CN106011775A - Preparation method of ultrathin self-supporting polymer film - Google Patents
Preparation method of ultrathin self-supporting polymer film Download PDFInfo
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- CN106011775A CN106011775A CN201610503165.XA CN201610503165A CN106011775A CN 106011775 A CN106011775 A CN 106011775A CN 201610503165 A CN201610503165 A CN 201610503165A CN 106011775 A CN106011775 A CN 106011775A
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/48—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating by irradiation, e.g. photolysis, radiolysis, particle radiation
- C23C16/483—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating by irradiation, e.g. photolysis, radiolysis, particle radiation using coherent light, UV to IR, e.g. lasers
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/01—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes on temporary substrates, e.g. substrates subsequently removed by etching
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- Physical Vapour Deposition (AREA)
Abstract
The invention discloses a preparation method of an ultrathin self-supporting polymer film. The growth of a polymer film monomolecular layer is realized by using a laser induced chemical vapor deposition mode, and the ultrathin self-supporting polymer film is obtained by a film separating technology. The method is characterized in that the condition that a polymer monomer enters a vacuum chamber in a molecular flow mode by accurate control over pulse gas inlet, gas flow and pressure; and when a substrate is coated with the polymer monomers on a monomer layer, a bundle of laser with low energy density induces the polymer monomers to be polymerized, and polymerization growth in the polymer monomolecular layer is realized. The self-supporting polymer film is obtained by a method of preparing a film separating layer on a substrate and removing the film separating layer, and the problem that an ultrathin polymer film is difficult to support is better solved. The polymer film which is 10nm in thickness and is supported on a round hole of 3mm can be obtained by adopting the method; and in addition, the preparation method has the advantages of fewer wasted raw materials, high rate of finished products and high practicality, and is a better method for obtaining the ultrathin self-supporting polymer film.
Description
Technical field
The present invention relates to a kind of method for manufacturing thin film, particularly relate to a kind of ultra-thin self-supporting
The preparation method of thin polymer film.
Background technology
Polymer self-supporting film is in the technical field such as Strong-field physics, atomic and molecular physics
There is the application that it is special.Wherein, the preparation method of thin polymer film be mainly spin coating and
Membrane, its raw material is exactly polymer itself, but the self-supporting that cannot obtain low thickness is thin
Film；And owing to dissolving a polymer in various solvent during preparing thin film, difficult
To obtain pure self-supporting film.
Summary of the invention
In order to overcome drawbacks described above, the invention provides a kind of ultra-thin self-supporting polymer
The preparation method of thin film, uses induced with laser CVD method to obtain the polymerization of ultra-thin self-supporting
Thing thin film.
The present invention is to solve that its technical problem be the technical scheme is that
The preparation method of a kind of ultra-thin self-supporting thin polymer film, comprises the following steps:
Step 1, substrate cleans, and prepares substrate and cleans up；
Step 2, prepared by release layer, plate last layer on a side surface of described substrate
The metal release layer of 20～50nm；
Step 3, fills sample, is fixed on sample carrier by the substrate being coated with metal release layer,
And sample carrier is suspended in the vacuum cavity of induced with laser CVD equipment, then this is swashed
The vacuum cavity of photoinduction CVD equipment is evacuated to 1.0～2.0 × 10-4Pa；
Step 4, arranges the parameter of induced with laser CVD, with not with polymer to be prepared
The gas of reaction is as carrier gas, and carrier gas total amount is set as a sccm, b sccm therein
Carrier gas be directly entered vacuum cavity, the carrier gas of (a-b) sccm additionally is with pulse
Mode, by the jar containing polymer monomer, makes carrier gas carry polymer monomer with drum
The form of bubble enters vacuum cavity, and control valve makes the vacuum in vacuum cavity be
2Pa, wherein, 4 a 6,2 b 3；
Step 5, the selection of laser, select laser wave according to the character of prepared material
Long, it is 10～20mJ/cm by the energy density after beam expanding lens2, laser frequency is
0.5～2Hz；
Step 6, the preparation of thin polymer film, with hydrogen as carrier gas by be prepared thin
The polymer monomer of film enters vacuum cavity in the way of molecular flow, when described substrate
When coating the polymer monomer of a monolayer on metal release layer, by described laser
Expose on this substrate, it is achieved the aggregation growth of polymer monomer monolayer, and root
The plated film time is selected, to obtain the thin film of different-thickness according to the film thickness needed；
Step 7, demoulding, the thin film prepared is put in acid solution, dissolves
Release layer, thin polymer film i.e. swims on acid solution face, by being cleaned multiple times, removes
Remove the metal ion in solution so that thin polymer film swims on the water surface；
Step 8, the self-supporting of thin film, preprepared metal rack with holes is inclined
Tiltedly put in water, slowly support thin polymer film；
Step 9, deposits, after thing film surface moisture natural evaporation to be polymerized is dry
Leave in drying cupboard stand-by.
As a further improvement on the present invention, in described step 1, described substrate is
Silicon chip, fused quartz or sapphire.
As a further improvement on the present invention, in described step 2, magnetic control is used to spatter
Penetrate or the mode of thermal evaporation plates metal release layer on a side surface of described substrate.
As a further improvement on the present invention, in described step 2, described metal
The surface roughness of release layer is less than 0.1nm.
As a further improvement on the present invention, in described step 2, described metal takes off
Metal in film layer is aluminum or ferrum.
As a further improvement on the present invention, in described step 4, hydrogen is with molecule
The mode of stream enters vacuum cavity.
As a further improvement on the present invention, in described step 4, ram charging
Persistent period is 10s, and interval time is 20s.
As a further improvement on the present invention, in described step 4, described carrier gas
Gas flow uses mass flowmenter to control, and its precision should be better than 0.1sccm.
As a further improvement on the present invention, in described step 4, described carrier gas is
Hydrogen, methane or other only carbon containing and the gas of hydrogen.
As a further improvement on the present invention, in described step 7, described acidity
Solution is hydrochloric acid or nitric acid, and its concentration is less than 0.1mol/L.
The invention has the beneficial effects as follows: the preparation side of this ultra-thin self-supporting thin polymer film
Method uses induced with laser CVD method to prepare thin film, is preparing the process of thin polymer film
Middle elder generation is coated in polymer monomer on the substrate of cleaning uniformly, then utilizes laser
Induction monomer whose is polymerized in a monolayer, forms meshed texture, significantly
Improve the internal stress of thin film.It addition, the method need not organic solvent, it is to avoid
Thin film is by organic solvent pollution, the purity of the prepared thin film of effective guarantee.
Detailed description of the invention
As a example by polymers polystyrene, illustrate that one of the present invention is ultra-thin below
The preparation method of self-supporting thin polymer film, comprises the following steps:
(1) magnetron sputtering technique is utilized to prepare in clean Si (100) substrate
A layer thickness is the metal Al layer of 20nm；
(2) dress sample, is fixed on the substrate being coated with Al layer on sample carrier, sample carrier
It is suspended in the vacuum chamber of induced with laser CVD equipment, vacuum cavity is sealed and takes out true
Empty to 1.0～2.0 × 10-4Pa；
(3) setting of induced with laser CVD parameter, selection hydrogen is as carrier gas, always
Amount is set as that 5sccm, the hydrogen of 3sccm therein are directly entered vacuum cavity, separately
The hydrogen of outer 2sccm in a pulsed fashion (persistent period of ram charging is 10s,
Interval is 20s) by cinnamic jar, make hydrogen carry styrene with bubbling
Form enter vacuum cavity, control valve makes the vacuum in vacuum cavity be 2Pa；
(4) selection of laser, selects optical maser wavelength according to the character of prepared material,
It is 10mJ/cm by the energy density after beam expanding lens2, laser frequency is set as 2Hz；
The plated film time is 30 minutes；
(5) taking out sample, tilting to put into concentration is 0.05mol/L acid solution
In, after polystyrene film swims on the water surface, floating thin film is transferred to pure
In water purification, it is transferred to again in pure water, transferase 45；
(6) metal rack of the punching that is prepared in advance is tilted to put in water, slowly
Support thin polymer film, polymer support is in metal rack.Utilize after 15 days
White light interference technique testing film is smooth, smooth, does not finds the situation that thin film subsides.
Wherein, in this example, optical maser wavelength selects 248nm, selects the theory of optical maser wavelength
According to being:
Styrene occurs the chemical equation being polymerized as follows:
The operation principle of laser-induced chemical vapour deposition is light initiation polymerization.Calculate
Finding that the photon energy of 248nm laser is about 5eV, ethylene double bond bond energy is about 6eV,
Double bond is opened required bond energy and is about 2.3eV, and phenyl ring fracture bond energy is about 6.15eV, C-H
Bond energy is about 4eV.It is not difficult to find out, under induced with laser, is easiest to fracture
Chemical bond is ethylene double bond, and the laser of 248nm can also make c h bond rupture.
Therefore, it is necessary to be accurately controlled laser energy density so that the reaction of material occurs
Absorb a laser photon process, and light absorbs and occurs in low energy reactions process,
Break and during ethylene double bond makes styrene be polymerized, protect c h bond and phenyl ring
On chemical bond be not destroyed.
Claims (10)
1. the preparation method of a ultra-thin self-supporting thin polymer film, it is characterised in that comprise the following steps:
Step 1, substrate cleans, and prepares substrate and cleans up；
Step 2, prepared by release layer, plate the metal release layer of last layer 20～50nm on a side surface of described substrate；
Step 3, fills sample, is fixed on sample carrier by the substrate being coated with metal release layer, and is suspended on by sample carrier in the vacuum cavity of induced with laser CVD equipment, then the vacuum cavity of this induced with laser CVD equipment is evacuated to 1.0～2.0 × 10-4Pa；
Step 4, arranges the parameter of induced with laser CVD, is set as a with not gas with polymer reaction to be prepared as carrier gas, carrier gas total amount
Sccm, the carrier gas of b sccm therein is directly entered vacuum cavity, the carrier gas of (a-b) sccm additionally is in a pulsed fashion by the jar containing polymer monomer, make carrier gas carry polymer monomer and enter vacuum cavity with the form of bubbling, and control valve makes the vacuum in vacuum cavity be 2Pa, wherein, 4 a 6,2 b 3；
Step 5, the selection of laser, select optical maser wavelength according to the character of prepared material, be 10～20mJ/cm by the energy density after beam expanding lens2, laser frequency is 0.5～2Hz；
Step 6, the preparation of thin polymer film, as carrier gas, the polymer monomer of thin film to be prepared is entered vacuum cavity in the way of molecular flow with hydrogen, when coating the polymer monomer of a monolayer on the metal release layer of described substrate, described laser is exposed on this substrate, realize the aggregation growth of polymer monomer monolayer, and film thickness as required selects the plated film time, to obtain the thin film of different-thickness；
Step 7, demoulding, the thin film prepared to be put in acid solution, dissolves release layer, thin polymer film i.e. swims on acid solution face, by being cleaned multiple times, removes the metal ion in solution so that thin polymer film swims on the water surface；
Step 8, the self-supporting of thin film, preprepared perforated metal frame tilt put in water, slowly support thin polymer film；
Step 9, deposits, and can leave in drying cupboard stand-by after thing film surface moisture natural evaporation to be polymerized is dry.
The preparation method of ultra-thin self-supporting thin polymer film the most according to claim 1, it is characterised in that: in described step 1, described substrate is silicon chip, fused quartz or sapphire.
The preparation method of ultra-thin self-supporting thin polymer film the most according to claim 1, it is characterised in that: in described step 2, use the mode of magnetron sputtering or thermal evaporation to plate metal release layer on a side surface of described substrate.
The preparation method of ultra-thin self-supporting thin polymer film the most according to claim 1, it is characterised in that: in described step 2, the surface roughness of described metal release layer is less than 0.1nm.
The preparation method of ultra-thin self-supporting thin polymer film the most according to claim 1, it is characterised in that: in described step 2, the metal in described metal release layer is aluminum or ferrum.
The preparation method of ultra-thin self-supporting thin polymer film the most according to claim 1, it is characterised in that: in described step 4, hydrogen enters vacuum cavity in the way of molecular flow.
The preparation method of ultra-thin self-supporting thin polymer film the most according to claim 1, it is characterised in that: in described step 4, the persistent period of ram charging is 10s, and interval time is 20s.
The preparation method of ultra-thin self-supporting thin polymer film the most according to claim 1, it is characterised in that: in described step 4, the gas flow of described carrier gas uses mass flowmenter to control, and its precision should be less than 0.1sccm.
The preparation method of ultra-thin self-supporting thin polymer film the most according to claim 1, it is characterised in that: in described step 4, described carrier gas is hydrogen, methane or other only carbon containing and the gas of hydrogen.
The preparation method of ultra-thin self-supporting thin polymer film the most according to claim 1, it is characterised in that: in described step 7, described acid solution is hydrochloric acid or nitric acid, and its concentration is less than 0.1mol/L.
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| CN201610503165.XA CN106011775B (en) | 2016-06-29 | 2016-06-29 | The preparation method of ultra-thin self-supporting thin polymer film |
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| CN201610503165.XA CN106011775B (en) | 2016-06-29 | 2016-06-29 | The preparation method of ultra-thin self-supporting thin polymer film |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107142449A (en) * | 2017-05-04 | 2017-09-08 | 中国工程物理研究院激光聚变研究中心 | A kind of preparation method of high-precision very small dimensions self-supporting beryllium film |
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| JP2002283090A (en) * | 2001-03-27 | 2002-10-02 | Mitsui Chemicals Inc | Deposit protective member for laser beam introducing optical window of laser ablation device, and method and device of laser ablation |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107142449A (en) * | 2017-05-04 | 2017-09-08 | 中国工程物理研究院激光聚变研究中心 | A kind of preparation method of high-precision very small dimensions self-supporting beryllium film |
| CN107142449B (en) * | 2017-05-04 | 2019-05-28 | 中国工程物理研究院激光聚变研究中心 | A kind of preparation method of high-precision very small dimensions self-supporting beryllium film |
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| CN106011775B (en) | 2018-09-07 |
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