CN105807466B - A kind of metal nanoparticle-liquid crystal array structure box production of photoelectricity regulation - Google Patents
A kind of metal nanoparticle-liquid crystal array structure box production of photoelectricity regulation Download PDFInfo
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
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Abstract
The present invention provides a kind of dynamic metal nano particle-liquid crystal composite array structure box production method of photoelectricity regulation, belongs to field of photoelectric technology.LSPR principle of the invention based on nanostructure polarization configuration, molecular configuration matching and noble metal nano particles, the standing wave that suddenly died using laser focuses capture deposition technique, variation laser suddenly dies standing wave light intensity magnitude, and then regulates and controls metal nano array-liquid crystal composite construction spatial shape；While regulating and controlling aggregation deposition using light field, different voltages are loaded between upper/lower electrode, electric field between electrodes variation is controllable metal nanoparticle-liquid crystal composite array structure space structure, realizes spectral response and photoelectricity regulation different in liquid crystal cell.The metal nanoparticle that the present invention makes-liquid crystal composite array structure box helps to provide new principle and new method for novel surface phasmon photoelectric display technology.
Description
Technical field
The invention belongs to field of photoelectric technology, and in particular to a kind of metal nanoparticle-liquid crystal array knot of photoelectricity regulation
The production of structure box.
Background technique
In information optical field, liquid crystal type opto-electronic device shows in light, photoswitch and in terms of there is weight
It applies.Liquid crystal-nano particle composite material is used in first to be improved in traditional liquid crystal display and memory device.In addition to
Application on traditional liquid crystal device is outer, using liquid crystal organization nano particle, can develop the material with special optical property
Material, such as photonic crystal and special optical material etc..
Surface plasma excimer (SPP) is that a kind of radiated based on external electromagnetic is intercoupled with metal surface free electron
Effect, so that the electronics cluster generated at metal and medium interface vibrates.SPP excitation can induce a series of unusual photo electrics
Matter, the super diffraction characteristic of sub-wavelength and non-radiative characteristic are expected to realize that energy of electromagnetic field regulation and local fields increase in nanoscale
By force.SPP nanocomposite optical device enhances ability to the transmission of special wavelength light, and (compares optics to the ultrahigh resolution of near field light
One magnitude of high resolution defined by diffraction limit) regulation so that using nanotechnology to the generation of optical information, conduct and obtain
The intensity, phase of light and polarization state are manipulated during taking, and are realized super diffraction limit, the regulation of hypersensitive optical information and are obtained
It is possibly realized.
Many studies have shown that when nano-particle diameter is suitable with liquid crystal molecule length, nano particle/dispersed liquid crystal system
In it is related interact, cause nano particle inside liquid crystal, surface or various fault locations realize various spot figures from group
It knits.In recent years, the research of the self-organizing behavior of nano particle is more in liquid crystal, mainly various dielectric materials or metal material
Self-organizing basic law of the glue crystalline substance micro-nano particle in liquid crystal.Full light regulation side in nano particle-liquid crystal hybrid system
Face is usually regulated and controled self-organization of nanoparticles in induction liquid crystal using additional light field, and then regulates and controls nano particle-liquid crystal device
Photoelectric characteristic.Under laser irradiation, it is dispersed in the local surface plasma resonance of the metal nanoparticle in liquid crystal
When (Localized Surface Plasmon Resonance, LSPR), surface field enhancement effect leads to nano particle and surface
The interaction of liquid crystal molecule is reinforced.
In terms of electric field regulates and controls nano particle-liquid crystal self-organizing, it is commonly referred to as mixed in anisotropy nano particle-liquid crystal
Liquid is closed, under the action of extra electric field excitation, nano particle swears direction towards that can be mechanically coupled to periphery liquid crystal orientation, into
And change the Extinction Characteristic of the specific wavelength of transmitted light.In general, anisotropy nano particle row of steering in isotropic fluid
It is 102~105V that cloth, which needs voltage, greatly limits its practical application.Liu et al. people is by carrying out polymeric wrap to gold nanorods
It is dispersed in liquid crystal after covering, forms the decentralized system of long-range order.Under DC Electric Field, in the system surface respectively to
The opposite sex interaction make it have preferable polarization sensitive, the photoelectric response speed of visible light and near infrared band greatly
Fastly, threshold value is down to 1V.
Summary of the invention
The present invention provides a kind of metal nanoparticle-liquid crystal array structure box production methods of photoelectricity regulation, can make
Make novel liquid crystal Electro-Optical Display, and chemical sensor and biosensor based on optical signalling.The present invention is to develop letter
Just, cheap and highly sensitive dynamic metal nano particle-liquid crystal composite array structure box with dynamic photoelectric regulation is mesh
, the LSPR principle based on nanostructure polarization configuration, molecular configuration matching and noble metal nano particles is suddenly died using laser and is stayed
Wave focuses capture deposition technique, and variation laser suddenly dies standing wave light intensity magnitude, and then regulates and controls metal nano array-liquid crystal composite construction
Spatial shape；While regulating and controlling aggregation deposition using light field, different voltages, electric field between electrodes variation are loaded between upper/lower electrode
I.e. controllable metal nanoparticle-liquid crystal composite array structure space structure, realize in liquid crystal cell different spectral response and
Photoelectricity regulation.
The present invention specifically adopts the following technical scheme that
A kind of dynamic metal nano particle-liquid crystal composite array structure box production method of photoelectricity regulation, specifically includes
Following steps:
Step 1. prepares metal nanoparticle colloid solution:
Gold, silver, copper nano particles colloidal solution are made using conventional method.By the aqueous solution containing Ag+ or Au3+ or Cu2+
It is mixed with reducing agent, atomic state metal is gathered into nanocluster quickly, completes metal nanoparticle colloid solution at this time
Preparation；
Step 2. dispersion in liquid crystal (4'- n-pentyl -4- cyanobiphenyl, that is, 5CB) by metal nanoparticle:
Metal nanoparticle colloid solution in step 1 is subjected to centrifugal treating, is then redissolved in deionized water, so
It is surface-functionalized to nano particle realization afterwards, realize the vertically oriented anchoring of liquid crystal.
Nano particle is realized surface-functionalized method particularly includes: nanoparticles solution is blended in methacryloxypropyl
In base propyl trimethoxy silicane (i.e. MPTMS) ethanol solution, centrifugal treating is carried out after sonicated to the mixture；Then
Again disperse in deionized water, to be added dimethyl hexadecyl base (i.e. DMOAP), then be redissolved in after mixture is ultrasonically treated
Deionized water obtains nano particle after surface modification.It disperses nano particle after surface modification in liquid crystal, centrifugal treating
It is scattered in methanol again afterwards, liquid crystal is then mixed into centrifuge tube.Finally the mixture is centrifuged to obtain finely dispersed receive
Rice grain-liquid crystal mixed liquor.
Step 3. makes liquid crystal cell cavity:
One layer of refractive index and close ITO (the i.e. Indium- of glass are plated in the upper surface of inverted positive four glass terrace with edge
Tin Oxide, tin indium oxide) transparent conducting glass film, electro-conductive glass film thickness is 40~100nm；Terrace with edge upper surface lid
It is pressed with the ITO electro-conductive glass of a piece of size identical as upper surface and forms cavity, cavity thickness with uv-curable glue support sealing
It is determined for 10~100um by solidification glue thickness, first fixes three faces, a face is stayed to pass through micro syringe for metal nanoparticle-
Liquid crystal mixed liquor injects in cavity, and then is uniformly distributed to form ultra-thin mixed solution layer in the cavity by capillary effect, then will
The sealing of this face, ultimately forms a rectangular closed cavity, and side length is 5~20mm, airtight cavity Edge Distance electro-conductive glass side
Along there is certain distance, the conducting surface connecting lead wire except cavity simultaneously connects voltage source, and the uv-curable glue between two layers of ITO is simultaneously
As insulating layer.
Step 4. prepares metal nanoparticle array liquid crystal cell:
The metal nanoparticle laser of building linear array single direction deposition suddenly dies stationary field: will meet the two of interference condition
Shu Jiguang is incident in opposite directions respectively at the opposite two sides of inverted positive four glass terrace with edge, and the incidence angle of two beam laser is equal, adjusts
The incidence angle for saving two beam laser is totally reflected the two same position on the inside of the positive four glass terrace with edge upper surface of inversion, is formed
Suddenly die standing wave, and the hot spot that two beam laser total reflections are formed at this time is completely coincident；
The metal nanoparticle laser of building lattice array deposition suddenly dies stationary field: it constructs two orthogonal laser and suddenly dies standing wave,
Four beam laser same position on the inside of positive four glass terrace with edge upper surface is totally reflected at this time, and hot spot overlapping light field vector is folded
Add；
Metal nanoparticle in liquid crystal laser suddenly die Standing Light Wave and electric field collective effect under deposit, deposition process
In constantly change incident intensity and voltage swing, i.e. change laser suddenly dies Standing Light Wave and electric field strength, obtains final metal
Nano-grain array shape completes metal nanoparticle array liquid crystal cell.
The frequency that interference condition described in step 4 refers specifically to two beam laser is identical, constant phase difference, direction of vibration are consistent.
Further, reducing agent described in step 1 is sodium citrate, while sodium citrate shortens aggregation as stabilizer
Process.
Further, the metal is silver, gold, copper etc..
Further, light intensity variation range is 20mw-100mw in step 4.
Further, the laser be H mode (i.e. TE) polarization laser, and the laser wavelength range be 532nm~
630nm。
Further, the resulting nano particle of step 1 is spherical or elliposoidal.
Further, glass material used by the positive truncated rectangular pyramids, refractive index are higher than 1.9, roughness less than 0.025
μm, permeability is higher than 99.5%, and the refractive index of liquid crystal is between 1.53-1.74.
The beneficial effects of the present invention are:
A kind of metal nanoparticle-liquid crystal array structure box production method of photoelectricity regulation provided by the invention, is swashing
Light suddenly die Standing Light Wave and electric field double action under, make metal nanoparticle-liquid crystal composite array structure box, facilitate for
Novel surface phasmon photoelectric display technology provides new principle and new method, and liquid crystal cell of the invention can be promoted energetically
The spectral response of liquid crystal type opto-electronic device, photoelectricity performance of control.
Detailed description of the invention
Fig. 1 is experiment flow figure of the present invention.
Fig. 2 is metal nano array structure liquid crystal cell cavity.
Fig. 3 is metal nanoparticle-liquid crystal composite array structure box experimental provision schematic diagram of photoelectricity regulation.
Specific embodiment
The present embodiment uses following scheme:
Step 1. prepares metal nanoparticle colloid solution:
Gold, silver nanometer grain preparation method is similar.By containing Ag+ solution and reduction of sodium citrate agent be mixed,
Atomic state metal is gathered into nanocluster quickly, obtains metal nanoparticle colloid solution, and wherein sodium citrate is simultaneously as steady
Determine agent and shortens accumulation process.
The dispersion in liquid crystal (such as 5CB) of step 2. metal nanoparticle:
Above-mentioned metal nanoparticle colloid solution is subjected to centrifugal treating, then is redissolved in deionized water.For in metal
Nano grain surface realizes the vertically oriented anchoring of liquid crystal, need to be used to realize to nano particle surface-functionalized (as modified
DMOAP), this method are as follows: nanoparticles solution is blended in MPTMS ethanol solution, it is sonicated to the mixture, then
Centrifugal treating is carried out, then disperses in deionized water, to be subsequently added into DMOAP again.After mixture is ultrasonically treated again again
It is dissolved in deionized water.It disperses nano particle after surface modification in liquid crystal (such as 5CB), is scattered in again after being centrifuged again
In methanol, it is then mixed into liquid crystal, is finally centrifuged the mixture to obtain finely dispersed nano particle-liquid crystal mixed liquor.
Step 3. makes nanostructure liquid crystal cell cavity:
Nanostructure liquid crystal cell cavity body structure as shown in Fig. 2, positive four glass terrace with edge use high refractive index flint glass,
Upper surface side length is 30mm, a height of 20mm, and four sides and upper surface angle are 50 °, upper surface plate one layer of refractive index with
The close electroconductive ITO film layer of glass (In2SnO3 is with a thickness of 70nm)；The sub- a piece of ITO electro-conductive glass of terrace with edge upper cover (lead by inside plating
Conductive film) and seal to form liquid crystal cell cavity with uv-curable glue, specifically, three faces are first fixed, a face is stayed to pass through micro note
Emitter injects metal nanoparticle-liquid crystal mixed liquor in cavity, and then is uniformly distributed to be formed in the cavity by capillary effect
Ultra-thin mixed solution layer, then this face is sealed, ultimately form a rectangular closed cavity, airtight cavity Edge Distance conduction glass
There is certain distance at glass edge, and the conducting surface connecting lead wire except cavity simultaneously connects voltage source, the uv-curable glue between two layers of ITO
It is used as insulating layer simultaneously.It is 20mm that cavity thickness, which are 30um side length, in the present embodiment.
Step 4. prepares metal nanoparticle array liquid crystal cell:
As shown in figure 3, wherein BS is beam-expanding collimation microscope group, PBS is power Amici prism, and M1/M2/M3 is reflecting mirror,
Middle LBE is beam expanding lens.
The metal nanoparticle laser of building linear array single direction deposition suddenly dies stationary field: will meet the two of interference condition
Shu Jiguang is incident in opposite directions respectively at the opposite two sides of inverted positive four glass terrace with edge, and the incidence angle θ of two beam laser is equal all
It is 50 °, the incidence angle for adjusting two beam laser makes the two complete in being inverted same position generation on the inside of positive four glass terrace with edge upper surface
Reflection forms the standing wave that suddenly dies, and the hot spot that two beam laser total reflections are formed at this time is completely coincident, and hot spot covers liquid crystal cell cavity institute
In region；
Metal nanoparticle in liquid crystal laser suddenly die Standing Light Wave and electric field collective effect under deposit, deposited
Constantly changing incident intensity and voltage swing in journey, (light intensity consecutive variations and variation range is 20mw-100mw, voltage continuously becomes
Change and variation range be 1V-30V), i.e. change laser suddenly dies standing wave field intensity and electric field strength, obtains final metal nano
Grain linear array shape, completes the production of metal nanoparticle array liquid crystal cell.
Claims (9)
1. a kind of dynamic metal nano particle-liquid crystal composite array structure box production method of photoelectricity regulation, specifically include with
Lower step:
Step 1. prepares metal nanoparticle colloid solution:
Aqueous solution containing Ag+ or Au3+ or Cu2+ is mixed with reducing agent, atomic state accumulation of metal is completed at nanocluster
The preparation of metal nanoparticle colloid solution；
Step 2. disperses metal nanoparticle in liquid crystal:
Metal nanoparticle colloid solution in step 1 is subjected to centrifugal treating, is then redissolved in deionized water, it is then right
Nano particle realization is surface-functionalized, realizes the vertically oriented anchoring of liquid crystal；
Step 3. makes liquid crystal cell cavity:
One layer of transparent electro-conductive glass film, ITO Indium-Tin are plated in the upper surface of inverted positive four glass terrace with edge
Oxide, that is, tin indium oxide, electro-conductive glass film thickness are 40~100nm；Terrace with edge upper surface lid is pressed with a piece of ITO electro-conductive glass simultaneously
Cavity is formed with uv-curable glue support sealing, three faces is first fixed, a face is stayed to pass through micro syringe for metal nanoparticle-
Liquid crystal mixed liquor injects in cavity, and then is uniformly distributed to form ultra-thin mixed solution layer in the cavity by capillary effect, then will
The sealing of this face, ultimately forms a rectangular closed cavity, and there is certain distance at airtight cavity Edge Distance electro-conductive glass edge,
Conducting surface connecting lead wire except cavity simultaneously connects voltage source, and the uv-curable glue between two layers of ITO is used as insulating layer simultaneously；
Step 4. prepares metal nanoparticle array liquid crystal cell:
The metal nanoparticle laser of building linear array single direction deposition suddenly dies stationary field: two beams for meeting interference condition are swashed
Light is incident in opposite directions respectively at the opposite two sides of inverted positive four glass terrace with edge, and the incidence angle of two beam laser is equal, adjusts two
The incidence angle of Shu Jiguang is totally reflected the two same position on the inside of the positive four glass terrace with edge upper surface of inversion, and formation is suddenly died
Standing wave, the hot spot that two beam laser total reflections are formed at this time are completely coincident；
Or the metal nanoparticle laser of building lattice array deposition suddenly dies stationary field: it constructs two orthogonal laser and suddenly dies standing wave,
Four beam laser same position on the inside of positive four glass terrace with edge upper surface is totally reflected at this time, and hot spot overlapping light field vector is folded
Add；
Metal nanoparticle in liquid crystal laser suddenly die Standing Light Wave and electric field collective effect under deposit, in deposition process not
Disconnected to change incident intensity and voltage swing, i.e. change laser suddenly dies Standing Light Wave and electric field strength, obtains final metal nano
Array of particles shape completes metal nanoparticle array liquid crystal cell.
2. a kind of dynamic metal nano particle-liquid crystal composite array structure box system of photoelectricity regulation as described in claim 1
Make method, it is characterised in that: realize in step 2 to nano particle surface-functionalized method particularly includes: by nano-particle colloid
Solution is blended in methacryloxypropyl trimethoxy silane ethanol solution, is carried out after sonicated to the mixture
Centrifugal treating；Then disperse in deionized water, dimethyl hexadecyl base to be added again, then after mixture is ultrasonically treated again
It is dissolved in deionized water and obtains nano particle after surface modification；It disperses nano particle after surface modification in liquid crystal, is centrifuged
It is scattered in methanol again after processing, liquid crystal is then mixed into centrifuge tube；Finally the mixture is centrifuged and is uniformly dispersed
Nano particle-liquid crystal mixed liquor.
3. a kind of dynamic metal nano particle-liquid crystal composite array structure box system of photoelectricity regulation as described in claim 1
Make method, it is characterised in that: the frequency that interference condition described in step 4 refers specifically to two beam laser is identical, constant phase difference, vibration
Direction is consistent.
4. a kind of dynamic metal nano particle-liquid crystal composite array structure box system of photoelectricity regulation as described in claim 1
Make method, it is characterised in that: the liquid crystal is 4'- n-pentyl -4- cyanobiphenyl, i.e. 5CB.
5. a kind of dynamic metal nano particle-liquid crystal composite array structure box system of photoelectricity regulation as described in claim 1
Make method, it is characterised in that: reducing agent described in step 1 is sodium citrate.
6. a kind of dynamic metal nano particle-liquid crystal composite array structure box system of photoelectricity regulation as described in claim 1
Make method, it is characterised in that: glass material used by the positive truncated rectangular pyramids, refractive index are higher than 1.9, roughness and are less than
0.025 μm, permeability is higher than 99.5%, and the refractive index of liquid crystal is between 1.53-1.74.
7. a kind of dynamic metal nano particle-liquid crystal composite array structure box system of photoelectricity regulation as described in claim 1
Make method, it is characterised in that: light intensity variation range is 20mw-100mw in step 4.
8. a kind of dynamic metal nano particle-liquid crystal composite array structure box system of photoelectricity regulation as described in claim 1
Make method, it is characterised in that: the laser is H mode polarization laser, and the laser wavelength range is 532nm~630nm.
9. a kind of dynamic metal nano particle-liquid crystal composite array structure box system of photoelectricity regulation as described in claim 1
Make method, it is characterised in that: liquid crystal cell cavity thickness are 10~100um, and side length is 5~20mm.
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| CN106847797B (en) * | 2017-01-17 | 2019-02-15 | 电子科技大学 | A kind of noble metal nano particles-quantum dot array luminescent device preparation method |
| CN108153109A (en) * | 2017-12-29 | 2018-06-12 | 深圳市华星光电技术有限公司 | The preparation method of photoetching agent pattern |
| CN108671972A (en) * | 2018-07-19 | 2018-10-19 | 广东工业大学 | The preparation method and Preparation equipment of metal-surface nano structure |
| CN109188576A (en) * | 2018-08-14 | 2019-01-11 | 华东师范大学 | A method of the Ai Li light field based on surface phasmon prepares nano material |
| CN111240049A (en) * | 2020-03-24 | 2020-06-05 | 东南大学 | High-speed response pure phase spatial light modulator |
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| CN102969400A (en) * | 2012-11-30 | 2013-03-13 | 电子科技大学 | Production method of light energy anti-reflection sheet provided with metal nano-particle array |
| CN104538837A (en) * | 2015-01-09 | 2015-04-22 | 电子科技大学 | Nanometer plasma array laser device and manufacturing method thereof |
| CN105136768A (en) * | 2015-07-27 | 2015-12-09 | 电子科技大学 | Preparation method of surface-enhanced Raman scattering (SERS) substrate polarized by metal nano particle array |
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| CN102969400A (en) * | 2012-11-30 | 2013-03-13 | 电子科技大学 | Production method of light energy anti-reflection sheet provided with metal nano-particle array |
| CN104538837A (en) * | 2015-01-09 | 2015-04-22 | 电子科技大学 | Nanometer plasma array laser device and manufacturing method thereof |
| CN105136768A (en) * | 2015-07-27 | 2015-12-09 | 电子科技大学 | Preparation method of surface-enhanced Raman scattering (SERS) substrate polarized by metal nano particle array |
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