CN103710679A - Hydrophobic layer, preparation method thereof, article provided with hydrophobic layer, and manufacturing method of mould - Google Patents
Hydrophobic layer, preparation method thereof, article provided with hydrophobic layer, and manufacturing method of mould Download PDFInfo
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- CN103710679A CN103710679A CN201210380980.3A CN201210380980A CN103710679A CN 103710679 A CN103710679 A CN 103710679A CN 201210380980 A CN201210380980 A CN 201210380980A CN 103710679 A CN103710679 A CN 103710679A
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Abstract
The invention discloses an article provided with a hydrophobic layer. The article comprises a base material and the hydrophobic layer. The hydrophobic layer is arranged on the surface of the base material by applying a reaction gas on the base material surface, and subjecting the base material to plasma treatment. Main component of the reaction gas is volatilizable alkylsilane molecule. Main components of the hydrophobic layer are silicon and oxygen, and thickness ranges from 300nm to 500<mu>m. The hydrophobic layer possesses excellent hydrophobicity, and high-temperature heating resistance; resistance against acid, alkali, and organic solvents is excellent; and stability of the hydrophobic layer in article preparation processes and using processes is improved.
Description
Technical field
The present invention relates to a kind of hydrophobic layer, refer to especially the good and resistant to elevated temperatures hydrophobic layer of a kind of chemical resistant properties.
Background technology
The wetting ability of article or hydrophobicity can by adjust the roughness of article surface or surface can and controlled.For example TaiWan, China certificate number I334879 patent proposes a kind of hydrophobic layer and method for making thereof, this hydrophobic layer is made in to the surface of article, can be by the lifting of surfaceness and surface can reduction, and present hydrophobic effect.
But general article are when processing and manufacturing, often need to process through peracid, alkali, organic solution, or impose high temperature process, therefore need a kind of tolerance to acid, alkali, organic solution good, and can bear the hydrophobic layer of heat, to promote hydrophobic layer in article making processes or the stability of using.
Summary of the invention
The object of the present invention is to provide a kind of good hydrophobicity that has, and good to the tolerance of acid, alkali, organic solution, and can bear hydrophobic layer of heat and preparation method thereof.
Hydrophobic layer of the present invention, is formed at a substrate surface.The making method of this hydrophobic layer, comprises following steps: (A) prepare a base material; (B) produce a reactant gases, this reactant gases main component is the alkyl silane molecule of volatilization state; (C) apply this reactant gases and a plasma in a surface of this base material; And (D) form a hydrophobic layer in this surface of this base material.
Preferably, the material of this base material is selected from the group that semiconductor material, glass, metal, plastic cement, rubber, high molecular polymer, stupalith, filamentary material, rock, soil material, cementing properties material and coating form.
Preferably, at this reactant gases of step (B), be that this precursor gas is nitrogen by passing into a precursor gas and mixing with the volatilization gas of a reaction soln, this reaction soln main component is liquid alkyl silane molecule.
Preferably, step (C) to should reactant gases and this base material place impose a plasma, this plasma is to be produced by a plasma cell; This plasma cell comprises that a cavity and is communicated in the jet pipe of this cavity; In step (C), imposing this isoionic thin step is: pass into one for generation of this isoionic process gas in this cavity, and apply a voltage in this jet pipe, make to circulate in this process gas in this jet pipe and dissociate and produce this plasma, and allow this plasma derive away from a mouth of pipe of this cavity from this jet pipe and put on this reactant gases and this base material.
On the other hand, in step (C), impose this isoionic thin step and can be also and pass into a process gas and this reactant gases in this cavity, and apply a voltage in this jet pipe, make to circulate in this process gas in this jet pipe and this reactant gases and dissociate and produce this plasma, and allow this plasma and this reactant gases away from a mouth of pipe derivation of this cavity, put on this base material from this jet pipe.
Furthermore, this process gas is the dried and clean air of pressure at least 5 kg/cm.
Preferably, the distance of this jet pipe and this base material is 5 to 30 centimetres.
Preferably, this hydrophobic layer mainly consists of silicon and oxygen.
Preferably, this step (A) is also bestowed a part at this base material and is covered this surperficial patterned layer; In this step (D), formed this hydrophobic layer covers the part surface that this patterned layer and this base material are not covered by this patterned layer; Step (D) also comprises a step (E) afterwards to be removed this patterned layer and is covered in the hydrophobic layer in this patterned layer, and forms the hydrophobic layer of a patterning.
Furthermore, the photoresistance that the material of this patterned layer is sensitization; Step (E) is to remove this patterned layer and peel off the hydrophobic layer in this patterned layer simultaneously by an organic solvent.
Preferably, the thickness of this hydrophobic layer is 300 nanometers to 500 micron.
Another object of the present invention, is providing a kind of article that use aforementioned hydrophobic layer.
So the present invention has the article that have hydrophobic layer, comprise a base material and a hydrophobic layer.Wherein, the material of this base material is selected from the group that semiconductor material, glass, metal, plastic cement, rubber, high molecular polymer, stupalith, filamentary material, rock, soil material, cementing properties material and coating form.This hydrophobic layer is made by aforementioned making method.
A further object of the present invention, is providing a kind of making method of mould, and this mould is that correspondence is made according to hydrophobic layer.
So the making method of mould of the present invention, comprises following steps: (A) prepare a hydrophobic layer, this hydrophobic layer is made with aforementioned making method; (B) by galvanoplastics, on the surface of this hydrophobic layer, form a metal level, the surface that this metal level is connected in this hydrophobic layer fits in the surface that this hydrophobic layer is corresponding completely; And (C) separated this metal level.
Preferably, step (B) comprises following thin step: (B1) by physical gas phase deposition technology or metal coating technology, cover a metal initial layers in the surface of this hydrophobic layer; And (B2) by electrochemical deposition technique, on this metal initial layers, form this metal level.
Beneficial effect of the present invention is: the hydrophobic layer that forms through plasma treatment of alkyl silane molecule by volatilization state has good hydrophobicity, chemical resistant properties and temperature tolerance, and promote hydrophobic layer, at article, manufacture the stability of the course of processing, and promote its durable degree.In addition, by the mould of hydrophobic layer respective production, the rough surface morphology of this hydrophobic layer can be transferred to a curable plastic material, and the hydrophobicity of promoting this plastic material.
Accompanying drawing explanation
Fig. 1 is a schematic diagram, and a preferred embodiment of the making method of hydrophobic layer of the present invention is described;
Fig. 2 is the making schema of this hydrophobic layer;
Fig. 3 and Fig. 4 are the application schematic diagram of this hydrophobic layer;
Fig. 5 is the schematic diagram of making a patterning hydrophobic layer;
Fig. 6 is the schema of making this patterning hydrophobic layer;
Fig. 7 is the surface topography map of this hydrophobic layer;
Fig. 8 is made the schema of a mould by this hydrophobic layer; And
Fig. 9 is the schematic diagram of making this mould.
Embodiment
About aforementioned and other technology contents, feature and effect of the present invention, in the detailed description of two preferred embodiments that coordinates below referenced in schematic, can clearly present.
Consulting Fig. 1 to Fig. 2 is a preferred embodiment of hydrophobic layer 12 of the present invention and preparation method thereof.
Step S1: prepare article 1, these article 1 can be mobil phone, integrated circuit (IC) chip, vial etc., but not as limit.Article 1 have a base material 11, the material of base material 11 be selected from semiconductor material, glass, metal, plastic cement, rubber, high molecular polymer, stupalith, filamentary material, rock (as marble, granite), soil material (as brick, watt, clay), the group that formed of cementing properties material (as cement, concrete, pitch and gypsum) and coating (as paint and clear lacquer).
Carry out before next step, can optionally to base material 11, carry out surface cleaning processing.For instance, if the material of base material 11 is silicon, can pass through RCA(Radio corporation of America) cleaning technique remove the filths such as organism, oxide compound and metal ion on base material 11 surfaces.But the cleaning of above-mentioned base material 11 non-essential execution step.
Step S2: produce a main component for the reactant gases 3 of the alkyl silane molecule of volatilization state.This reactant gases 3 is by passing into a precursor gas and mixing with the volatilization gas of a reaction soln.Herein, this precursor gas is nitrogen, and this reaction soln main component is liquid alkyl silane molecule
Specifically, the reaction soln that comprises liquid alkyl silane molecule is contained in an encloses container and (in figure, is not drawn), and pass into nitrogen in this encloses container, after mixing with nitrogen, the gaseous state alkyl silane molecule of volatilization is the reactant gases 3 that is used to form hydrophobic layer 12.
Specify, the precursor gas that the present embodiment is used is nitrogen, but not as limit, can be also the gases such as argon gas, atmosphere, only otherwise produce chemical reaction with gaseous state alkyl silane molecule.
Step S3: apply this reactant gases 3 in a surface of base material 11 by an airway 22, and in imposing a plasma 5 corresponding to reactant gases 3 and base material 11 contact positions, and make that reactant gases 3 dissociates, upgrading deposit film be in base material 11 surfaces, and forms hydrophobic layer 12.
Herein, plasma 5 is to be produced by a plasma cell 21.Plasma cell 21 comprises that a cavity 211 and is communicated in the jet pipe 212 of this cavity 211.Pass into a process gas 4 for generation of plasma 5 after cavity 211, apply a voltage in jet pipe 212, make to circulate in process gas 4 in jet pipe 212 and dissociate and produce plasma 5, reactant gases 3 and base material 11 contact positions are derived and put on to this plasma 5 from jet pipe 212 away from a mouth of pipe 213 of this cavity 211.
In said process, process gas 4 is the dried and clean air (Clean dry air, CDA) of pressure at least 5 kg/cm, and jet pipe 212 is 5 to 30 centimetres with the distance of base material 11, and concrete numerical value depends on the needs.
Specify, above-mentioned reactant gases 3 also can directly pass into the cavity 211 of plasma cell 21, and by high-voltage, is dissociated and produced plasma 5 after mixing with process gas 4, and forms hydrophobic layer 12 on base material 11 surfaces.
Step S4: hydrophobic layer 12 is formed at base material 11 surfaces via step S3.Wherein, the thickness of hydrophobic layer 12 is by applying the Time dependent of reactant gases 3 with plasma 5, and preferably thickness is 300 nanometers to 500 micron, but not as limit.
Table one
It with reference to table one, is the Characteristics Detection result of hydrophobic layer 12.As shown in Table 1, hydrophobic layer 12 mainly consists of silicon and oxygen, its surperficial degree of roughness with and hydrophobic group effectively increase hydrophobicity, and still there is good hydrophobicity after acid, alkali, organic solution and pyroprocessing, and can promote the surface hydrophobicity of base material 11.
With reference to Fig. 3.For instance, article 1 can be integrated circuit (IC) chip that comprises an encapsulating shell 13 and many pins 14.A circuit card (not drawing in figure) is fixed in general ic core sector-meeting by scolding tin, in the heat-processed of scolding tin Reflow Soldering (reflow), the scolding tin surface tension that is positioned at pin 14 bottoms reduces, and by capillarity along pin 14, climb and rise to encapsulating shell 13 places, and causing scolding tin to damage the potential risk of encapsulating shell 13, this is " climbing tin " phenomenon.If hydrophobic layer 12 is made in respectively to the position of pin 14 between its bottom and encapsulating shell 13 by preceding method, because hydrophobic layer 12 has high temperature tolerance and scolding tin cannot be attached to hydrophobic layer 12 surfaces, and can in the heat-processed of scolding tin Reflow Soldering (reflow), avoid climbing tin phenomenon, to promote process rate.
With reference to Fig. 4.In addition, article 1 can be also mobil phones.Hydrophobic layer 12 is made in to mobil phone surface, by its hydrophobicity, can promotes the waterproof degree of mobil phone and keep it clean.
Specify, said integrated circuit chip, mobil phone, only for illustrating, can not limit with this Application Areas of hydrophobic layer 12, as long as base material 11 material matchings of article 1 are in hydrophobic layer 12.
With reference to Fig. 1, Fig. 5 and Fig. 6.The difference of the present invention's the second preferred embodiment and the first preferred embodiment is, this hydrophobic layer 12 also further defines corresponding shape by semiconductor technology, and detailed content is described as follows.
Step F 1: with reference to Fig. 5 a, form a part by photoetching technique (Photolithography) on base material 11 surfaces and cover this surperficial patterned layer 15.Herein, the photoresistance that the material of patterned layer 15 is sensitization.
Step F 2: with reference to Fig. 5 b, by the method for aforementioned making hydrophobic layer 12, be not subject to the part surface of patterned layer 15 coverings to cover one deck hydrophobic layer 12 in patterned layer 15 and base material 11.
Step F 3: remove patterned layer 15 and peel off the hydrophobic layer 12 in patterned layer 15 simultaneously by an organic solvent.Herein, this organic solvent is acetone, but not as limit, as long as can remove patterned layer 15.
Step F 4: with reference to Fig. 5 c, complete one and define the patterning hydrophobic layer 12 of specified shape by patterned layer 15.
As above stated specification, according to step S1 to S3, chemical resistant properties and the good hydrophobic layer 12 of temperature tolerance can be produced, and the hydrophobic layer 12 of patterning can be further by manufacture of semiconductor fabrication techniques, gone out by step F 1 to F4, and the range of application of promoting hydrophobic layer 12.
In addition, consult Fig. 7 to Fig. 9, because hydrophobic layer 12 has uneven surface (as Fig. 7), promote its hydrophobicity, so the present invention also provides a kind of mould 6 that copies hydrophobic layer 12 surface topographies.By this mould 6, at curable plastic material, (as polydimethylsiloxane, surface PDMS) impresses, and the surface topography of hydrophobic layer 12 can be transferred to the surface of plastic material, and the hydrophobicity of promoting this plastic material.
Below for making the step of mould 6.
Step M1: with reference to Fig. 9 a, prepare a hydrophobic layer 12 with abovementioned steps S1 to S3 or step F 1 to F4.
Step M2: form mould 6(as Fig. 9 b on hydrophobic layer 12 surfaces).
This step is to make mould 6 with precise electrotyping technology (Electroforming).Specifically, first on the surface 121 of hydrophobic layer 12, for example, by physical gas phase deposition technology (evaporation coating technique or sputter technology) or other metal coating technology, cover layer of metal initial layers (Seed layer).For instance, this metal initial layers can be the double-level-metals such as chromium and copper, titanium and copper, but not as limit.
Then, by electrochemical deposition technique (Electrochemical deposition), on this metal initial layers, deposit the metal level that one deck is thicker, and form mould 6.The material of mould 6 can be nickel, nickel cobalt (alloy) or copper, but not as limit.
In the process of electrochemical deposition, mould 6 is metal refinings and forming gradually from the surface 121 of hydrophobic layer 12, so surface 61 patterns of mould 6 are complementary to the surface 121 of hydrophobic layer 12, and can carry out the function of transfer printing.
Step M3: surface 121 separation by mould 6 from hydrophobic layer 12, and make mould 6(as Fig. 9 c).
After the surface of mould 6 61 is impressed on plastic material surface, is solidified, the surface of plastic material can form the pattern on the surface 61 that is complementary to mould 6, the effect of this practice is equivalent to the pattern on the surface of hydrophobic layer 12 121 to be transferred to the surface of plastic material, and makes this plastic material promote its hydrophobicity by the increase of surfaceness.
In sum, by the alkyl silane molecule of volatilization state, through plasma 5, process and the hydrophobic layer 12 that forms has good hydrophobicity, chemical resistant properties and high temperature tolerance, and can promote the stability of hydrophobic layer 12 in the manufacturing processed of various article 1, and promote its durable degree.In addition, because hydrophobic layer 12 has good chemical resistant properties, and can produce by semiconductor technology the hydrophobic layer 12 of patterning, to promote its range of application.Come again, by the mould 6 of hydrophobic layer 12 respective production, the rough surface morphology of hydrophobic layer 12 can be transferred to the surface of curable plastic material, and the hydrophobicity of further promoting this plastic material.
Only as described above, it is only preferred embodiment of the present invention, when not limiting scope of the invention process with this, the simple equivalence of generally doing according to the present patent application the scope of the claims and invention description content changes and modifies, and all still remains within the scope of the patent.
Claims (20)
1. a making method for hydrophobic layer, is characterized in that, this making method comprises following steps:
(A) prepare a base material;
(B) produce a reactant gases, this reactant gases main component is the alkyl silane molecule of volatilization state;
(C) apply this reactant gases and a plasma in a surface of this base material; And
(D) form a hydrophobic layer in this surface of this base material.
2. the making method of hydrophobic layer as claimed in claim 1, is characterized in that: the material of this base material is selected from the group that semiconductor material, glass, metal, plastic cement, rubber, high molecular polymer, stupalith, filamentary material, rock, soil material, cementing properties material and coating form.
3. the making method of hydrophobic layer as claimed in claim 1, it is characterized in that: this reactant gases of step (B) is by passing into a precursor gas and mixing with the volatilization gas of a reaction soln, this precursor gas is nitrogen, and this reaction soln main component is liquid alkyl silane molecule.
4. the making method of hydrophobic layer as claimed in claim 1, is characterized in that: at this plasma of step (C), be to be produced by a plasma cell, this plasma cell comprises that a cavity and is communicated in the jet pipe of this cavity; This reactant gases of step (C) and this plasma are to put on respectively the corresponding surface of this base material, and imposing this isoionic thin step is: pass into one for generation of this isoionic process gas in this cavity, and apply a voltage in this jet pipe, make to circulate in this process gas in this jet pipe and dissociate and produce this plasma, and allow this plasma derive away from a mouth of pipe of this cavity from this jet pipe and put on this reactant gases and this base material.
5. the making method of hydrophobic layer as claimed in claim 4, is characterized in that: this process gas is the dried and clean air of pressure at least 5 kg/cm.
6. the making method of hydrophobic layer as claimed in claim 4, is characterized in that: the distance range of this jet pipe and this base material is 5 to 30 centimetres.
7. the making method of hydrophobic layer as claimed in claim 1, is characterized in that: at this plasma of step (C), be to be produced by a plasma cell; This plasma cell comprises that a cavity and is communicated in the jet pipe of this cavity; In step (C), imposing this isoionic thin step is: pass into a process gas and this reactant gases in this cavity, and apply a voltage in this jet pipe, make to circulate in this process gas in this jet pipe and this reactant gases and dissociate and produce this plasma, and allow this plasma and this reactant gases away from a mouth of pipe derivation of this cavity, put on this base material from this jet pipe.
8. the making method of hydrophobic layer as claimed in claim 7, is characterized in that: this process gas is the dried and clean air of pressure at least 5 kg/cm.
9. the making method of hydrophobic layer as claimed in claim 7, is characterized in that: the distance range of this jet pipe and this base material is 5 to 30 centimetres.
10. the making method of hydrophobic layer as claimed in claim 1, is characterized in that: this hydrophobic layer mainly consists of silicon and oxygen.
The making method of 11. hydrophobic layers as claimed in claim 1, is characterized in that: this step (A) is also bestowed a part at this base material and covered this surperficial patterned layer; In this step (D), formed this hydrophobic layer covers the part surface that this patterned layer and this base material are not covered by this patterned layer; Step (D) also comprises a step (E) afterwards to be removed this patterned layer and is covered in the hydrophobic layer in this patterned layer, and forms the hydrophobic layer of a patterning.
The making method of 12. hydrophobic layers as claimed in claim 11, is characterized in that: the photoresistance that the material of this patterned layer is sensitization; Step (E) is to remove this patterned layer and peel off the hydrophobic layer in this patterned layer simultaneously by an organic solvent.
The making method of 13. hydrophobic layers as claimed in claim 1, is characterized in that: the thickness of this hydrophobic layer is 300 nanometers to 500 micron.
14. 1 kinds of hydrophobic layers, are formed at a substrate surface, it is characterized in that: this hydrophobic layer is made by the making method of any one in claim 1 to 13.
15. 1 kinds of article with hydrophobic layer, is characterized in that: these article comprise
One base material; And
One hydrophobic layer, is formed at this substrate surface,
Wherein, this hydrophobic layer is made by the making method of any one in claim 1 to 13.
16. article with hydrophobic layer as claimed in claim 15, is characterized in that: this base material is the metal pins of an integrated circuit (IC) chip, and this hydrophobic layer is to be formed between the bottom and top of this metal pins.
17. 1 kinds of article with hydrophobic layer, is characterized in that: these article comprise
One base material; And
One hydrophobic layer, by a reactant gases that puts on this substrate surface, through plasma treatment, be formed at this substrate surface, the main component of this reactant gases is the alkyl silane molecule of volatilization state, and this hydrophobic layer main component is that silicon and oxygen and thickness are 300 nanometers to 500 micron.
18. article with hydrophobic layer as claimed in claim 17, is characterized in that: the material of this base material is selected from the group that semiconductor material, glass, metal, plastic cement, rubber, high molecular polymer, stupalith, filamentary material, rock, soil material, cementing properties material and coating form.
The making method of 19. 1 kinds of moulds, is characterized in that, this making method comprises following steps
(A) prepare a hydrophobic layer, this hydrophobic layer is made with the making method of any one in claim 1 to 13;
(B) by galvanoplastics, on the surface of this hydrophobic layer, form a metal level, the surface that this metal level is connected in this hydrophobic layer fits in the surface that this hydrophobic layer is corresponding completely; And
(C) separated this metal level, and form this mould.
The making method of 20. moulds as claimed in claim 19, is characterized in that: step (B) comprises following thin step:
(B1) by physical gas phase deposition technology or metal coating technology, cover a metal initial layers in the surface of this hydrophobic layer; And
(B2) by electrochemical deposition technique, on this metal initial layers, form this metal level.
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| CN107978613A (en) * | 2017-12-15 | 2018-05-01 | 中芯集成电路（宁波）有限公司 | Semiconductor light-sensing device and its photosensitive surface processing method |
| CN110970314A (en) * | 2019-12-17 | 2020-04-07 | 华中科技大学 | Micro-welding point interconnection method for graphical nanoparticles in chip packaging and product |
| CN111050258A (en) * | 2019-12-31 | 2020-04-21 | 歌尔股份有限公司 | Dustproof structure, microphone packaging structure and electronic equipment |
| CN111736242A (en) * | 2019-09-10 | 2020-10-02 | 合肥工业大学 | A kind of preparation method of microlens array based on patterned hydrophobic layer |
| CN111751911A (en) * | 2019-09-10 | 2020-10-09 | 合肥工业大学 | A kind of preparation method of variable-focus liquid microlens array based on patterned hydrophobic layer |
| CN111781775A (en) * | 2019-09-10 | 2020-10-16 | 合肥工业大学 | Preparation method of liquid crystal microlens array based on thickness gradient distribution alignment film |
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| CN111736242A (en) * | 2019-09-10 | 2020-10-02 | 合肥工业大学 | A kind of preparation method of microlens array based on patterned hydrophobic layer |
| CN111751911A (en) * | 2019-09-10 | 2020-10-09 | 合肥工业大学 | A kind of preparation method of variable-focus liquid microlens array based on patterned hydrophobic layer |
| CN111781775A (en) * | 2019-09-10 | 2020-10-16 | 合肥工业大学 | Preparation method of liquid crystal microlens array based on thickness gradient distribution alignment film |
| CN110970314A (en) * | 2019-12-17 | 2020-04-07 | 华中科技大学 | Micro-welding point interconnection method for graphical nanoparticles in chip packaging and product |
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