CN102880003B - Laser write-through organic thermal etching material and preparation method thereof - Google Patents
Laser write-through organic thermal etching material and preparation method thereof Download PDFInfo
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- CN102880003B CN102880003B CN201210421357.8A CN201210421357A CN102880003B CN 102880003 B CN102880003 B CN 102880003B CN 201210421357 A CN201210421357 A CN 201210421357A CN 102880003 B CN102880003 B CN 102880003B
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Abstract
The invention discloses a laser write-through organic thermal etching material and a preparation method thereof. The material is prepared by adopting 2-methyl resorcinol or 1,2,3-trisphenol and aldehydes having condensation reaction under the catalysis of acid. The material is used for laser write-through to prepare convex micrometer or nano-scale pattern structures, no femtosecond laser pulse or multi-layer film structures are needed, and only microsecond pulse or continuous laser and single layer film structures are needed, so that the requirements on laser equipment are reduced, the process is simplified, the cost is reduced, and the efficiency is increased; and in addition, compared with a laser thermal etching inorganic material which is used for producing films by using a magnetron sputtering or evaporation plating method under a high vacuum condition, the organic thermal etching material can be dissolved in organic solvents and can be used for producing films by adopting a simple spinning coating method, so that the cost in making films is further reduced, and the film making efficiency is increased.
Description
Technical field
The present invention relates to laser direct-writing material, particularly organic hot etching material of a kind of laser direct-writing and preparation method thereof.This material is made up of cup [4] aromatic hydrocarbons derivant, can be used for micron and the nano-scale pattern structure of laser direct-writing projection.
Background technology
In recent years, laser direct-writing draughtsmanship gets more and more people's extensive concerning, because its equipment is simple, without the mask of exposure, technique is simple, low (the list of references: T.C.Chong of cost, M.H.Hong, and L.P.Shi, Laser & Photonics Reviews, 4(2010), 123).Utilize femto-second laser pulse direct writing technology; researcher has obtained different protruding figure structure in surfaces of various materials; graphic structure (list of references 1:Kuznetsov AI, Koch J, the Chichkov BN.Appl Phys A 2009 of for example taper, convexity and nozzle shape; 94:221 – 30; List of references 2:Han ZH, Zhou CH, Dai EW.Chin Opt Lett 2008; 6 (8): 619 – 21; List of references 3:Shiu TR, Grigoropoulos CP, Cahill DG, Greif R.J Appl Phys 1999; 86 (3): 1311 – 6).These structures can be used as optical coating and play increase transmitance or antireflecting effect (list of references: M.A.Tsai; et al; OPTICS EXPRESS; 19 (2011), A28-A34) or for the preparation of bionic structure (list of references: Liu CY, Chuang JF; Yu TC; Wang K, Nano/Micro Engineered and Molecular Systems (NEMS), 2012; 7th IEEE International Conference:388-91) or for the preparation of small feds and for the preparation of the Micro Channel Architecture (list of references: Chen H of biological chemistry checkout equipment; Liu X; Muthuraman H; Zou J; Wang J; Dai Q, Huo Q, Adv.Mater.2006; 18:2876-9) etc.
It is due to its pulse energy high concentration that femtosecond laser is used to directly write graphic structure; can melt or even ablator in time very; make to cause at short notice some special physical chemistry effects and induce the formation of projection or other graphic structures; effect (the list of references 1:Korte F such as such as kalimeris dagger-axe Buddhist nun convection current, material gasification and thermoplastic distortion; Koch J, Chichkov BN.Appl Phys A 2004; 79:879 – 81; List of references 2:NakataY, Miyanaga N, Okada T.Appl Surf Sci 2007; 253 (15): 6555 – 7; List of references 3:Mescheryakov YP, Bulgakova NM.Appl Phys A 2006; 82:363 – 8).But because femto-second laser pulse produces harshlyer to requirement for environmental conditions, needed femto-second laser itself is also more expensive, make the cost of this femtosecond pulse direct writing technology and efficiency still be difficult to reach the demand of actual production.Recently, there is researcher to utilize multi-layer film structure, also successfully prepared neat protruding graphic structure (list of references: Dun A, Wei J, Gan F.Appl Phys A 2010 with nanosecond laser pulses; 100:401 – 7).Their principle is that after the volatile material based on lower floor absorbs light, generation heat makes material gasify to prop up the membraneous material on upper strata, thereby forms protruding graphic structure.This multi-layer film structure is made up of inorganic material, need to carry out masking by the method for magnetron sputtering or evaporation, and multi-layer film structure itself just needs multiple tracks coating process, makes technique more complicated, and efficiency is also lower, has limited its widespread use.
Summary of the invention
The object of the present invention is to provide organic hot etching material of a kind of laser direct-writing and preparation method thereof, this material dissolves in organic solvent, available easy spin coating method masking.This material, can be at the graphic structure of single thin film format surface projection, without using femto-second laser pulse or multi-layer film structure under the effect of microsecond or continuous laser.
Technical solution of the present invention is as follows:
The organic hot etching material of a kind of laser direct-writing, is with aldehydes, condensation reaction generation to occur under sour catalysis by 1,2,3-trisphenol or 2-methylresorcinol, and its general formula of molecular structure is as follows:
Wherein: Y representation hydroxy or methyl, X represents 4-hydroxy benzenes or n-hexyl or 3 cyclohexene groups.
The preparation method of the organic hot etching material of laser direct-writing of the present invention acts on following reaction equation:
Concrete synthesis step is:
<1> claims synthesis material, is by weight percentage
Percentage by weight the raw materials weighing of selected synthesis material;
<2> is by described 1,2,3-trisphenol or 2-methylresorcinol are dissolved in the mixed solution of described ethanolic solution or ethanol and deionized water, pass under nitrogen protection, stir and drip lentamente described concentrated hydrochloric acid, and then lentamente by described aldehyde compound adding dropwise, be finally stirring reaction 0.5-22 hour at 20 DEG C～78 DEG C in temperature;
After <3> reaction, leave standstill cooling 1～2 hour, through decompress filter and dry, obtain target product.
Described aldehyde compound is n-Heptaldehyde or 4-hydroxy benzaldehyde or 3-cyclohexene-1-formaldehyde.
Technique effect of the present invention:
Laser straight of the present invention forms based on cup [4] aromatic hydrocarbons derivant with hot etching machine material.This material has the following advantages compared with preparing protruding graphic structure material with existing laser direct-writing:
(1) this material dissolves in organic solvent, can adopt easy spin coating proceeding masking, and this need to be with compared with the method for vacuum magnetic-control sputtering or evaporation masking with inorganic material masking, and without high-vacuum apparatus, both cost-saved, masking efficiency is higher simultaneously.
(2) at the protruding graphic structure of this material film surface preparation, only need to use microsecond laser pulse or continuous laser, this with need to prepare compared with protruding graphic structure with femto-second laser pulse, reduced the requirement to directly writing laser equipment, reduced cost.
(3) at the protruding graphic structure of this material film surface preparation, only need single-layer membrane structure, this prepares compared with protruding graphic structure with needing multi-layer film structure, has simplified film layer structure, has simplified technique, has also reduced cost, has improved efficiency.
Brief description of the drawings
Fig. 1 is the pattern design sketch that utilizes point-like protruding figure structure that the material obtaining in the embodiment of the present invention 5 obtains under the effect of 405nm microsecond pulse laser to obtain after atomic force scanning.
Fig. 2 is the pattern design sketch that utilizes wire protruding figure structure that the material obtaining in the embodiment of the present invention 5 obtains under the effect of 405nm continuous laser to obtain after atomic force scanning.
Fig. 3 is the organic hot etching material molecule general structure figure of laser direct-writing of the present invention.
Embodiment
Provide specific embodiments of the invention below and can further be well understood to the present invention, but they not limitation of the invention.
Embodiment 1:
Preparation method's step of the present embodiment is as follows:
<1> takes the synthesis material of following percentage by weight:
1,2,3-trisphenol: 8.4wt%; Concentrated hydrochloric acid: 16.8wt%; 4-hydroxy benzaldehyde: 8.1wt%; Ethanol: 66.7wt%.
<2> is dissolved in 1,2,3-trisphenol in ethanolic solution, pass under nitrogen protection, stir and drip lentamente concentrated hydrochloric acid, and then lentamente by 4-hydroxy benzaldehyde adding dropwise, stirring reaction 12 hours at 78 DEG C, reaction equation is as above-mentioned;
After <3> reaction finishes, leave standstill cooling 2 hours, product is separated out from reaction solution, leach the product of gained, 50 DEG C of vacuum drying obtain 2,8,14,20-tetra-4-hydroxy benzenes-4,6,10,12,16,18,22,24,25,26,27,28-ten dihydroxy cup [4] aromatic hydrocarbons.
Electron impact mass spectra test: theoretical molecular C
52h
40o
16: 920.23, mass spectrum 943.2(M+Na)
Embodiment 2:
Preparation method's step of the present embodiment is as follows:
<1> takes the synthesis material of following percentage by weight:
1,2,3-trisphenol: 5.6wt%; Concentrated hydrochloric acid: 22.3wt%; N-Heptaldehyde: 5.1wt%; Ethanol: 44.7wt%; Deionized water: 22.3wt%.。
<2> is dissolved in 1,2,3-trisphenol in the solution of ethanol and deionized water, pass under nitrogen protection, stir and drip lentamente concentrated hydrochloric acid, and then lentamente by n-Heptaldehyde adding dropwise, stirring reaction 22 hours at 78 DEG C, reaction equation is as above-mentioned;
After <3> reaction finishes, leave standstill cooling 2 hours, product is separated out from reaction solution, leach the product of gained, 65 DEG C of vacuum drying obtain 2,8,14,20-tetra-n-hexyl-4,6,10,12,16,18,22,24,25,26,27,28-ten dihydroxy cup [4] aromatic hydrocarbons.
Electron impact mass spectra test: theoretical molecular C
52h
72o
12: 888.5, mass spectrum 911.5(M+Na)
Embodiment 3:
Preparation method's step of the present embodiment is as follows:
<1> takes the synthesis material of following percentage by weight:
1,2,3-trisphenol: 5.6wt%; Concentrated hydrochloric acid: 22.5wt%; 3-cyclohexene-1-formaldehyde: 4.9wt%; Ethanol: 33.5wt%; Deionized water: 33.5wt%.。
<2> is by 1,2,3-trisphenol is dissolved in the solution of ethanol and deionized water, pass under nitrogen protection, stir and drip lentamente concentrated hydrochloric acid, and then lentamente by 3-cyclohexene-1-formaldehyde adding dropwise, stirring reaction 18 hours at 78 DEG C, reaction equation is as above-mentioned;
After <3> reaction finishes, leave standstill cooling 1 hour, product is separated out from reaction solution, leach the product of gained, 65 DEG C of vacuum drying obtain 2,8,14,20-tetra-3-cyclohexene-4,5,6,10,11,12,16,17,18,22,23,24-ten dihydroxy cup [4] aromatic hydrocarbons.
Electron impact mass spectra test: theoretical molecular C
52h
56o
12: 872.38, mass spectrum 895.4(M+Na)
Embodiment 4:
Preparation method's step of the present embodiment is as follows:
<1> takes the synthesis material of following percentage by weight:
2-methylresorcinol: 5.6wt%; Concentrated hydrochloric acid: 22.5wt%; 3-cyclohexene-1-formaldehyde: 4.9wt%; Ethanol: 33.5wt%; Deionized water: 33.5wt%.。
<2> is dissolved in 2-methylresorcinol in the solution of ethanol and deionized water, pass under nitrogen protection, stir and drip lentamente concentrated hydrochloric acid, and then lentamente by 3 cyclohexene-1-formaldehydes adding dropwise, stirring reaction 0.5 hour at 25 DEG C, reaction equation is as above-mentioned;
After <3> reaction finishes, leave standstill cooling 1 hour, product is separated out from reaction solution, leach the product of gained, 65 DEG C of vacuum drying obtain 2,8,14,20-tetra-3-cyclohexene-5,11,17,23-tetramethyl-4,6,10,12,16,18,22,24-eight hydroxyl cup [4] aromatic hydrocarbons.
Electron impact mass spectra test: theoretical molecular C
56h
64o
8: 864.46, mass spectrum 887.5(M+Na)
Embodiment 5:
Preparation method's step of the present embodiment is as follows:
<1> takes the synthesis material of following percentage by weight:
2-methylresorcinol: 5.6wt%; Concentrated hydrochloric acid: 22.3wt%; N-Heptaldehyde: 5.1wt%; Ethanol: 50.25wt%; Deionized water: 16.75wt%.。
<2> is dissolved in 2-methylresorcinol in the solution of ethanol and deionized water, pass under nitrogen protection, stir and drip lentamente concentrated hydrochloric acid, and then lentamente by n-Heptaldehyde adding dropwise, stirring reaction 0.5 hour at 20 DEG C, reaction equation is as above-mentioned;
After <3> reaction finishes, leave standstill cooling 2 hours, product is separated out from reaction solution, leach the product of gained, 65 DEG C of vacuum drying obtain 2,8,14,20-tetra-n-hexyl-5,11,17,23-tetramethyl-4,6,10,12,16,18,22,24-eight hydroxyl cup [4] aromatic hydrocarbons.
Electron impact mass spectra test: theoretical molecular C
56h
80o
8: 880.59, mass spectrum 903.6(M+Na)
Embodiment 6:
Preparation method's step of the present embodiment is as follows:
<1> takes the synthesis material of following percentage by weight:
2-methylresorcinol: 4.5wt%; Concentrated hydrochloric acid: 18.1wt%; 4-hydroxy benzaldehyde: 4.4wt%; Ethanol: 73wt%.
<2> is dissolved in 2-methylresorcinol in ethanolic solution, pass under nitrogen protection, stir and drip lentamente concentrated hydrochloric acid, and then lentamente by 4-hydroxy benzaldehyde adding dropwise, stirring reaction 10 hours at 78 DEG C, reaction equation is as above-mentioned;
After <3> reaction finishes, leave standstill cooling 2 hours, product is separated out from reaction solution, leach the product of gained, 50 DEG C of vacuum drying obtain 2,8,14,20-tetra-4-hydroxy benzenes methyl-5,11,17,23-tetramethyl 4,6,10,12,16,18,22,24-eight hydroxyl cup [4] aromatic hydrocarbons.
Electron impact mass spectra test: theoretical molecular C
52h
48o
12: 912.31, mass spectrum 935.3(M+Na)
Utilize the organic hot etching material of laser direct-writing of the present invention to carry out the graphic structure embodiment of laser direct-writing projection:
<1> in propylene glycol methyl ether acetate solution, is spun on organic the laser direct-writing obtaining in above-described embodiment 5 hot etching material dissolves on substrate, obtains being applicable to the homogeneous film of laser mapping;
<2> utilizes focusing pulse laser action on film, can obtain the protruding figure structure of point-like.Fig. 1 is the 3-D effect shape appearance figure that these point-like protruding figure structures obtain after the scanning of atomic force pattern, and it is 405nm that focusing pulse swashs light wavelength, and laser pulse width is 50 μ s, and laser power is 10 milliwatts.
Utilize and focus on continuous wave laser action on film, can obtain the protruding figure structure of wire.Fig. 2 is the 3-D effect shape appearance figure that these wire bulge-structures obtain after the scanning of atomic force pattern, and the straight writing rate of continuous laser is 70 mm/second, and laser power is 12.5 milliwatts.
The organic hot etching material of laser direct-writing obtaining in other embodiment uses the same method and can obtain the protruding figure structure of same effect, pardons me and here repeats no more.
Although the present invention has been described in detail and has quoted as proof some specific embodiments, to those skilled in the art, only otherwise it is obvious leaving that the spirit and scope of the present invention can make various changes and revise.
Claims (2)
1. the organic hot etching material of laser direct-writing, is characterized in that the general molecular formula of this material is as follows:
Wherein: Y representation hydroxy or methyl, X represents 4-hydroxy benzenes, n-hexyl or 3-cyclohexene group.
2. the preparation method of the organic hot etching material of laser direct-writing claimed in claim 1, is characterized in that the step of the method is as follows:
1. the synthetic raw material using and the span of percentage by weight thereof are:
Percentage by weight the raw materials weighing of selected synthesis material;
2. by described 1; 2; 3-trisphenol or 2-methylresorcinol are dissolved in the mixed solution of described ethanol or ethanol and deionized water; pass under nitrogen protection; stir and drip lentamente described concentrated hydrochloric acid; then described aldehyde compound dropwise being added, is finally stirring reaction 0.5～22 hour at 20 DEG C～78 DEG C in temperature, and reaction equation is as follows:
3. after reaction, leave standstill cooling 1～2 hour, decompress filter is dry, obtains the organic hot etching material of target product.
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Citations (3)
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| CN1084284A (en) * | 1992-07-10 | 1994-03-23 | 阿克佐公司 | Comprise non-linear optical waveguiding material with a plurality of donor-pi-acceptor systems adulterants |
| US6168900B1 (en) * | 1997-03-13 | 2001-01-02 | Nec Corporation | Chemically amplified resist |
| JP2007254548A (en) * | 2006-03-22 | 2007-10-04 | Mitsubishi Chemicals Corp | Optical recording medium and pigment for forming its recording layer |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1084284A (en) * | 1992-07-10 | 1994-03-23 | 阿克佐公司 | Comprise non-linear optical waveguiding material with a plurality of donor-pi-acceptor systems adulterants |
| US6168900B1 (en) * | 1997-03-13 | 2001-01-02 | Nec Corporation | Chemically amplified resist |
| JP2007254548A (en) * | 2006-03-22 | 2007-10-04 | Mitsubishi Chemicals Corp | Optical recording medium and pigment for forming its recording layer |
Non-Patent Citations (2)
| Title |
|---|
| 多光子光刻用的杯[4]芳烃分子玻璃正性光刻胶;李浩等;《影像科学与光化学》;20120930;第30卷(第5期);347-357 * |
| 李浩等.多光子光刻用的杯[4]芳烃分子玻璃正性光刻胶.《影像科学与光化学》.2012,第30卷(第5期),347-357. |
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Effective date of registration: 20211110 Address after: 311421 No. 328, Daqiao South Road, Chunjiang street, Fuyang District, Hangzhou City, Zhejiang Province Patentee after: Hangzhou Institute of Optics and precision machinery Address before: 201800 P.O. Box 800-211, Jiading District, Shanghai Patentee before: Shanghai Institute of Optics and precision machinery, Chinese Academy of Sciences |