CN101293409B - Metallic-organic complex function thin film with stepped construction and uses thereof - Google Patents
Metallic-organic complex function thin film with stepped construction and uses thereof Download PDFInfo
- Publication number
- CN101293409B CN101293409B CN200810039211A CN200810039211A CN101293409B CN 101293409 B CN101293409 B CN 101293409B CN 200810039211 A CN200810039211 A CN 200810039211A CN 200810039211 A CN200810039211 A CN 200810039211A CN 101293409 B CN101293409 B CN 101293409B
- Authority
- CN
- China
- Prior art keywords
- thickness
- film
- thin film
- nanometer
- complex function
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Images
Abstract
The invention belongs to the technical fields of nanometer materials, functional films and optical information storage, in particular to a metal-organic compound functional film with a laminated structure and applications thereof. The compound functional film is formed by laminating a plurality of films; the orders of a plurality of films are: a floor, a metal layer, an organic layer and a metal layer with nanometer thickness; wherein, the organic layer adopts a molecular material containing heterocyclic ketene condensation amine which is replaced by cyano-group; the metal layer with nanometer thickness adapts silver; the compound film can be used as an optical information storage medium and can be directly written by laser; besides, the self of the compound film can obtain controllable color change and can realize to the displaying of a plurality of colors by controlling the thickness of the metal layer with a nanometer thickness; therefore, the compound film can be used as color display material and has application values on the aspects of anti-forgery technical field, trade mark protection, etc.
Description
Technical field
The invention belongs to nano material, function film and optical information technical field of memory, be specifically related to a kind of metallic-organic complex function thin film and application thereof with stepped construction.
Technical background
Have two key issues to further develop in the laser intelligence technical field of memory: the one, the optical storage system that development is advanced, the 2nd, develop novel optical storage media.At present; Nano material and technical application have been caused people's attention in the light scientific domain; Still there are many technical problems to need to solve in function film and the device but how effectively nano material is integrated into, comprise feasibility and the cost of preparation method, material screening, technology etc.
The inventor once developed the substituted heterocyclic ketene semiamine contained molecular material of cyanic acid early stage, and had realized the multiplet electricity memory function of organic film device.([1] xuwei, Lv Yinxiang, Central China one, substituted heterocyclic ketene semiamine contained molecular material of cyanic acid and preparation method thereof, application for a patent for invention 02111272.X; [2] Peng Guo; Yuan-Wei Dong; Xin Ji, Yin-Xiang Lu, Wei Xu.Nonvolatile multilevel conductance and memory effect inmolecule-based devices.IEEE Electron Device Letters; 2007,28 (7): 572-574)
The substituted heterocyclic ketene semiamine contained molecular material of cyanic acid is the organic molecule that one type of more special having pushes away the electrophilic characteristic, and molecular material itself also has well stability.This quasi-molecule material application in the light scientific domain also needs further exploitation, hopes to replace traditional azo metal dye and diarylethene dyestuff etc., becomes one type of high performance optical information storage medium and uses material.([3] Zhao Jianfeng, Lei Yuping, Xu Limin, Guo Wenyong, the Application and Development of azo metal dye in DVD R optical storage media, Gansu oil and chemical industry, 2007 the 1st phases, the 1st～5 page; [4] Zheng Nan, Liu Zhijing, azobenzene polymer optical storage progress, micro-nano electronic technology, 2006 the 3rd phases, 130～134; [5] Liu Xuedong, Shi Ming, Zhang Fushi, synthetic and the multistage storage experimental study of organic photochromic material, functional material and device journal, 2006,12 (2): 117～119; [6] Jiang Tao, information storage frontier---Hologram Storage and material thereof, information-recording material, 2006,7 (6): 32～36.)
The present invention adopts the substituted heterocyclic ketene semiamine contained molecular material of cyanic acid as organic dielectric layer, realizes concrete optical function and optical information memory function with the composite bed of organic layer and ultrathin nanometer metal level as functional layer.Both expand the application of organic molecule material, solved the preparation of nano material and the integration problem of function film again, thereby developed the method for preparing function film that a kind of simple possible.
Summary of the invention
The objective of the invention is to propose a kind of metallic-organic complex function thin film and application thereof with stepped construction of optical function and optical information memory function.
Metallic-organic complex function thin film provided by the invention is piled up by plural layers and forms, and the order of plural layers is: the metal level of substrate, metal level, organic layer, nano thickness, its structure is as shown in Figure 1.Core texture wherein is the metal level of depositing nano thickness on the organic layer surface, and the metal level of organic layer and nano thickness is together as functional layer; Metal level on the substrate surface as a setting or the reflecting layer.
The metallic-organic complex function thin film that the present invention's proposition has stepped construction, substrate wherein can be adopted metal or inorganic material as long as surfacing does not require the material composition, also can adopt polymeric material; Metal level adopts aluminium or gold, and thickness is the 50-300 nanometer; Organic layer adopts the substituted heterocyclic ketene semiamine contained molecular material of cyanic acid, and thickness is the 30-150 nanometer; The metal level of nano thickness adopts silver (Ag), and thickness is less than 30 nanometers (for example 1-30 nanometer).
In the present invention, the substituted heterocyclic ketene semiamine contained molecular material of cyanic acid that is used to make organic layer specifically can adopt: 2-(hexahydropyrimidine-2-subunit) malononitrile; The structural formula of this molecular material is as shown in Figure 2, and English name is 2-(hexahydropyrimidin-2-ylidene)-malononitrile, is called for short HPYM.
The present invention also proposes to have the preparation method of the metallic-organic complex function thin film of stepped construction; Concrete steps are following: and in the smooth substrate of cleaning (such as: wave carrier piece); Adopt the method AM aluminum metallization film or the golden film (thickness 50～300 nanometers) of vacuum thermal evaporation; Deposit organic layer HPYM (thickness 30～150 nanometers) then, and then depositing ultrathin silverskin (thickness is 1～30 nanometer).Promptly accomplish the preparation of function film.
The present invention also proposes to have the application of the metallic-organic complex function thin film of stepped construction, one of be as colour development material.When the thickness of the silver-colored film above the organic layer changed near 30 nanometers from 1 nanometer, obvious variation can take place in the color of film, can obtain various color respectively.The color that is film can be controlled through the thickness of controlling silver-colored film.The complex function thin film of this controllable color can realize that multiple color shows to have using value aspect field of anti-counterfeit technology and the trademark protection.
It is as optical information storage medium that the another kind that the present invention also proposes to have the metallic-organic complex function thin film of stepped construction is used.When the thickness of ultra-thin silverskin is 2～8 nanometers, this complex function thin film signal that can enough laser writes direct can be seen the LASER SPECKLE of light therefore can be used as the optical information storage medium use under light microscope.If there is not the ultra-thin silverskin of this 2～8 nanometer thickness, reality has proved and can't write with laser; If the thickness of silverskin excessive (such as surpassing 15 nanometers) will just write very difficulty with laser.
SEM (SEM) is observed proof, and for being written into the zone, surface micro-structure changes at least, and forms with nanostructured.Explain that there are difference in the laser write area and the structure of write area not.
Description of drawings
Fig. 1 is the structural representation with metallic-organic complex function thin film of stepped construction.
Fig. 2 is the molecular material HPYM that is used to prepare organic layer
Fig. 3 is used as the optics colour development material for the Al/HPYM/Nano-Ag complex function thin film, and the color of film from left to right is respectively lilac, blueness, khaki, light yellow; Corresponding with it, the thickness of silver-colored ultrathin membrane is about respectively: 2 nanometers, 5 nanometers, 10 nanometers, 18 nanometers.
Fig. 4 is used as optical storage media for Al/HPYM/5nm Ag complex function thin film, can enough laser-light write go into, and shows as bright spot at the optical reflection microscopically..
Fig. 5 is not for there being the aluminium reflecting layer, and HPYM/5nm Ag film is used as optical storage media, can enough laser-light write go into yet, but shows as dim spot at the optical reflection microscopically.
Fig. 6 forms images to the same area with optics perflectometer and SEM respectively after many information points write for carrying out with laser again.Wherein, (a) image that obtains of optical reflection microscopic examination; (b) image that obtains of sem observation; (c) SEM is to 2 full resolution prictures that spot became wherein.
Label among the figure: 1 is substrate; 2 is metal level; 3 is organic layer (HPYM); 4 is nano thickness metal level (Ag)
The specific embodiment
Below through embodiment further describe the metallic-organic complex function thin film with stepped construction the preparation method and
Two kinds of purposes
Embodiment 1 (the Al/HPYM/Nano-Ag complex function thin film is used as the optics colour development material)
Wave carrier piece with cleaning is substrate, 10
-3Under the pressure of Pa magnitude with the aluminium film of method vapor deposition 300 nanometer thickness of vacuum thermal evaporation as metal level, and then the HPYM molecular layer (evaporation rate 0.7 of vapor deposition 106 nanometer thickness
About), last deposit thickness is less than the silver-colored superthin layer (evaporation rate 0.5 of 30 nanometers
About).Promptly accomplish the preparation of Al/HPYM/Nano-Ag complex function thin film.
Adopt said method to prepare following 4 kinds of complex function thin films respectively.The thickness of aluminium film and HPYM molecular layer is all identical in these 4 kinds of complex function thin films, but the thickness of ultra-thin silverskin is about respectively: 2 nanometers, 5 nanometers, 10 nanometers, 18 nanometers.(thickness of film is by the monitoring of Sigma SQM-160 calibrator)
These 4 kinds of films show various colors respectively in atmospheric environment, shown in the photo among Fig. 3.In the photo (from left to right), 4 kinds of film colors are respectively: lilac, blueness, khaki, light yellow.Corresponding with these 4 kinds of colors, the thickness of silver-colored ultrathin membrane is about respectively: 2 nanometers, 5 nanometers, 10 nanometers, 18 nanometers.
Embodiment 2 (the Al/HPYM/Nano-Ag complex function thin film is used as optical storage media)
Wave carrier piece with cleaning is substrate, 10
-3Under the pressure of Pa magnitude with the aluminium film of method vapor deposition 70～300 nanometer thickness of vacuum thermal evaporation as metallic reflector, and then the HPYM molecular layer of about 100 nanometer thickness of vapor deposition, the silver-colored superthin layer (evaporation rate 0.5 of last about 5 nanometers of deposit thickness
About).Promptly accomplish the preparation of Al/HPYM/5nm-Ag complex function thin film.
This complex function thin film can enough laser-light write be gone into, and is as shown in Figure 4.After two bright spots among the figure are represented to write with wavelength 632.8 nanometer lasers (power is less than 5 milliwatts), at the image of optical reflection microscopically, about 1～2 micron of the diameter of bright spot.
If there is not the aluminium reflecting layer in the complex function thin film, information writes a little and under light microscope, becomes dim spot, and is as shown in Figure 5.After two dim spots among the figure are represented to write with wavelength 632.8 nanometer lasers, at the image of optical reflection microscopically, about 1～2 micron of the diameter of dim spot.
The present embodiment explanation, acting in the complex function thin film is the silver layer of organic layer and nano thickness.Under light microscope, when the aluminium reflecting layer is arranged, write the point reflection performance and obviously strengthen; When not having the aluminium reflecting layer, writing a transmission increases, and reflection dies down.
For further checking optical information writes the spot and the difference of write area not, the Al/HPYM/5nm-Ag complex function thin film is carried out multiple spot write, and then with optics perflectometer and SEM the same area is formed images respectively.Fig. 6 (a) is after many information points write, the image that the optical reflection microscopic examination obtains; Fig. 6 (b) is the image that corresponding zone obtains with sem observation; Fig. 6 (c) is a SEM to 2 full resolution prictures that spot became wherein.
Explanation is observed in experiment, and the image that image that observation by light microscope obtains and sem observation obtain meets fully.High-resolution SEM image shows that also there is microstructure change in write area, compares obviously different with write area not.After laser write, the surface of write area had nanostructured to form, and with the tiny generation of chapping.
Claims (5)
1. metallic-organic complex function thin film with stepped construction is characterized in that being piled up by plural layers and forms, and the order of plural layers is: the metal level of substrate, metal level, organic layer, nano thickness; Wherein, said metal level is aluminium film or golden film, and thickness is the 50-300 nanometer; Said organic layer is 2-(hexahydropyrimidine-2-subunit) malononitrile film, and thickness is the 30-150 nanometer; The metal level of said nano thickness adopts silverskin, and thickness is the 1-30 nanometer.
2. the metallic-organic complex function thin film with stepped construction according to claim 1 is characterized in that said silver film thickness is the 2-8 nanometer.
3. the preparation method with metallic-organic complex function thin film of stepped construction according to claim 1; It is characterized in that concrete steps are: in the smooth substrate of cleaning, adopt the method AM aluminum metallization film or the golden film of vacuum thermal evaporation, thickness is 50～300 nanometers; Deposit organic layer 2-(hexahydropyrimidine-2-subunit) malononitrile film then; Thickness is 30～150 nanometers, and then the deposition silverskin, and thickness is 1～30 nanometer.
4. application with metallic-organic complex function thin film of stepped construction as the optics colour development material as claimed in claim 1.
5. application with metallic-organic complex function thin film of stepped construction as optical storage media as claimed in claim 2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810039211A CN101293409B (en) | 2008-06-19 | 2008-06-19 | Metallic-organic complex function thin film with stepped construction and uses thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810039211A CN101293409B (en) | 2008-06-19 | 2008-06-19 | Metallic-organic complex function thin film with stepped construction and uses thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101293409A CN101293409A (en) | 2008-10-29 |
| CN101293409B true CN101293409B (en) | 2012-09-05 |
Family
ID=40064066
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200810039211A Expired - Fee Related CN101293409B (en) | 2008-06-19 | 2008-06-19 | Metallic-organic complex function thin film with stepped construction and uses thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101293409B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5853638B2 (en) * | 2011-11-24 | 2016-02-09 | セイコーエプソン株式会社 | Half mirror and image display device |
| CN102436110B (en) * | 2011-12-08 | 2015-01-07 | 电子科技大学 | Flexible electro-chromic device |
| CN107475673A (en) * | 2017-08-11 | 2017-12-15 | 太仓碧奇新材料研发有限公司 | The preparation method of five layers of interlayer structure three-stable state photochromic film |
| CN107475674A (en) * | 2017-08-11 | 2017-12-15 | 太仓碧奇新材料研发有限公司 | The preparation method of three-stable state Photochromic |
| CN109468053B (en) * | 2018-09-26 | 2021-03-30 | 江苏乘鹰新材料股份有限公司 | Color-changeable UV (ultraviolet) -composite laser coating composition |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1513843A (en) * | 2002-04-04 | 2004-07-21 | 复旦大学 | Cyano substituted heterocyclic ketene semiamine contained molecular material and its preparation method |
| CN1949555A (en) * | 2006-11-09 | 2007-04-18 | 复旦大学 | Organic film device with reversible bistable information storage function |
-
2008
- 2008-06-19 CN CN200810039211A patent/CN101293409B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1513843A (en) * | 2002-04-04 | 2004-07-21 | 复旦大学 | Cyano substituted heterocyclic ketene semiamine contained molecular material and its preparation method |
| CN1949555A (en) * | 2006-11-09 | 2007-04-18 | 复旦大学 | Organic film device with reversible bistable information storage function |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101293409A (en) | 2008-10-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101293409B (en) | Metallic-organic complex function thin film with stepped construction and uses thereof | |
| Higgins et al. | Anisotropic spinodal dewetting as a route to self-assembly of patterned surfaces | |
| EP2059398B1 (en) | Security articles and devices containing coded holographic platelets and methods of manufacturing the same | |
| US6876570B2 (en) | Field addressable rewritable media | |
| KR102485172B1 (en) | Printed body with hot stamping foil and laminated optical decoration | |
| US8970955B2 (en) | Zero-order diffractive filter and method for manufacturing thereof | |
| TW200846854A (en) | An article with micro indicia security enhancement | |
| US20080024866A1 (en) | Zero-order diffractive filter | |
| US10836918B2 (en) | Microparticles and apparatus for smart ink production | |
| EP3196681A1 (en) | Security film | |
| TW200816094A (en) | Document of value having security element | |
| WO2009140088A1 (en) | Multi-layer articles capable of forming color images | |
| Dhara et al. | Transition from Spin Dewetting to continuous film in spin coating of Liquid Crystal 5CB | |
| US6853478B2 (en) | Color display with molecular light valve | |
| Wu et al. | Ultrathin photonic crystal film with supersensitive thermochromism in air | |
| Wang et al. | A reversible photochromic switch based on self-assembly of layered double hydroxide and decatungstate | |
| KR100504274B1 (en) | A method for making a transparent article including a microembossed image | |
| Pham et al. | Polymer nanostructured material for the recording of biometric features | |
| JP2008007638A (en) | Adhesive layer composition for transfer foil | |
| CN1977325A (en) | Optical data storage medium and combi-foil cover for the production thereof | |
| WO2018194167A1 (en) | Hot-stamping foil, hot-stamping foil production method, and printing body equipped with laminated optical decoration body | |
| Yuan et al. | Optical tape for high capacity three-dimensional optical data storage | |
| CN112606588A (en) | Optical color-changing gold stamping material | |
| Marichez et al. | Doped sol-gel based microstructured layers to improve the light emission of luminescent coatings | |
| JP4867526B2 (en) | Anti-counterfeit magnetic tape transfer sheet and card |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| ASS | Succession or assignment of patent right |
Owner name: SHANGHAI HONGDUN ANTI-COUNTERFEIT MATERIAL CO., LT Free format text: FORMER OWNER: FUDAN UNIVERSITY Effective date: 20130531 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| COR | Change of bibliographic data |
Free format text: CORRECT: ADDRESS; FROM: 200433 YANGPU, SHANGHAI TO: 201203 PUDONG NEW AREA, SHANGHAI |
|
| TR01 | Transfer of patent right |
Effective date of registration: 20130531 Address after: Cailun Road, Zhangjiang Town Pudong New Area Shanghai City No. 150 201203 Patentee after: Shanghai HongDun Anti-Counterfeit Material Co., Ltd. Address before: 220 Handan Road, Shanghai, No. 200433 Patentee before: Fudan University |
|
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20120905 Termination date: 20180619 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |