CN104882540B - Molecular plane parallel to Si/SiO2Preparation method of porphyrin monomolecular layer on surface - Google Patents
Molecular plane parallel to Si/SiO2Preparation method of porphyrin monomolecular layer on surface Download PDFInfo
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- 150000004032 porphyrins Chemical class 0.000 title claims abstract description 39
- 238000000034 method Methods 0.000 title claims abstract description 13
- 239000000758 substrate Substances 0.000 claims abstract description 26
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 19
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 19
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 19
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 19
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 19
- 239000010409 thin film Substances 0.000 claims abstract description 7
- 239000000126 substance Substances 0.000 claims abstract description 6
- 229910021645 metal ion Inorganic materials 0.000 claims abstract 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 125000000524 functional group Chemical group 0.000 claims 2
- 125000001841 imino group Chemical group [H]N=* 0.000 claims 2
- 229910004298 SiO 2 Inorganic materials 0.000 claims 1
- 229910004283 SiO 4 Inorganic materials 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims 1
- 238000001338 self-assembly Methods 0.000 abstract description 9
- 230000001105 regulatory effect Effects 0.000 abstract 1
- -1 alkyl organosilanes Chemical class 0.000 description 33
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 20
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 18
- 239000010408 film Substances 0.000 description 16
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 15
- 238000010992 reflux Methods 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 12
- 238000002360 preparation method Methods 0.000 description 12
- 239000002904 solvent Substances 0.000 description 11
- 238000005160 1H NMR spectroscopy Methods 0.000 description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 10
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 10
- 238000005481 NMR spectroscopy Methods 0.000 description 10
- 229910052739 hydrogen Inorganic materials 0.000 description 10
- 239000001257 hydrogen Substances 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 8
- 239000011368 organic material Substances 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 238000010586 diagram Methods 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 6
- 239000012153 distilled water Substances 0.000 description 6
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- 229910052710 silicon Inorganic materials 0.000 description 6
- 239000010703 silicon Substances 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- RNGSTWPRDROEIW-UHFFFAOYSA-N [Ni].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 Chemical compound [Ni].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 RNGSTWPRDROEIW-UHFFFAOYSA-N 0.000 description 5
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 5
- UIIMBOGNXHQVGW-UHFFFAOYSA-M sodium bicarbonate Substances [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 239000002356 single layer Substances 0.000 description 4
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- RGHHSNMVTDWUBI-UHFFFAOYSA-N 4-hydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1 RGHHSNMVTDWUBI-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- NUSORQHHEXCNQC-UHFFFAOYSA-N [Cu].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 Chemical compound [Cu].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 NUSORQHHEXCNQC-UHFFFAOYSA-N 0.000 description 2
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000006298 dechlorination reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000013067 intermediate product Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 150000001282 organosilanes Chemical class 0.000 description 2
- SLIUAWYAILUBJU-UHFFFAOYSA-N pentacene Chemical compound C1=CC=CC2=CC3=CC4=CC5=CC=CC=C5C=C4C=C3C=C21 SLIUAWYAILUBJU-UHFFFAOYSA-N 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000013545 self-assembled monolayer Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- UGNWTBMOAKPKBL-UHFFFAOYSA-N tetrachloro-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(Cl)=C(Cl)C1=O UGNWTBMOAKPKBL-UHFFFAOYSA-N 0.000 description 2
- 239000011592 zinc chloride Substances 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- VEFLKXRACNJHOV-UHFFFAOYSA-N 1,3-dibromopropane Chemical class BrCCCBr VEFLKXRACNJHOV-UHFFFAOYSA-N 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- 229910021577 Iron(II) chloride Inorganic materials 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 229910007339 Zn(OAc)2 Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000013086 organic photovoltaic Methods 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 150000003233 pyrroles Chemical class 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- DJWUNCQRNNEAKC-UHFFFAOYSA-L zinc acetate Chemical compound [Zn+2].CC([O-])=O.CC([O-])=O DJWUNCQRNNEAKC-UHFFFAOYSA-L 0.000 description 1
- FUTVBRXUIKZACV-UHFFFAOYSA-J zinc;3-[18-(2-carboxylatoethyl)-8,13-bis(ethenyl)-3,7,12,17-tetramethylporphyrin-21,24-diid-2-yl]propanoate Chemical compound [Zn+2].[N-]1C2=C(C)C(CCC([O-])=O)=C1C=C([N-]1)C(CCC([O-])=O)=C(C)C1=CC(C(C)=C1C=C)=NC1=CC(C(C)=C1C=C)=NC1=C2 FUTVBRXUIKZACV-UHFFFAOYSA-J 0.000 description 1
Classifications
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having potential barriers
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having potential barriers
- H10K10/40—Organic transistors
- H10K10/46—Field-effect transistors, e.g. organic thin-film transistors [OTFT]
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/30—Coordination compounds
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K2102/00—Constructional details relating to the organic devices covered by this subclass
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
Abstract
Charge transport in Organic Thin Film Transistors (OTFTs) occurs in a few molecular layers near the insulating/semiconducting layer interface, so the nature of this interface layer plays a crucial role in the performance of the device. The invention utilizes a self-assembly and surface chemical growth method to prepare Si/SiO2Preparing a porphyrin monomolecular layer on the substrate, and enabling a large ring plane of the porphyrin monomolecular layer to be parallel to the surface of the substrate; by using different metal ions (Zn)2+，Fe2+，Cu2+，Ni2+，Co2+) The formed porphyrin monomolecular layer with rich electronic structure is used for regulating Si/SiO2Surface potential and charge distribution; a method for effectively preparing the face-on arrangement of the organic molecules is provided, and the influence of the face-on arrangement on the performance of the device is further researched.
Description
Technical field
Charge transmission in Organic Thin Film Transistors (OTFT) is happened at several points near insulating layer/semiconductor layer interface
Sublayer, therefore the property at this interface plays conclusive effect for the performance of device.The present invention utilizes Chemical self-assembly work
Skill is to Si/SiO2Substrate is surface modified, and changes Si/SiO2The property of substrate surface, to which effectively control organic molecule is pressed
According to face-on mode ordered arrangements, influence of the research molecule face-on ordered arrangements to device performance.
Background technology
The problems such as there are high cost, environmental pollutions relative to traditional silicon-based film transistor (Si-TFT), polycrystalline organic thin film
Body pipe (OTFT) have many advantages, such as low cost, easy processing, can large area manufacture, it is aobvious to can be applied to liquid crystal display, organic light emission
Show, organic photovoltaic, Radio Frequency Identification Technology and sensor etc., by academia, industrial quarters in-depth study.
In OTFT devices, several organic material molecular layers in inorganic matter substrate interface are conductive channels, organic
The arrangement mode of molecule directly determine carrier transport ability, carrier density, electrode surface work content (M.P.Nikiforov,
U.Zerweck, P.Milde, C.Loppacher, T.H.Park, H.T.Uyeda, M.J.Therien, L.Eng, and
D.Bonnell, Nano Lett. 2008,8,110.), to determine the quality of device performance, therefore prepare ordered arrangement, nothing
Defect, big crystal grain organic material be just to seem extremely important.Organic molecule has face-on, and (i.e. planes of molecules is parallel to substrate
Plane) and two kinds of arrangement modes of edge-on (i.e. there are one inclination angles with substrate plane for planes of molecules), study face-on and edge-
On arrangement modes influence device performance extremely important.
In general, organic material is directly in Si/SiO2The film that surface is formed is arranged according to edge-on modes.Scientific research personnel
Attempt to obtain face-on arrangements by modifying interface.Fragrance of the terminal with halogen, alkyl organosilanes's
Self-assembled film promotes more pentacene molecules to take face-on arrangement modes, but pentacene is arranged with polycrystalline form
Row (K.P.Pernstich, S.Haas, D.Oberhoff, C.Goldmann, D.J.Gundlach, B.Batlogg,
A.N.Rashid, and G.Schitter, J. Appl.Phys.2004,96,6431.).Draw the positions meso on porphyrin ring
Enter long alkyl chain (n-C18H37), carboxyl, pyridine groups (J.Otsuki, E.Nagamine, T.Kondo, K.Iwasaki,
M.Asakawa, and K.Miyake, J.Am.Chem. Soc.2005,127,10400.) so that porphyrin monofilm can be according to
Face-on modes arrange.Equally, the single layer membrane molecule formed on the smooth graphite electrode of atom level (0001) be face-on (i.e.
Planes of molecules is parallel to substrate plane) mode arranges；But continue the organic material of deposition, the row of changing on monofilm
Row mode, mainly arranged in a manner of edge-on (F. Bussolotti, S.W.Han, Y.Honda, and R.Friedlein,
Phys.Rew.B 2009,79,245410.), it is clear that the intermolecular strong π-π interactions of organic material change the side of its arrangement
Formula.
And up to now, prepare bulky grain, organic material molecule yet there are no report according to the OTFT that face-on modes arrange
Road.Inorganic matter substrate has the crystal structure different from organic material, lattice constant or lattice symmetry inconsistent, it is desirable to control
Organic material ordered arrangement, it is necessary first to reduce the influence of inorganic matter substrate different crystalline lattice structure.This project utilizes self assembly, change
The methods of student's length, the porphyrin monolayers that planes of molecules is parallel to substrate surface using strong chemical bond are fixed on Si/
SiO2On substrate；Then it is interacted to the strong π-π for being deposited on organic molecule above using the planar structure of its height conjugation
Power, control organic molecule are arranged according to face-on modes.
Invention content
The invention is characterized in that a kind of method that the method by chemical bonding prepares the double-deck self-assembled film is provided, in Si/
SiO2Stable porphyrin (formula 2) monolayer is prepared on inorganic matter substrate, macrocyclic structure is parallel to substrate surface.
According to an aspect of the present invention, a kind of method being used to form the double-deck self-assembled film is provided, step includes：
1, the synthesis of maleimide organosilane (formula 1), two class compounds of porphyrin (formula 2)
Formula 1：
Formula 2：
2, planes of molecules is parallel to Si/SiO2The preparation of the porphyrin monolayers on surface
(a) to Si/SiO2Substrate is cleaned and is activated, to be formed on its surface hydroxyl group；
(b) in Si/SiO2The self-assembled film of maleimide organosilane is formed on substrate；
(c) it is connected on the self-assembled film of maleimide organosilane using the method that surface chemistry is grown
Porphyrin monolayers make porphyrin macrocyclic structures be parallel to substrate surface, and monolayer is stablized.
Description of the drawings
Clearer it will understand above and other feature and advantage of the invention in conjunction with following attached drawing and detailed description,
In：
Fig. 1 self assembly flow diagrams；
Fig. 2 bare silicon wafer water contact angle test schematic diagrams；
Fig. 3 maleimide organosilane (formula 1) Self_assembled monolayers water contact angle test schematic diagram；
Fig. 4 porphyrin (formula 2) Self_assembled monolayers water contact angle test schematic diagram；
The XPS schematic diagrames of Fig. 5 N 1s；
The XPS schematic diagrames of Fig. 6 S 2P；
Fig. 7 maleimide organosilane hydrogen nuclear magnetic resonance spectrograms；
Fig. 8 maleimide organosilane carbon-13 nmr spectra figures；
Fig. 9 4- (3- bromines propoxyl group) benzaldehyde hydrogen nuclear magnetic resonance spectrogram；
Figure 10 4- (3- (ethanethioyl) propoxyl group) benzaldehyde hydrogen nuclear magnetic resonance spectrogram；
Figure 11 5,10,15,20- tetra- (4- (3- ethanethioyls propoxyl group) phenyl) porphyrin hydrogen nuclear magnetic resonance spectrogram；
Figure 12 5,10,15,20- tetra- (4- (3- ethanethioyls propoxyl group) phenyl) porphyrin carbon-13 nmr spectra figure；
Figure 13 5,10,15,20- tetra- (4- (3- ethanethioyls propoxyl group) phenyl) Cob altporphyrin hydrogen nuclear magnetic resonance spectrogram；
Figure 14 5,10,15,20- tetra- (4- (3- ethanethioyls propoxyl group) phenyl) nickel-porphyrin hydrogen nuclear magnetic resonance spectrogram；
Figure 15 5,10,15,20- tetra- (4- (3- ethanethioyls propoxyl group) phenyl) copper porphyrin hydrogen nuclear magnetic resonance spectrogram；
Figure 16 5,10,15,20- tetra- (4- (3- ethanethioyls propoxyl group) phenyl) zinc protoporphyrin hydrogen nuclear magnetic resonance spectrogram；
Figure 17 5,10,15,20- tetra- (4- (3- ethanethioyls propoxyl group) phenyl) ferriporphyrin hydrogen nuclear magnetic resonance spectrogram；
Figure 18 5,10,15,20- tetra- (4- (3- mercaptopropyloxies) phenyl) nickel-porphyrin hydrogen nuclear magnetic resonance spectrogram.
The detailed description of preferred embodiment
The preferred embodiment of the present invention is described in detail below so that advantages and features of the invention can be easier to by
Those skilled in the art understand that.
Example 1：
(1) synthesis of self-assembled material maleimide organosilane.
The dichloromethane of the drying of 200ml and the maleic two of 1.73g (17.6mmol) are added in the flask of 500ml
Acid anhydrides, nitrogen protection, stirring.The 3-aminopropyltriethoxysilane of 3.90g (17.6mmol) is dissolved in 20ml dryings
In dichloromethane, it is added in flask, 1h is stirred at room temperature.Revolving removes solvent, obtains white powder intermediate product, dry, claims
Weight.
The toluene of the drying of 200ml and above-mentioned gained white intermediate product, N are added in the flask of 250ml2Protection.
Take 2.40g (17.6mmol) ZnCl2, it is added in reaction system immediately, is warming up to 80 DEG C.Finally by 2.84g (17.6mmol)
Hexa methyl di silicon imide be dissolved in the toluene of 20ml, be added dropwise in reaction system, react 5h.It is cooled to room temperature, mistake
Filter out ZnCl2, rotate and remove solvent, obtain colourless oil liquid, yield 50%.1H NMR(400MHz；CDCl3)：δ6.66
(2H, s), 3.77 (6H, m), 3.48 (2H, t), 1.65 (2H, m), 1.19 (9H, t), 0.56 (2H, t)13C NMR(400
MHz)：δ 170.94,134.12,58.54,40.51,22.22,18.35,7.85.
(2) synthesis of self-assembled material porphyrin (formula 2).
The preparation of 4- (3- bromines propoxyl group) benzaldehyde：
By 2.46g (12.2mmol) 1,3- dibromopropanes, 0.5g (4.1mmol) parahydroxyben-zaldehyde, 0.428g
(6.1mmol) K2CO3It is added in the flask equipped with 30ml acetone, N2Protection.1h is stirred at 80 DEG C, after reaction, is stopped
Heating, 0 DEG C is cooled to by system.Revolving removes solvent, and a small amount of distilled water is added, and three times with chloroform extraction, merges organic phase,
Appropriate anhydrous MgSO is added4It is dry, after standing half an hour, it is filtered to remove MgSO4, revolving removing chloroform, chromatographic column separating-purifying
(ethyl acetate: petroleum ether=1: 4), obtain colourless oil liquid, yield 51%.1H NMR(400MHz；CDCl3)：δ9.89
(1H, s), 7.83 (2H, d), 7.00 (2H, d), 4.20 (2H, t), 3.61 (2H, t), 2.36 (2H, m)
The preparation of 4- (3- (ethanethioyl) propoxyl group) benzaldehyde：
0.729g (3mmol) 4- (3- bromines propoxyl group) benzaldehyde is added in the flask equipped with 30ml DMF, N2It protects and cold
But to 0 DEG C.0.342g (3mmol) KSAc is dissolved in 5ml DMF, and reaction system is added dropwise in 30min, and room temperature stirs 3 h.Reaction knot
Shu Hou, revolving remove DMF, a small amount of water are added, and are extracted 3 times with chloroform, a small amount of water dissolution is added in remaining residue in reaction bulb
It is extracted 3 times with chloroform afterwards, merges organic phase, appropriate anhydrous MgSO is added4, stand half an hour.It is filtered to remove MgSO4, revolving removing
Chloroform, chromatographic column separating-purifying (ethyl acetate: petroleum ether=1: 4), obtain white solid, yield 93%.1H NMR
(400MHz；CDCl3)：δ 9.91 (1H, s), 7.84 (2H, d), 7.00 (2H, d), 4.12 (2H, t), 3.09 (2H, t), 2.37
(3H, s), 2.13 (2H, m)
The preparation of 5,10,15,20- tetra- (4- (3- ethanethioyls propoxyl group) phenyl) porphyrins：
Pyrroles 0.067g (1mmol) and 0.238g (1mmol) 4- (3- (ethanethioyl) propoxyl group) benzaldehyde will newly be steamed
It is dissolved in and 30ml CH is housed2Cl2Flask in, N2Protection.0.114g (1mmol) trifluoroacetic acid is dissolved in 2ml CH2Cl2In, slowly add
Enter reaction system, 0.170g (0.75mmol) tetrachloroquinone (TCQ) is added after 1.5h is stirred in dark, flow back 1 h, reaction knot
Beam.Stopping heating, after system is cooled to room temperature, appropriate triethylamine is added, is filtered after standing half an hour, revolving removes solvent,
Chromatographic column separating-purifying obtains violet solid, yield 30%.1H NMR(400MHz；CDCl3)：δ 8.87 (8H, s), 8.13
(8H, d), 7.26 (8H, d), 4.30 (8H, t), 3.24 (8H, t), 2.43 (12H, s), 2.27 (8H, m)13C NMR(400
MHz)：δ 195.86,158.60,135.61,134.77,119.72,112.72,77.33,77.01,76.70,66.49,
30.74,29.53,26.08.
The preparation of 5,10,15,20- tetra- (4- (3- ethanethioyls propoxyl group) phenyl) Cob altporphyrins：
30mg (0.026mmol) porphyrin is dissolved in 30ml chloroforms, N2Protection, is heated to reflux, by 129.52mg (0.52
mmol)Co(OAc)2·4H2Reflux system is added in O, is heated to reflux 5h, reaction terminates.System is cooled to room temperature, and revolving removes dechlorination
It is imitative, CH is added2Cl2It is dissolved, with 10% NaHCO3Solution washs, then is washed with distilled water 2 times, anhydrous MgSO4It is dry,
Filtering, revolving remove solvent, chromatograph post separation, obtain red solid, yield 88%.1H NMR(400MHz； CDCl3)：δ9.44
(8H, br), 5.55 (8H, br), 4.03 (8H, br), 3.13 (8H, br), 2.78 (12H, br)
The preparation of 5,10,15,20- tetra- (4- (3- ethanethioyls propoxyl group) phenyl) nickel-porphyrins：
30mg (0.026mmol) porphyrin is dissolved in 30ml DMF, N2Protection, is heated to reflux, by 64.0mg (0.26
mmol)Ni(OAc)2·4H2Reflux system is added in O, is heated to reflux 5h, reaction terminates.System is cooled to room temperature, and revolving removes
CH is added in DMF2Cl2It is dissolved, with 10% NaHCO3Solution washs, then is washed with distilled water 2 times, anhydrous MgSO4It is dry,
Filtering, revolving remove solvent, chromatograph post separation, obtain red solid, yield 89%.1H NMR(400 MHz；CDCl3)：δ8.78
(8H, s), 7.91 (8H, d), 7.19 (8H, d), 4.24 (8H, t), 3.20 (8H, t), 2.41 (12H, s), 2.22 (8H, m)
The preparation of 5,10,15,20- tetra- (4- (3- ethanethioyls propoxyl group) phenyl) copper porphyrins：
30mg (0.026mmol) porphyrin is dissolved in 30ml chloroforms, N2Protection, is heated to reflux, by 52mg (0.26mmol)
Cu(OAc)2·H2Reflux system is added in O, is heated to reflux 5h, reaction terminates.System is cooled to room temperature, and revolving removes chloroform, is added
CH2Cl2It is dissolved, with 10% NaHCO3Solution washs, then is washed with distilled water 2 times, anhydrous MgSO4It is dry, it filters, rotation
Solvent is evaporated off, chromatographs post separation, obtains red solid, yield 85%.1H NMR(400MHz；CDCl3)：δ 7.07 (8H, br),
4.20 (8H, br), 3.17 (8H, br), 2.38 (12H, br), 2.19 (8H, br)
The preparation of 5,10,15,20- tetra- (4- (3- ethanethioyls propoxyl group) phenyl) zinc protoporphyrins：
30mg (0.026mmol) porphyrin is dissolved in 30ml chloroforms, N2Protection, is heated to reflux, by 113.9mg (0.52
mmol)Zn(OAc)2·2H2Reflux system is added in O, is heated to reflux 5h, reaction terminates.System is cooled to room temperature, and revolving removes dechlorination
It is imitative, CH is added2Cl2It is dissolved, with 10% NaHCO3Solution washs, then is washed with distilled water 2 times, anhydrous MgSO4It is dry,
Filtering, revolving remove solvent, chromatograph post separation, obtain violet solid, yield 98%.1H NMR (400MHz；CDCl3)：δ8.97
(8H, s), 8.12 (8H, d), 7.25 (8H, d), 4.30 (8H, t), 3.20 (8H, t), 2.37 (12H, s), 2.24 (8H, m)
The preparation of 5,10,15,20- tetra- (4- (3- ethanethioyls propoxyl group) phenyl) ferriporphyrins：
30mg (0.026mmol) porphyrin is dissolved in 30ml chloroforms, N2Protection, is heated to reflux, by 51.69mg (0.26
mmol)FeCl2·4H2Reflux system is added in O, is heated to reflux 5h, reaction terminates.System is cooled to room temperature, and revolving removes chloroform,
CH is added2Cl2It is dissolved, with 10% NaHCO3Solution washs, then is washed with distilled water 2 times, anhydrous MgSO4It is dry, mistake
Filter, revolving remove solvent, chromatograph post separation, obtain black solid, yield 70%.1H NMR(400MHz； CDCl3)：δ8.97
(8H, s), 8.12 (8H, d), 7.25 (8H, d), 4.30 (8H, t), 3.20 (8H, t), 2.37 (12H, s), 2.24 (8H, m)
The preparation of 5,10,15,20- tetra- (4- (3- mercaptopropyloxies) phenyl) nickel-porphyrins：
It weighs 120mg Ni- porphyrins to be placed in the flask of the methanol equipped with 60ml chloroforms and 18ml, N2Protection.It weighs
182mg 20%CH3NaS aqueous solutions are added in the methanol of 0.5ml in above-mentioned solution, and about 1.5h is stirred at room temperature, passes through TLC
(ethyl acetate: CH2Cl2=1: 50) being monitored reaction process, solvent is evaporated after the reaction was complete, water and chloroform is added to be extracted
It takes three times, organic phase adjusts PH=6 with dilute HCl, then with chloroform recovery organic solution, adds anhydrous MgSO4It is dry, it filters, revolving
Solvent is removed, post separation (ethyl acetate: CH is chromatographed2Cl2=1: 50), obtaining red solid, yield 30%.1H NMR
(400MHz；CDCl3)：δ 8.78 (8H, s), 7.91 (8H, d), 7.19 (8H, d), 4.24 (8H, t), 3.20 (8H, t), 2.41
(12H, s), 2.22 (8H, m)
(3) preparation of self-assembled film
Step 1：The silicon chip that size is 1 × 1cm with acetone, ethyl alcohol, ultra-pure water sonic oscillation 10min and is used into N successively2It blows
It is dry；
Step 2：By clean Si/SiO2Substrate UV-O330min is irradiated, to be formed on its surface hydroxyl group；
Step 3：Silicon chip after activation is immersed in toluene (drying) solution of the maleimide organosilane of 10ml
In (10-3M), N2Protection, is heated to 75 DEG C, self assembly 36h, in Si/SiO2One layer of maleimide of self assembly on substrate
The self-assembled film of organosilane；
Step 4：Using reacting for maleimide and thiol, silicon chip is immersed in the THF solution of the porphyrin of 2ml
(5×10-4M), N2Protection, is heated to 55 DEG C, self assembly 30h, will be with there are four the compound porphyrin of sulfydryl (- SH)
It is connected to Si/SiO2On the surfaces /maleimide organosilane so that porphyrin is big, and plane of a loop is parallel to electrode surface.
(4) characterization of material
(a) x-ray photoelectron spectroscopy (XPS)
Fig. 5 is the XPS schematic diagrames of N 1s, and it is in maleimide organosilane that combination, which can be the peak of 397ev, in figure
The characteristic peak position of contained N element is set, this shows maleimide organosilane in Si/SiO2Surface self-organization success.
Fig. 6 is in Si/SiO2Porphyrin monolayer S 2p XPS spectrums on substrate.By comparing different self assemblies
The chemical environment of S 2p illustrates the bonding state of sulfydryl and substrate in film, further characterizes the self-assembled film of different sulfydryl porphyrins.
The combination of the S 2p elements of S-H under non-bond styles can should be 163-164eV, and be in the S of key and the S-C under state
The combination of 2p elements can should be 162eV.The combination of the XPS characteristic peaks of S 2p elements can be about 162eV in Fig. 6, this shows S-C
The formation of key, i.e. porphyrin are successfully connected to Si/SiO2On the surfaces /maleimide organosilane.It is another in Fig. 6
It is the oxidation peak of S 2p that one combination, which can be the characteristic peak of 168eV, this shows the sulfydryl (- SH) in porphyrin in self assembly
There is part to be aoxidized in the process.
(b) water contact angle
By contact angle determination, system characterizes SiO caused by surface modification2The variation of surface wettability.Fig. 2 is
SiO2The contact angle on surface is 49.77 °, and Fig. 3 is that the surface contact angle of maleimide organosilane self-assembled films is
67.97 °, the surface contact angle of Fig. 45,10,15,20- tetra- (4- (3- mercaptopropyloxies) phenyl) nickel-porphyrin self-assembled film is
88.90 °, maleimide organosilane self-assembled films top group Malaysia acid imide contains hydrophilic radical-carbonyl,
And the porphyrin monolayers being bonded do not have hydrophilic radical, so water contact angle increases, this also turns out maleimide
Organosilane self-assembled films are successfully prepared with porphyrin monomolecular films.
Claims (4)
1. a kind of prepare for modifying organic thin film transistor substrate Si/SiO2Surface and the porphyrin that is arranged in a manner of face-on point
The method of sublayer, it is characterised in that in Si/SiO2One layer of 3- dimaleoyl imino propyl-triethoxysilicane of surface self-organization point
Son recycles four functional groups of Porphyrin Molecule end to occur with the double bond in 3- dimaleoyl imino propyl-triethoxysilicanes
Chemical bonding forms one layer of Porphyrin Molecule, and macrocyclic structure is parallel to substrate surface, is arranged in a manner of face-on.
It a kind of is prepared for modifying organic thin film transistor substrate Si/SiO 2. according to claim 12Surface and with
The method for the Porphyrin Molecule layer that face-on modes arrange, it is characterised in that the metal ion that complex compound is formed with porphyrin is Zn2+,
Fe2+, Cu2+, Ni2+, Co2+In any one.
It a kind of is prepared for modifying organic thin film transistor substrate Si/SiO 3. according to claim 12Surface and with
The method for the Porphyrin Molecule layer that face-on modes arrange, it is characterised in that the functional group of Porphyrin Molecule side chain terminal be amino (-
NH2), any one in sulfydryl (- SH).
It a kind of is prepared for modifying organic thin film transistor substrate Si/SiO 4. according to claim 12Surface and with
The method for the Porphyrin Molecule layer that face-on modes arrange, it is characterised in that the number of Porphyrin Molecule side chain carbon is in 3-11
Any one.
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| Surface-Promoted Thioether Linkage between Proto- or Hemato porphyrins and Thiol-Silanized Quartz: Formation of Self-Assembled Monolayers and Interaction with Imidazole and Carbon Monoxide;Denis L. Pilloud, et al.;《Langmuir》;19980723;第14卷;page 4809-4818 * |
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