CN109722666A - The preparation method and metallic film mold intermediate of metallic film mold with surface micro-nano structure - Google Patents
The preparation method and metallic film mold intermediate of metallic film mold with surface micro-nano structure Download PDFInfo
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- CN109722666A CN109722666A CN201711048920.0A CN201711048920A CN109722666A CN 109722666 A CN109722666 A CN 109722666A CN 201711048920 A CN201711048920 A CN 201711048920A CN 109722666 A CN109722666 A CN 109722666A
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Abstract
The present invention provides the preparation methods of the metallic film mold with surface micro-nano structure and metallic film mold intermediate.The described method includes: providing the template with surface micro-nano structure；By the first physical vapour deposition (PVD), the first anti-sticking metal layer of nanometer grade thickness is formed on the surface of the surface micro-nano structure of the template, and there is the first binding force between the first anti-sticking metal layer and template；And by the first plating, the first electroplated metal layer of micron order thickness is formed on the described first anti-sticking metal layer, there is the second binding force between first electroplated metal layer and the first anti-sticking metal layer；Wherein, first binding force is less than the second binding force, and the first anti-sticking metal layer acts also as conductive layer in first plating step.Method of the invention can ideally replicate the three-dimensional surface micro-nano structure of template, to obtain the metallic film mold with required surface micro-nano structure.
Description
Technical field
The present invention relates to electrochemical fields, and in particular to the preparation method of the metallic film mold with surface micro-nano structure
With metallic film mold intermediate.
Background technique
Nano/micron structure be widely used in improve opto-electronic device performance, opto-electronic device include display,
Solar battery and light emitting diode.This optimization derives from photon and opto-electronic device in the phase interaction of micron and nano-scale
With.Therefore, in order to reduce unit area cost, obtaining large area and efficient nano/micron structure preparation process seems outstanding
It is important.
Roll-to-roll hot padding and roll-to-roll ultraviolet nanometer/micron imprint process are to realize large area high efficiency nano/micron
The ideal scheme of structure preparation.However, huge challenge first is that production meet the large-area nano of the roll-to-roll machine of technical grade/
Micrometer structure metallic film mold.
Production large area mold is the committed step of roll-to-roll Nano/micron coining.Laser writing technology has been used for
The preparation of technical grade large-area metal film die makes micro-meter scale metallic film mold using laser direct writing equipment, still
Structure size is but only capable of reaching micron level.On the other hand, this technique not only relies on expensive equipment, and is fabricated to
This height, while it is long to make large area mold elapsed time.High cost hinders the city of nano/micron structure optoelectronic applications
Field occupation rate.For example, it is estimated that the metallic film mold of one size 400mm × 400mm of production is needed more than 1000 dollars.
Most of micro-nano application industries can not receive cost high in this way.In addition, by the use in several periods, mould structure meeting
It destroys to need replacing.Meanwhile the micrometer structure type that the technique can make is limited.For example, nanocone and nano pyramid
Structure cannot be directly obtained by laser direct writing equipment in metal surface.Different types of nano/micron structure can be used for
Different application, as nanocone can be used for the antireflective application of photovoltaic industry.Traditional metallic film mould manufacturing method can not expire
The needs of these novel Nano/micron technologies of foot and development.
Summary of the invention
For solve it is above-mentioned the problems of in the prior art, the present invention provides a kind of gold with surface micro-nano structure
The preparation method for belonging to film die, additionally provides a kind of metallic film mold intermediate.
Specifically, the present invention provides:
(1) a kind of preparation method of the metallic film mold with surface micro-nano structure, includes the following steps:
The template for having surface micro-nano structure is provided；
By the first physical vapour deposition (PVD), nanometer grade thickness is formed on the surface of the surface micro-nano structure of the template
First anti-sticking metal layer has the first binding force between the first anti-sticking metal layer and template；And
By the first plating, the first electroplated metal layer of micron order thickness is formed on the described first anti-sticking metal layer, it should
There is the second binding force between first electroplated metal layer and the first anti-sticking metal layer；
Wherein, first binding force is less than the second binding force, and the first anti-sticking metal layer is in first electricity
Conductive layer is acted also as in plating step.
(2) method according to (1), further includes following steps:
After the first plating, the described first anti-sticking metal layer and the template with surface micro-nano structure are removed；From
And the metallic film mold intermediate being made of the described first anti-sticking metal layer and first electroplated metal layer is obtained, the gold
Belonging to film die intermediate has minus micro-nano structure corresponding with the template.
(3) method according to (2), further includes following steps:
By the second physical vapour deposition (PVD), formed on the minus micro-nano structure surface of the metallic film mold intermediate
The anti-sticking metal layer of the second of nanometer grade thickness has third knot between the second anti-sticking metal layer and metallic film mold intermediate
With joint efforts；And
By the second plating, the second electroplated metal layer of micron order thickness is formed on the described second anti-sticking metal layer, it should
There is the 4th binding force between second electroplated metal layer and the second anti-sticking metal layer；
Wherein, the third binding force is less than the 4th binding force.
(4) method according to (1), wherein the first anti-sticking metal layer is the metal layer with a thickness of 1nm-100 μm,
The metal layer is formed by e-beam vacuum deposition technology；First electroplated metal layer is the gold with a thickness of 1-200 μm
Belong to layer.
(5) method according to (4), wherein the first anti-sticking metal layer is formed by one of following metal, institute
Stating metal is gold, silver, copper, iron, nickel, titanium, cobalt, chromium, platinum, rhodium, palladium and its alloy；First electroplated metal layer is by following metal
One of formed, the metal be gold, silver, copper, iron, nickel, titanium, cobalt, chromium, platinum, rhodium, palladium and its alloy.
(6) method according to (3), wherein the second anti-sticking metal layer is the metal layer with a thickness of 1nm-100 μm,
The metal layer is formed by e-beam vacuum deposition technology；Second electroplated metal layer is the gold with a thickness of 1-200 μm
Belong to layer.
(7) method according to (6), wherein the second anti-sticking metal layer is formed by one of following metal, institute
Stating metal is gold, silver, copper, iron, nickel, titanium, cobalt and chromium；Second electroplated metal layer is formed by one of following metal, institute
Stating metal is copper, nickel, cobalt and chromium.
(8) method according to (1), wherein the template with surface micro-nano structure is that its surface has silica
The Silicon Wafer of layer, the first anti-sticking metal layer are gold, and first electroplated metal layer is copper.
(9) method according to (1), wherein the second anti-sticking metal layer is nickel, second electroplated metal layer is
Nickel.
(10) method according to (1), wherein the offer includes leading to the step of having the template of surface micro-nano structure
Cross the end shape that magnetron sputtering technique changes the surface micro-nano structure.
(11) method according to (10) wherein the surface micro-nano structure is micro-nano pyramid, and passes through magnetic
Control sputtering technology changes the micro-nano pyramidal top angle.
(12) method according to (1), wherein the template is any one in the template as made from following method
Kind:
The template made of electron beam exposure；
The template made of photoetching and etching technique；
The template made of nano-imprinting method；
The template made of electrochemical oxidation and wet etching.
(13) method according to (1), wherein the surface micro-nano structure be micro-nano pyramid, it is micro-nano cone, it is micro-
Nano-pillar, micro-nano point or micro-nano hole.
(14) method according to (1), wherein template is any one in following template: silicon template, metal form,
Metal oxide template, plastic formwork.
(15) method according to (14), wherein the metal oxide template is to be lost by electrochemical oxidation and wet process
Alumina formwork made of carving.
(16) method according to (1) is wherein the template with surface micro-nano structure is large area template
It is formed and the edge of at least two pieces lesser templates is mutually stitched together.
(17) method according to (16) in the splicing step, is led to wherein the lesser template is Silicon Wafer
The a part for cutting off the silicon wafer the edge of the circle is crossed, will there is the Silicon Wafer at the edge after cutting to be placed side by side on a horizontal plane, two
The cut edge of item is parallel to each other and there are small gaps therebetween, then by being somebody's turn to do with the glue filling of UV curable
Gap simultaneously carries out ultra-violet curing, to obtain large area template.
(18) a kind of metallic film mold intermediate, the metallic film mold intermediate are by with surface micro-nano knot
Pass through the anti-sticking metal of physical vapour deposition (PVD) then re-plating metal in the template of structure, then the template is stripped down and is formed
, the anti-sticking metal layer which is obtained by physical vapour deposition (PVD) and the electroplated metal layer obtained by plating
It constitutes, which has minus micro-nano structure corresponding with the template.
(19) method according to (18), wherein the anti-sticking metal layer is formed by one of following metal, it is described
Metal be gold, silver, copper, iron, nickel, titanium, cobalt, chromium, platinum, rhodium, palladium and its alloy, the anti-sticking metal layer with a thickness of 1nm-100 μ
m；The electroplated metal layer is formed by one of following metal, the metal be gold, silver, copper, iron, nickel, titanium, cobalt, chromium, platinum,
Rhodium, palladium and its alloy, the electroplated metal layer with a thickness of 1-200 μm.
The property between metal and different materials with different binding forces is dexterously utilized in the present invention, and passes through physics gas
Mutually deposition is used in combination with plating, develops a kind of preparation method of metallic film mold with surface micro-nano structure, together
When additionally provide a kind of metallic film mold intermediate.Compared with the prior art, the present invention has the following advantages and good effect:
1. method of the invention is by dexterously using the property between metal and different materials with different binding forces, making
Obtaining can easily be removed from template by the metallic film mold of template duplicating, without destroying template, make its prototype structure will not
It is changed, therefore template may be reused, to effectively save cost；At the same time, template can ideally be replicated
Three-dimensional surface micro-nano structure (including nanostructure and micrometer structure), to obtain the metal foil with required surface micro-nano structure
Film die.
2. method of the invention is suitble to the template using various different materials, metallic film mold making process is expanded
The scope of application.
3. the metallic film mould that method of the invention can obtain nanoscale and micron-sized various different shapes and size
Have surface micro-nano structure, including micro-nano pyramid, micro-nano cone, micro-nano column, micro-nano point or micro-nano hole structure, therefore
It is more wide in range for the selection of die surface micro-nano structure.
4. by the present invention in that with physical vapour deposition (PVD) and electroplating technology, so that the preparation process cost of metallic film mold
It is low, the used time is few, can be achieved large-scale production.
5. template lesser for size, the present invention can obtain the template of large area by splicing process, thus to obtain big
Area nanometer/micrometer structure metallic film mold.Therefore, the present invention breaches area limitation, suitable for Nano/micron coining
Size requirement.
6. operation of the present invention is simple, the used time is few, it is high-efficient, be suitable for industrial production.
Detailed description of the invention
Fig. 1 a is sweeping for the silicon template with inverted pyramid structure array obtained by the lithography and etching technique of standard
Retouch electron micrograph；Fig. 1 b is the electron scanning micrograph for being covered with the silicon template of chromium；
Fig. 2 is the signal for showing the process for preparing metallic film mold in one embodiment of the invention using silicon template
Figure；
Fig. 3 is template used in one embodiment of the invention and gained mold electron scanning micrograph；Wherein
Fig. 3 a is the electron scanning micrograph for being covered with the silicon template of chromium metal layer；Fig. 3 b is the scanning for being covered with the copper mould of gold
Electron micrograph；Fig. 3 c is the electron scanning micrograph for having defective nickel mold；Fig. 3 d is in golden etching liquid
The electron scanning micrograph of nickel mold after impregnating one minute；
Fig. 4 a is the schematic diagram for showing silicon template splicing process；Fig. 4 b is big for the two panels Silicon Wafer obtained by splicing process
The photo of small silicon template；Fig. 4 c is the photo of the resulting large scale nickel mold of the silicon template as shown in Fig. 4 b；
Fig. 5 is to show the stream for preparing metallic film mold in another embodiment of the invention by template of anodised aluminium
The schematic diagram of journey；
Fig. 6 is template used in another embodiment of the invention and gained mold electron scanning micrograph；Its
Middle Fig. 6 a is the electron scanning micrograph of the anodic oxidation aluminium formwork in 1.2 μm of periods；Fig. 6 b is the copper mould for being covered with gold
Electron scanning micrograph；Fig. 6 c is to show the electron scanning micrograph for having defective nickel mold；Fig. 6 d is to show
The electron scanning micrograph of nickel mold after being impregnated one minute in golden etching liquid out；
Fig. 7 a is the photo of the anodic oxidation aluminium formwork of 30cm × 15cm；Fig. 7 b is the anodic oxidation aluminium formwork as shown in Fig. 7 a
The photo of the large area nickel mold of resulting 25cm × 14cm.
Fig. 8 is to show showing for the process for preparing metallic film mold in another embodiment of the invention by template of plastics
It is intended to；
Fig. 9 a is the photo after plastic formwork is gold-plated；Fig. 9 b is the photo of the nickel mold prepared by template of plastics；Fig. 9 c
It is respectively the electron scanning micrograph for showing the micro-structure of plastic formwork and nickel mold with d.
Specific embodiment
Description below by way of specific embodiment and the invention will be further described referring to attached drawing, but it is pair that this, which is not,
Limitation of the invention, those skilled in the art's basic thought according to the present invention, can make various modifications or improvements, but only
Basic thought of the invention is not departed from, is all within the scope of the present invention.
In the presence of solving the problems, such as the above-mentioned prior art, prepared by developing low-cost, high efficiency, the technique of scale
Large-area nano/micrometer structure metallic film mold, the present inventor innovatively propose using metal and different materials it
Between with different binding forces property, and be used cooperatively physical vapour deposition (PVD) and plating so that by template preparation receive
During rice/micrometer structure metallic film mold, gained replicated architecture body can be removed easily from corresponding template, without
Template is destroyed, be changed the initial surface micro-nano structure of template will not, and at the same time, can ideally replicate template
Three-dimensional surface micro-nano structure (including nanostructure and micrometer structure) thus can get the metal with required surface micro-nano structure
Film die.
Cleverly conceived based on above-mentioned, the system of the present invention provides a kind of metallic film mold with surface micro-nano structure
Preparation Method includes the following steps:
A kind of template with surface micro-nano structure is provided；
By the first physical vapour deposition (PVD), nanometer grade thickness is formed on the surface of the surface micro-nano structure of the template
First anti-sticking metal layer has the first binding force between the first anti-sticking metal layer and template；And
By the first plating, the first electroplated metal layer of micron order thickness is formed on the described first anti-sticking metal layer, it should
There is the second binding force between first electroplated metal layer and the first anti-sticking metal layer；
Wherein, first binding force is less than the second binding force, and the first anti-sticking metal layer is in first electricity
Conductive layer is acted also as in plating step.
It, can be by the described first anti-sticking metal layer and the tool since first binding force is less than the second binding force
There is the template of surface micro-nano structure easily to remove, obtains by the described first anti-sticking metal layer and the first electroplated metal layer institute
The metallic film mold intermediate of composition, the metallic film mold intermediate have minus micro-nano knot corresponding with the template
Structure.In turn, it based on above-mentioned design of the invention, using the minus micro-nano structure, and continues through using having with different materials
The anti-sticking metal layer of different binding forces, and pass through the combination of physical vapour deposition (PVD) and plating, duplication obtains having with the template
The metallic film mold of identical three-dimensional surface micro-nano structure.
Therefore, specifically, method of the invention further includes following steps: anti-sticking by described first after the first plating
Metal layer and the template with surface micro-nano structure are removed；To obtain by the described first anti-sticking metal layer and described first
The metallic film mold intermediate that electroplated metal layer is constituted, the metallic film mold intermediate have corresponding with the template
Minus micro-nano structure.
More specifically, method of the invention further includes following steps: by the second physical vapour deposition (PVD), in the metal
The second anti-sticking metal layer of nanometer grade thickness, the second anti-sticking gold are formed on the minus micro-nano structure surface of film die intermediate
Belonging to has third binding force between layer and metallic film mold intermediate；And by the second plating, in the described second anti-sticking gold
Belong to the second electroplated metal layer that micron order thickness is formed on layer, between second electroplated metal layer and the second anti-sticking metal layer
With the 4th binding force；Wherein, the third binding force is less than the 4th binding force.
More specifically, method of the invention further include will be in the described second anti-sticking metal layer and the metallic film mold
Mesosome removing, to obtain metallic film mold.
The term as used herein " surface micro-nano structure " refers to the surface texture of micron order or nano-grade size, for example, micro-
Meter level surface micro-nano structure includes micron pyramid, micron cone, micron column, micron point or micron openings etc.；Nanoscale Surface micro-nano
Structure includes nano pyramid, nano-pore, nanocone etc.；These may be collectively referred to as micro-nano pyramid, it is micro-nano cone, it is micro-nano
Column, micro-nano point or micro-nano hole etc..
The term as used herein " minus micro-nano structure " refers to and the form ruler of corresponding " surface micro-nano structure " entirety
It is very little identical, but direction is completely on the contrary, for example, if " surface micro-nano structure " is nanometer inverted pyramid, corresponding " minus
Micro-nano structure " is the positive pyramid of nanometer.
The term as used herein " template with surface micro-nano structure " refers to surface micro-nano structure, for passing through object
The combination of physical vapor deposition and plating is to manufacture material used in the metallic film mold with similar face micro-nano structure.Example
Such as, in the present invention certain embodiments described below, for specific purpose, in the surface micro-nano knot of template original material
Apply oxide skin(coating) or other materials on structure, the template formed in this way still there is surface micro-nano structure and be used for after the first object
Physical vapor deposition, then the oxide skin(coating) and/or the other materials are referred to as template together with template original material, that is,
It says, the oxide skin(coating) and the other materials also belong within the implication scope of " template with surface micro-nano structure ".
Method of the invention is suitable for any surface of solids, the template of various different materials can be used, and also fit
For various surface micro-nano structures.For example, any one template used that can be in following template: silicon template, metal form,
Metal oxide template, plastic formwork.The template can be any one in the template as made from following method: by electricity
Beamlet exposes manufactured template；The template made of photoetching and etching technique；The template made of nano-imprinting method；By electrification
Learn template made of oxidation and wet etching.In certain embodiments, the metal oxide template is by electrochemistry oxygen
The alumina formwork changed and there is surface micro-nano structure made of wet etching.Electrochemical method it is cheap and independent of
Complicated equipment.In certain embodiments, template used is to obtain surface in silicon wafer surface by lithography and etching technology
Micro-nano structure and manufactured silicon template.In certain embodiments, the plastic formwork is polymethyl methacrylate (PMMA).
Be also possible to other plastics, as polystyrene plastics (PS), polystyrene plastics (PC), polystyrene plastics (PP),
Polystyrene plastics (PVC), polystyrene plastics (PE) and uv-curable glue etc..The surface micro-nano structure of template can be
Micro-nano pyramid (including inverted pyramid and positive pyramid), micro-nano cone, micro-nano column, micro-nano point or micro-nano hole.Its
Middle micro-nano hole structure can be used for many applications, such as antireflection layer, super capacitor and anti-fog layer.
For the purposes of the present invention, in certain embodiments, one layer of oxygen can be covered in the surface micro-nano structure of template
The binding force between the oxide skin(coating) and the first anti-sticking metal layer is electroplated less than the first anti-sticking metal layer and first in compound layer
Binding force between metal layer, to achieve the effect that template is easily isolated with the first anti-sticking metal layer.As described above, the oxygen
Compound layer also belongs within the implication scope of " template with surface micro-nano structure " as described herein.For example, in silicon template
In situation, which can also include the silica being deposited thereon, which also belongs to the implication scope of " silicon template "
Within.
On the other hand, it is a discovery of the invention that the variation of the end shape or angle of template surface micro-nano structure is to raising material
It is significant with device performance.For example, the end shape or angle of change material surface micro-nano structure can change material
Absorbing properties and surface hydrophobic, this can largely widen the application scenarios of metallic film mold.
The end shape or angle for changing template surface micro-nano structure can be by utilizing such as magnetron sputtering technique on surface
The top of micro-nano structure covers one layer of other material to realize.For example, in the embodiment depicted in fig. 1, being splashed by magnetic control
It penetrates technology and covers one layer of chromium on the surface of the inverted pyramid structure array of silicon template, to change the top folder of inverted pyramid
Angle.As described above, which also belongs to containing for " template with surface micro-nano structure " as described herein
Within adopted range.In the case where being deposited with silicon oxide layer in silicon template, the silicon oxide layer preferably is deposited after covering chromium.
Preferably, the template with surface micro-nano structure is that large area template can be and pass through as needed
The edge of at least two pieces lesser templates is mutually stitched together and is formed.According to needs are applied, which can
Think any size, such as 7cm × 14cm.In this way, the present invention can effectively and at low cost prepare the Nano/micron of large area
Structural metal film die.An example for by template splicing and finally obtaining large area mold is as shown in Figure 4.
Particularly, when lesser template is Silicon Wafer, following splicing step can be used: by cutting off the silicon wafer the edge of the circle
A part, will have the Silicon Wafer at edge after cutting be placed side by side on a horizontal plane, two cut edges are each other
There are small gap (should minimize gap) in parallel and therebetween, then by filling the seam with the glue of UV curable
Gap simultaneously carries out ultra-violet curing, to obtain large area template.
In the present invention, the physical vapour deposition (PVD) can be any physical gas phase deposition technology, including vapor deposition and electricity
Beamlet vacuum deposition etc..
In the method for the invention, it is preferred that the first anti-sticking metal layer is the metal layer with a thickness of 1nm-1 μm,
Such as 1nm-100nm, the thickness of the first anti-sticking metal layer is most preferably 100nm, which can be heavy by electron beam vacuum
Product technology is formed.
It is also preferred that first electroplated metal layer is the metal layer with a thickness of 1 μm -200 μm, such as 1 μm -100 μm,
The thickness of first electroplated metal layer is most preferably 100 μm.
The first anti-sticking metal is preferably selected from gold, silver, copper, iron, nickel, titanium, cobalt, chromium, platinum, rhodium, palladium and its alloy
One kind, first plating metal are preferably selected from one in gold, silver, copper, iron, nickel, titanium, cobalt, chromium, platinum, rhodium, palladium and its alloy
Kind, condition is binding force between the first anti-sticking metal layer and template less than the first electroplated metal layer and the described first anti-sticking metal
Binding force between layer.
In a preferred embodiment of the present invention, the template with surface micro-nano structure is that its surface has silica
Layer Silicon Wafer, the first anti-sticking metal be gold, the first plating metal be copper, gold and silica between binding force be less than gold with
Binding force between copper.
In another preferred embodiment of the present invention, with surface micro-nano structure template alumina formwork, first
Anti-sticking metal is gold, and the first plating metal is copper, and the binding force between gold and anodised aluminium is less than the combination between Jin Yutong
Power.
It can be seen that of the invention being contemplated that makes the first binding force less than the second binding force, therefore can be easily by
One anti-sticking metal layer is removed with the template with surface micro-nano structure, to not destroy template, and obtains having and the template
The metallic film mold intermediate of corresponding minus micro-nano structure.
In the method for the invention, it is preferred that the second anti-sticking metal layer is the metal layer with a thickness of 1nm-1 μm,
Such as 1nm-100nm, the thickness of the second anti-sticking metal layer is most preferably 100nm, which can be heavy by electron beam vacuum
Product technology is formed.
It is also preferred that second electroplated metal layer is the metal layer with a thickness of 1 μm -200 μm, such as 1 μm -100 μm,
The thickness of second electroplated metal layer is most preferably 100 μm.
The second anti-sticking metal is preferably selected from one of metals such as gold, silver, copper, iron, nickel, titanium, cobalt, chromium, and described
Two plating metals are preferably selected from one of metals such as copper, nickel, cobalt, chromium, and condition is the second anti-sticking metal layer and metallic film mould
Has the binding force between intermediate less than the binding force between the second electroplated metal layer and the second anti-sticking metal layer.
In a preferred embodiment, the described second anti-sticking metal layer is formed by nickel, second electroplated metal layer
It is formed by nickel.
In a preferred embodiment of the present invention, metallic film mold intermediate is formed by gold and copper, and golden structure
At the minus micro-nano structure surface of metallic film mold intermediate, the second anti-sticking metal is nickel, and the second plating metal is nickel, second
Binding force between anti-sticking metallic nickel and gold is less than the binding force between the second anti-sticking metallic nickel and the second plating metal nickel.
It can be seen that of the invention being contemplated that makes third binding force less than the 4th binding force, therefore can be easily by
Two anti-sticking metal layers and mold intermediate with minus micro-nano structure corresponding with template are removed, to be had and template
The metallic film mold of identical surface micro-nano structure.Here, " the mold intermediate " or " metallic film mold intermediate "
Refer to identical concept, it, can also be by cage when for the metallic film mold relative to the second anti-sticking metal layer and finally obtained
System ground is known as template.
Physical vapour deposition (PVD) used in the present invention and plating are known in the art mature technology, according to different purposes
It can choose different physical gas phase deposition technology and condition and electroplating technology and condition with material.
The flow diagram of one embodiment of the invention is as shown in Figure 2.Another specific implementation of the invention
The flow diagram of scheme is as shown in Figure 5.
In some cases, may remain in the surface micro-nano structure of the metallic film mold stripped down it is a small amount of come
From the metal residue for the metal layer being in contact with it before removing, at this point, it is preferred that entire gained mold is immersed selective etching liquid
In, the selective etching liquid to two kinds of metals have high selection etching ratio, so as to from surface micro-nano structure selectively
Metal residue is removed, it is final to obtain the metallic film mold with the micro-nano structure interface of complete display.It is worth noting that
It can be used repeatedly for etching liquid, while etch period only needs several seconds.This is very suitable to the extensive of large-area metal film die
Industrial production.
For example, in one embodiment, as shown in Fig. 3 c-d, having in the inverted pyramid structure of gained nickel mold
Golden residue immerses entire mold in golden etching liquid 1 minute, which has high selection etching ratio to gold and nickel, it
After obtain clearly inverted pyramid nano-structural interfaces.In another embodiment, as shown in Fig. 6 c-d, gained nickel mold
There are some golden residues in nano-pore structure, obtain clearly inverted pyramid nano-structural interfaces with same method.
The present invention also provides a kind of metallic film mold intermediates, which is by having
Pass through physical vapour deposition (PVD) (such as vapor deposition) anti-sticking metal then re-plating metal in the template of surface micro-nano structure, then by institute
Template is stated to strip down and formed, anti-sticking metal layer which is obtained by physical vapour deposition (PVD) and by
Obtained electroplated metal layer is electroplated to constitute, which has minus micro-nano knot corresponding with the template
Structure.
Preferably, the anti-sticking metal layer is gold, silver, copper, iron, nickel, titanium, cobalt, chromium, platinum, rhodium, palladium and its alloy, institute
State anti-sticking metal layer with a thickness of 1nm-1 μm, such as 1nm-100nm；The electroplated metal layer be gold, silver, copper, iron, nickel, titanium,
Cobalt, chromium, platinum, rhodium, palladium and its alloy, the electroplated metal layer with a thickness of 1 μm -200 μm, such as 1 μm -100 μm.
Since metallic film mold intermediate of the present invention has minus micro-nano structure corresponding with the template,
And since the binding force between different materials, the minus micro-nano knot is rationally utilized in present invention cooperation physical vapour deposition (PVD) and plating
Structure also keeps not being destroyed as the surface micro-nano structure of template, and therefore, which can be repeatedly sharp
With, so as to simplify metallic film mold preparation section, only need to be by the metallic film mold intermediate, can be obtained
Ideally replicate the metallic film mold of the surface micro-nano structure of template.This is very beneficial for the big of large-area metal film die
Technical scale production.
The contents of the present invention are further explained and described in mode by the following examples, but these examples are not understood that
For the limitation to protection scope of the present invention.
Embodiment
Unless stated otherwise, otherwise in following example method therefor and technology use the old process of this field, operation,
Material, instrument and condition carry out.
Embodiment one: using silicon as the nickel Mold Making process of template
Firstly, the lithography and etching technology by standard obtains nanometer inverted pyramid structure array (figure in silicon wafer surface
1a), common silicon face inverted pyramid anisotropic etching liquid is tetramethyl ammonium hydroxide solution.The technology is known, therefore
It is not described in detail herein.Then, change angle (Fig. 1 b and the figure on pyramid top by magnetron sputtering about 800nm crome metal
3a), the condition of magnetron sputtering is 1.5 × 10-5(torr) air pressure ar gas environment is held in the palm, radio-frequency sputtering energy is 600 watts, frequency
13.56 megahertzs.Thus the template with surface micro-nano structure for being used to prepare metallic film mold is obtained.
Template wafer is cleaned, deposits the silicon oxide layer and 100nm of 50nm in silicon wafer surface by electron beam evaporation plating later
Layer gold (Fig. 2 a-b and Fig. 3 b).The electro-coppering in the layer gold deposited later, gold are good plating seed layers.It is specific and
Speech, prepares copper sulphate mixed solution with the sulfuric acid of the copper sulphate of 180-220g/L, 50-70g/L, and in this, as electroplate liquid；With
Gold-plated wafer is as cathode, using 10cm × 20cm × 0.5cm copper plate as anode.Solution temperature is room temperature, passes through direct current
Power supply applies the current density of 1.5 amperes/square decimeter between anodic-cathodic, to realize about 100 μ on the surface of layer gold
The metal copper deposition (Fig. 2 c) of m.After plating, since binding force is very weak between silica and gold, and it is less than between gold and copper
Binding force, therefore, after cutting off adhesion edge, manual separation gold and silica, thus silicon template is recycled, and obtains
The film die intermediate (Fig. 2 c-d) being made of gold and copper.
Later, 100nm metallic nickel is deposited on the surface of the layer gold of the film die intermediate by electron beam evaporation plating
As anti-sticking layer.Then with the nickel sulfate of 260-300g/L, the nickel chloride of 35-45g/L, 40-50g/L boric acid be made mixing it is molten
Liquid, and in this, as electroplate liquid, at 55 DEG C, using metallic film mold intermediate as cathode, with 10cm × 20cm × 0.5cm
Nickel plate as anode, apply the current density of 1 ampere/square decimeter between anodic-cathodic by DC power supply, thus
100 μm of nickel layer (Fig. 2 e-f) is electroplated on the anti-sticking layer.After plating, adhesion edge, manual separation nickel anti-sticking layer and layer gold are cut off,
Thus to obtain the nickel mold (Fig. 2 f-g) for the nanometer inverted pyramid structure array for replicating the silicon template, and by the film
The recycling of mold intermediate.
Gained nickel mold is observed with scanning electron microscope, finds that there are some golden residues (Fig. 3 c) in inverted pyramid.
Entire mold is immersed into golden etching liquid (10g KI, 2.5g I2, 100ml H2O it 1 minute in), is fallen thus to obtain clearly nanometer golden
Word tower structure interface (Fig. 3 d).
The present embodiment is also spliced silicon wafer circle template, to obtain large form, then carries out above-mentioned nickel mold
Preparation process.Firstly, cutting the part edge of silicon formwork structure by machine, pay attention to keeping the smooth of interface.Then will own
Wafer splice on the substrate for be stained with double faced adhesive tape, between micro gap by the filling of ultraviolet glue and ultra-violet curing, it is purple
Outer cured condition is ultraviolet wavelength: 395nm, intensity: 100 μm/cm2, the time: 2 minutes, thus to obtain large area template and
Final nickel mold (Fig. 4 b-c).
Embodiment two: using aluminium oxide as the nickel Mold Making process of template
The manufacturing process of mold is as shown in Figure 5.Firstly, aluminium foil is impregnated in an acidic solution, then apply suitable straight
Galvanic electricity pressure obtains nano-pore structure by multi-step electrochemical oxidation and wet etching.Wherein, for the metal of electrochemical oxidation
It is raffinal (99.999%), using the aluminium flake of area equation as cathode.The formula of anodic oxidation solution is that volume ratio is 1:1
Aqueous citric acid solution and ethylene glycol, wherein the citric acid content in aqueous citric acid solution be 1% weight.First time anodic oxidation
Condition are as follows: bath temperature is -5 DEG C, applies 480V direct current and stays overnight.Then, the high-purity aluminium flake after oxidation is put into 60 DEG C
30 minutes in first secondary aluminium etching liquid (phosphate aqueous solution of the chromic acid aqueous solution of 1.5% weight and 6% weight), alumina is carved
Layer.Second of anodic oxidation is -5 DEG C using the same terms but time difference, i.e. bath temperature, is applied 480V direct current 3 hours.
Then sample is immersed into etching 20 minutes in second of etching liquid (phosphate aqueous solution of 53 DEG C of 5% weight), by each to different
Property etching expanded hole diameter.Thus to obtain anodic oxidation aluminium formwork.Fig. 6 a illustrates the scanning electron microscopy of nano-pore structure
Mirror figure, Fig. 7 a illustrate the photo of the anodic oxidation aluminium formwork of 30cm × 15cm.
Anodic oxidation aluminium formwork is cleaned, the layer gold of 100nm is deposited on alumina formwork surface by electron beam evaporation plating later
(Fig. 5 a-b).The electro-coppering in the layer gold deposited later, specifically, with the copper sulphate of 180-220g/L, 50-70g/L
Copper sulphate mixed solution is made in sulfuric acid, and in this, as electroplate liquid, using gold-plated aluminium oxide as cathode, with 10cm × 20cm ×
The copper plate of 0.5cm is applied between anodic-cathodic under conditions of solution temperature is room temperature by DC power supply as anode
The current density of 1.5 amperes/square decimeter.To realize about 100 μm of metal copper deposition (Fig. 5 c) on the surface of layer gold.Plating
Afterwards, since the binding force between aluminium oxide and gold is less than the binding force between gold and copper, it can easily gold and aluminium oxide stripping
It leaves, thus recycles alumina formwork, and obtain the film die intermediate (figure with column structure being made of gold and copper
5d).Later, by electron beam evaporation plating, the conduct of 100nm metallic nickel is deposited on the surface of the layer gold of the film die intermediate
Anti-sticking layer.Then at 55 DEG C, with then with the nickel sulfate of 260-300g/L, the nickel chloride of 35-45g/L, 40-50g/L boron
Mixed solution is made in acid, and in this, as electroplate liquid, at 55 DEG C, using metallic film mold intermediate as cathode, with 10cm
The nickel plate of × 20cm × 0.5cm applies the electricity of 1 ampere/square decimeter by DC power supply as anode between anodic-cathodic
Current density, so that 100 μm of nickel layer (Fig. 2 e-f) be electroplated on the anti-sticking layer.After plating, adhesion edge, manual separation nickel are cut off
Anti-sticking layer and layer gold, thus to obtain the nickel mold (Fig. 5 e-f) for the nano-pore structure for replicating the alumina formwork, and will
The film die intermediate recycling.Gained nickel mold is observed with scanning electron microscope, finds that there are some gold in nano-pore
Residue (Fig. 6 c).Entire mold is immersed into golden etching liquid (10g KI, 2.5g I2, 100ml H2O 1 minute in), thus to obtain
Clearly nano-pore structure interface (Fig. 6 d).Fig. 7 b illustrates the photo of the large area nickel mold of gained 25cm × 14cm.
Embodiment three: using plastics as the Mold Making process of template
The manufacturing process of mold is as shown in Figure 8.Fig. 8 a is the template with nano-pillar, and material is poly-methyl methacrylate
Ester (PMMA).The layer gold of 100nm is deposited in polymethyl methacrylate (PMMA) template surface by electron beam evaporation plating, Fig. 9 a is
Template photo after gold-plated.Then at 55 DEG C, with the nickel sulfate of 260-300g/L, the nickel chloride of 35-45g/L, 40-50g/L
Boric acid mixed solution is made, and in this, as electroplate liquid, at 55 DEG C, using the plastic formwork after gold-plated as cathode, with
10cm × 20cm × 0.5cm nickel plate applies 1 ampere/square decimeter as anode, by DC power supply between anodic-cathodic
Current density, so that 100 μm of nickel layer be electroplated on the anti-sticking layer (layer gold).After plating, adhesion edge, manual separation are cut off
Nickel anti-sticking layer and layer gold, thus to obtain nickel mold (Fig. 8 b-c).Fig. 9 c-d shows the micro-structure of plastic formwork and nickel mold respectively.
Fig. 9 b illustrates the photo of the nickel mold finally obtained.
Claims (19)
1. a kind of preparation method of the metallic film mold with surface micro-nano structure, includes the following steps:
The template for having surface micro-nano structure is provided；
By the first physical vapour deposition (PVD), the first of nanometer grade thickness is formed on the surface of the surface micro-nano structure of the template
Anti-sticking metal layer has the first binding force between the first anti-sticking metal layer and template；And
By the first plating, the first electroplated metal layer of micron order thickness is formed on the described first anti-sticking metal layer, this first
There is the second binding force between electroplated metal layer and the first anti-sticking metal layer；
Wherein, first binding force is less than the second binding force, and the first anti-sticking metal layer is in the first plating step
Conductive layer is acted also as in rapid.
2. according to the method described in claim 1, further including following steps:
After the first plating, the described first anti-sticking metal layer and the template with surface micro-nano structure are removed；To
To the metallic film mold intermediate being made of the described first anti-sticking metal layer and first electroplated metal layer, the metal foil
Film die intermediate has minus micro-nano structure corresponding with the template.
3. according to the method described in claim 2, further including following steps:
By the second physical vapour deposition (PVD), nanometer is formed on the minus micro-nano structure surface of the metallic film mold intermediate
Second anti-sticking metal layer of grade thickness, the second anti-sticking metal layer have in conjunction with third between metallic film mold intermediate
Power；And
By the second plating, the second electroplated metal layer of micron order thickness is formed on the described second anti-sticking metal layer, this second
There is the 4th binding force between electroplated metal layer and the second anti-sticking metal layer；
Wherein, the third binding force is less than the 4th binding force.
4. according to the method described in claim 1, wherein the described first anti-sticking metal layer is the metal with a thickness of 1nm-100 μm
Layer, which formed by e-beam vacuum deposition technology；First electroplated metal layer is with a thickness of 1-200 μm
Metal layer.
5. according to the method described in claim 4, wherein the described first anti-sticking metal layer is formed by one of following metal, institute
Stating metal is gold, silver, copper, iron, nickel, titanium, cobalt, chromium, platinum, rhodium, palladium and its alloy；First electroplated metal layer is by following metal
One of formed, the metal be gold, silver, copper, iron, nickel, titanium, cobalt, chromium, platinum, rhodium, palladium and its alloy.
6. according to the method described in claim 3, wherein the described second anti-sticking metal layer is the metal with a thickness of 1nm-100 μm
Layer, which formed by e-beam vacuum deposition technology；Second electroplated metal layer is with a thickness of 1-200 μm
Metal layer.
7. according to the method described in claim 6, wherein the described second anti-sticking metal layer is formed by one of following metal, institute
Stating metal is gold, silver, copper, iron, nickel, titanium, cobalt and chromium；Second electroplated metal layer is formed by one of following metal, institute
Stating metal is copper, nickel, cobalt and chromium.
8. according to the method described in claim 1, wherein the template with surface micro-nano structure is that its surface has oxidation
The Silicon Wafer of silicon layer, the first anti-sticking metal layer are gold, and first electroplated metal layer is copper.
9. second electroplated metal layer is according to the method described in claim 1, wherein the described second anti-sticking metal layer is nickel
Nickel.
10. according to the method described in claim 1, wherein described offer the step of there is the template of surface micro-nano structure include,
Change the end shape of the surface micro-nano structure by magnetron sputtering technique.
11. according to the method described in claim 10, wherein the surface micro-nano structure is micro-nano pyramid, and passing through magnetic
Control sputtering technology changes the micro-nano pyramidal top angle.
12. according to the method described in claim 1, wherein the template is any one in the template as made from following method
Kind:
The template made of electron beam exposure；
The template made of photoetching and etching technique；
The template made of nano-imprinting method；
The template made of electrochemical oxidation and wet etching.
13. according to the method described in claim 1, wherein the surface micro-nano structure be micro-nano pyramid, it is micro-nano cone, it is micro-
Nano-pillar, micro-nano point or micro-nano hole.
14. according to the method described in claim 1, wherein template is any one in following template: silicon template, metal mold
Plate, metal oxide template, plastic formwork.
15. according to the method for claim 14, wherein the metal oxide template is by electrochemical oxidation and wet process
Alumina formwork made of etching.
16. according to the method described in claim 1, wherein the template with surface micro-nano structure is large area template,
It is to be formed and the edge of at least two pieces lesser templates is mutually stitched together.
17. according to the method for claim 16, wherein the lesser template is Silicon Wafer, in the splicing step,
By cutting off a part of the silicon wafer the edge of the circle, will there is the Silicon Wafer at the edge after cutting to be placed side by side on a horizontal plane,
Two cut edges are parallel to each other and there are small gaps therebetween, then by being filled with the glue of UV curable
The gap simultaneously carries out ultra-violet curing, to obtain large area template.
18. a kind of metallic film mold intermediate, which is by with surface micro-nano structure
Pass through the anti-sticking metal of physical vapour deposition (PVD) then re-plating metal in template, then the template stripped down and is formed,
The anti-sticking metal layer that the metallic film mold intermediate is obtained by physical vapour deposition (PVD) and the electroplated metal layer structure obtained by plating
At the metallic film mold intermediate has minus micro-nano structure corresponding with the template.
19. described according to the method for claim 18, wherein the anti-sticking metal layer is formed by one of following metal
Metal be gold, silver, copper, iron, nickel, titanium, cobalt, chromium, platinum, rhodium, palladium and its alloy, the anti-sticking metal layer with a thickness of 1nm-100 μ
m；The electroplated metal layer is formed by one of following metal, the metal be gold, silver, copper, iron, nickel, titanium, cobalt, chromium, platinum,
Rhodium, palladium and its alloy, the electroplated metal layer with a thickness of 1-200 μm.
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