumoelectric is collaborative, adopt imprint lithography apparatus, this equipment comprises gas circuit distribution plate 2, plummer 4 and flexible compound mould 1, and the method comprises the following steps:
1) as shown in Fig. 1 (a), the air drain 5 on gas circuit distribution plate 2 is switched to vacuum state, the PET opaque backing layer 1-1 back side of flexible compound mould 1 is adsorbed under vacuum and is fixed on gas circuit distribution plate 2;
2) as shown in Fig. 1 (b), the 4 inches of GaN epitaxy sheet samples 3 being coated with 550nm ultraviolet solidified nano impression glue mr-06 are installed on sample plummer 4, between sample 3 and flexible compound mould 1, remain 200um interval; Flexible compound mould 1 and sample 3 constitute one group contact right, and by the air drain 5 on gas circuit distribution plate 2 by contact to being divided into four sub regions;
3) as shown in Fig. 1 (c), between flexible compound mould 1 and sample 3 surface, apply 200v voltage 7, define the sandwich capacity plate antenna structure of flexible compound mould-clearance and liquid impression glue-sample;
4) as shown in Fig. 1 (d), from one end of flexible compound mould 1, road air drain 5 negative pressure of gas circuit distribution plate 2 is switched to atmospheric pressure state; The flexible compound mould 1 of this air drain 5 correspondence is released, and gradually near also contacting the sample 3 being coated with liquid impression glue under the effect of electrostatic attraction;
5) as shown in Fig. 1 (d), under the effect of electrostatic force, flexible compound mould 1 and sample 3 contact surface area increase gradually; The direction that osculatory is expanded is parallel with air drain 5 direction; In the region that flexible compound mould 1 contacts with sample 3, under the acting in conjunction of electrostatic attraction and electric capillary force, the nanometer column structure of flexible compound mould 1, completely fill by liquid state impression glue;
6) as shown in Fig. 1 (e), air drain 5 contiguous on gas circuit distribution plate 2 is switched to atmospheric pressure state from vacuum successively, under electrostatic forcing, flexible compound mould 1 and sample 3 surface be complete conform gradually; And achieve the graphical of whole sample 3 surface liquid impression glue;
7) as shown in Fig. 1 (f), uv-exposure 30s, the adhesive curing of liquid impression, and close impressed voltage 7;
8) as shown in Fig. 1 (g), a road air drain 5 of gas circuit distribution plate 2 one end is switched to vacuum state from atmospheric pressure, under the effect of vacuum power, corresponding region flexible compound mould 1 is departed from the impression glue of solidification;
9) as shown in Fig. 1 (h), gas circuit distribution plate 2 Shang Ge road air drain 5 is switched to vacuum state from atmospheric pressure successively, realize the impression demoulding, complete the nano-imprint process process of whole sample, manufacture result as shown in Figure 2.
In the present embodiment, gas circuit distribution plate 2 adopts PMMA material, and thickness is 10mm, front is uniform five road air drains 5, air drain 5 degree of depth 3mm, broadband 1mm.Flexible compound mould 1, adopt PET (polyethylene terephthalate) opaque backing layer 1-1, ITO (electro-conductive glass) transparency conducting layer 1-2, hPDMS (hard dimethyl silicone polymer) functional structure layer 1-3 three-decker, thickness is followed successively by 200um, 50nm, 20um.Flexible compound mould 1 is 350nm diameter, and 500nm is high, is spaced apart the column structure array of 600nm.
With reference to Fig. 3, described flexible compound mould 1 comprises back sheet 1-1, transparency conducting layer 1-2 and functional structure layer 1-3, and have flexibility, conduction, transparent feature, its manufacturing step is as follows simultaneously:
1) as shown in Fig. 3 (a), beamwriter lithography mode is utilized to manufacture wafer scale master mold 6, and at surface deposition one deck 10nm octafluorocyclobutane (C
4f
8) reduce its surface energy;
2) as shown in Fig. 3 (b), magnetron sputtering 50nmITO transparency conducting layer 1-2 in back sheet 1-1 one side;
3) as shown in Fig. 3 (c), the liquid hPDMS of spin coating in 1000 turns/2 minutes on wafer scale master mold 6;
4) as shown in Fig. 3 (d), bonding ITO and liquid hPDMS, and 65 DEG C solidify 4 hours, and hPDMS is solidified completely, form functional structure layer 1-3;
5) as shown in Fig. 3 (e), the demoulding from wafer scale master mold 6, flexible compound mould 1 has manufactured.
Claims (8)
1. the large-area nano imprint lithography method that a pneumoelectric is collaborative, adopt imprint lithography apparatus, this equipment comprises gas circuit distribution plate (2), plummer (4) and flexible compound mould (1), it is characterized in that, comprises the following steps:
1) flexible compound mould is installed: the air drain (5) on gas circuit distribution plate (2) is switched to vacuum state, and flexible compound mould (1) non-working surface adsorbs under vacuum and is fixed on gas circuit distribution plate (2);
2) sample to be processed is installed: be installed on sample plummer (4) by the sample (3) of coating impression glue, remain the interval of a 50 ~ 300um between sample (3) and flexible compound mould (1); Flexible compound mould (1) and sample (3) constitute one group contact right, and by the air drain (5) on gas circuit distribution plate (2) by contact to being divided into respective sub-areas;
3) outer field voltage loads: the voltage (7) applying 100 ~ 500V between flexible compound mould (1) and sample (3) surface, defines the sandwich capacity plate antenna structure of flexible compound mould-clearance and liquid impression glue-sample substrate;
4) wing region starts: from one end of flexible compound mould (1), road air drain (5) negative pressure of gas circuit distribution plate (2) is switched to atmospheric pressure state; The flexible compound mould (1) that this air drain (5) is corresponding is released, and gradually near also contacting the sample (3) being coated with liquid impression glue under the effect of electrostatic attraction;
5) wing regional structure has shifted: under the effect of electrostatic force, and flexible compound mould (1) and sample (3) contact surface area increase gradually; The direction that osculatory is expanded is parallel with air drain (5) direction; In the region that flexible compound mould (1) contacts with sample (3), under the acting in conjunction of electrostatic attraction and electric capillary force, the nanostructured of flexible compound mould (1), completely fill by liquid state impression glue;
6) Zone Full structure has shifted: upper for gas circuit distribution plate (2) contiguous air drain 5 is switched to atmospheric pressure state from vacuum successively, under electrostatic forcing, flexible compound mould (1) and sample (3) surface be complete conform gradually; And achieve the graphical of whole sample (3) surface liquid impression glue;
7) solidify: the adhesive curing of liquid impression, and close impressed voltage (7);
8) demoulding: a road air drain (5) of gas circuit distribution plate (2) one end is switched to vacuum state from atmospheric pressure, under the effect of vacuum power, makes corresponding region flexible compound mould (1) depart from the impression glue of solidification;
9) impressed: gas circuit distribution plate (2) Shang Ge road air drain (5) is switched to vacuum state from atmospheric pressure successively, realized the impression demoulding, complete the nano-imprint lithography process of whole sample.
2. the large-area nano imprint lithography method that a kind of pneumoelectric according to claim 1 is collaborative, it is characterized in that: described flexible compound mould (1) comprises back sheet (1-1), transparency conducting layer (1-2) and functional structure layer (1-3), have flexibility, conduction, transparent feature, its manufacturing step is as follows simultaneously:
1) electron-beam direct writing method is utilized to manufacture wafer scale master mold (6), at nanostructured face deposition fluorine octafluorocyclobutane;
2) at the upper magnetron sputtering transparency conducting layer (1-2) of back sheet (1-1);
3) in the liquid functional layer material of wafer scale master mold (6) spin coating in upper 1000 turns/2 minutes;
4) utilize oxygen gas plasma process transparency conducting layer, bonding transparency conducting layer (1-2) and liquid functional layer material, and solidify completely;
5) from the demoulding wafer scale master mold (6), flexible compound mould (1) has manufactured.
3. the large-area nano imprint lithography method that a kind of pneumoelectric according to claim 1 is collaborative, it is characterized in that: described gas circuit distribution plate (2) manufactured materials is organic glass (PMMA), or optical glass (Glass).
4. the large-area nano imprint lithography method that a kind of pneumoelectric according to claim 1 is collaborative, it is characterized in that: the quantity of the upper air drain (5) of described gas circuit distribution plate (2) increases according to different sample (3) warpage and increases, and (3) warpage reduces and reduces per sample.
5. the large-area nano imprint lithography method that a kind of pneumoelectric according to claim 1 is collaborative, it is characterized in that: the vacuum negative pressure size that the upper air drain (5) of described gas circuit distribution plate (2) applies, knockout press required for different sample (3) object increases and increases, and reduces and reduce according to required knockout press.
6. the large-area nano imprint lithography method that a kind of pneumoelectric according to claim 1 is collaborative, it is characterized in that: the described voltage (7) applied with sample (3) surface at flexible compound mould (1), according to different air drains (5) number, impression glue type change, specific inductive capacity is high, then required voltage is lower, specific inductive capacity is low, then required voltage is higher.
7. the large-area nano imprint lithography method that a kind of pneumoelectric according to claim 2 is collaborative; it is characterized in that: described wafer scale master mold (6) take silicon as master mold base material; according to semicon industry standard process flows; adopt optical lithography, electron-beam direct writing or laser interference lithography micro-nano graph method, and make master mold in conjunction with etching technics.
8. the large-area nano imprint lithography method that a kind of pneumoelectric according to claim 2 is collaborative, is characterized in that: described transparency conducting layer (1-2) adopts tin indium oxide (ITO), mixes the transparent conductive material of the tin ash (FTO) of fluorine.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110632824A (en) * | 2019-09-11 | 2019-12-31 | 中国科学院光电技术研究所 | Method for improving position precision of template transfer printing flexible substrate microstructure |
| CN118092075A (en) * | 2024-04-28 | 2024-05-28 | 苏州新维度微纳科技有限公司 | Nanoimprint gluing method, gluing structure and nanoimprint method |
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| CN103869611A (en) * | 2014-03-27 | 2014-06-18 | 西安交通大学 | Method for manufacturing three-layer composite structured transparent soft mold for full-chip nano-imprint lithography in situ |
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| CN118092075A (en) * | 2024-04-28 | 2024-05-28 | 苏州新维度微纳科技有限公司 | Nanoimprint gluing method, gluing structure and nanoimprint method |
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