CN103788101A - Cross-linked metalloporphyrin nanocrystal and preparation method thereof, and manufacturing method for optical detector - Google Patents

Cross-linked metalloporphyrin nanocrystal and preparation method thereof, and manufacturing method for optical detector Download PDF

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CN103788101A
CN103788101A CN201210427590.7A CN201210427590A CN103788101A CN 103788101 A CN103788101 A CN 103788101A CN 201210427590 A CN201210427590 A CN 201210427590A CN 103788101 A CN103788101 A CN 103788101A
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metalloporphyrin
nanocrystalline
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CN103788101B (en
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潘革波
王凤霞
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Suzhou Institute of Nano Tech and Nano Bionics of CAS
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Suzhou Institute of Nano Tech and Nano Bionics of CAS
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    • C07—ORGANIC CHEMISTRY
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    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/22—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains four or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/54—Organic compounds
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B7/00—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions
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    • G01J—MEASUREMENT OF INTENSITY, VELOCITY, SPECTRAL CONTENT, POLARISATION, PHASE OR PULSE CHARACTERISTICS OF INFRARED, VISIBLE OR ULTRAVIOLET LIGHT; COLORIMETRY; RADIATION PYROMETRY
    • G01J1/00—Photometry, e.g. photographic exposure meter
    • G01J1/48—Photometry, e.g. photographic exposure meter using chemical effects
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    • H10K85/30—Coordination compounds
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    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
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    • H10K85/341—Transition metal complexes, e.g. Ru(II)polypyridine complexes
    • H10K85/346—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising platinum
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    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
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Abstract

The invention relates to the technical field of preparation and application of nano-materials, especially to a cross-linked metalloporphyrin nanocrystal and a preparation method thereof and a manufacturing method for an optical detector. The cross-linked metalloporphyrin nanocrystal is of a one-dimensional netted or dendritic structure formed by mutual crosslinking of metalloporphyrin nanowires. A metalloporphyrin compound and an organic solvent are mixed to obtain a mixed solution, and annealing is carried out so as to obtain the cross-linked metalloporphyrin nanocrystal. The invention further provides the manufacturing method for the optical detector with the metalloporphyrin nanocrystal as an organic detection layer. The preparation method provided by the invention is easy to operate and has low energy consumption and a wide application scope; the prepared optical detector has the characteristics of preparation through solubilization, high flexibility and sensitivity, good stability, etc. and has wide application values.

Description

Crosslinked metalloporphyrin is nanocrystalline and preparation method thereof and the making method of photo-detector
Technical field
The present invention relates to nano material preparation and applied technical field, especially a kind of have the metalloporphyrin of crosslinking structure and an application in photodetection field thereof.
Background technology
Organic photo-detector has the advantages such as high sensitivity, low noise, repeatability due to it, cause that people note widely.From the material of detector optical detection layer, mainly comprise film-type and monocrystalline type.The photo-detector of based thin film type is easy to realize flexible, large-area preparation, but the optical detection layer of film-type is generally the structure of polycrystalline or amorphous, causes large dark state electric current, low resolving power.Comparatively speaking, organic single-crystal especially one dimension Nano structure monocrystalline has the advantages such as large specific surface area, few lattice imperfection, has therefore shown high resolving power take one dimension Nano structure as the detector of optical detection layer.But because the controllability of monocrystalline is poor, therefore the photo-detector repeatability take above-mentioned one dimension Nano structure as optical detection layer is poor, is difficult to realize large-area preparation.Therefore, how to realize simple to operate, degree of crystallinity is high, the preparation that specific surface area is large, be applicable to large-area optical detection layer, is to realize in organic photo-detector low cost, high sensitivity preparation process, needing a key issue solving.
Porphyrin compound, as the important component part of taking oxygen carrier and biological enzyme in photosynthetic center, life entity, has excellent effect at energy transfer party mask, shows excellent photoelectric characteristic simultaneously.Metal porphyrins has large conjugated molecule structure simultaneously, be easy to be self-assembled into by non covalent bond effect nanocrystalline and by the nanocrystalline film forming, but above-mentioned nanostructure preparation process complexity, degree of crystallinity is not high, specific surface area is less, so that be that the detector cost of optical detection layer is higher, dark current is larger, sensitivity is lower based on above-mentioned nanostructure, and be not suitable for the large-area production of industrialization.
Summary of the invention
For addressing the above problem, the invention provides a kind of crosslinked metalloporphyrin nanocrystalline and its preparation method and application.Be applied in the making of photo-detector as organic detecting layer nanocrystalline this crosslinked metalloporphyrin, there is feature highly sensitive, high stability, and making method be simple and convenient, applied widely.
This crosslinked metalloporphyrin nanocrystalline structure, metalloporphyrin nano wire is cross-linked with each other into the netted or branched structure of one dimension.
Wherein, described metalloporphyrin nanowire diameter is 10～2000nm; Length is 5～1000 μ m.
The present invention also provides this crosslinked metalloporphyrin nanocrystalline preparation method, and its step is that the mixing solutions of metal porphyrins and organic solvent formation is transferred on dash receiver, then carries out anneal; In described mixing solutions, the concentration of metal porphyrins is 0.05～10mg/mL.
Wherein, described anneal is to control 50～150 ℃ of temperature, keeps 10～60 minutes.
Wherein, described organic solvent comprises at least one in chloroform, chlorobenzene, dimethylbenzene, orthodichlorobenzene, 1-Methoxy-2-propyl acetate, glycol methyl ether acetate, octane.
Further, the central metal element of described metal porphyrins is zinc, cobalt, nickel, indium, copper, magnesium or platinum.
Further, described transfer method comprises spin coating, drips the one in film, immersion, roller coat, Electrospun, aerosol spray printing, ink jet printing, intaglio printing or silk screen printing.
The present invention also provides another kind of described crosslinked metalloporphyrin nanocrystalline making method, different from above-mentioned making method, and described metal porphyrins is used on porphyrin ring and replaces with substituent metal porphyrin derivative.
Wherein, described substituting group be ester group, hydroxyl or the alkyl that is no more than 4 carbon atoms at least one.
The present invention also provides this crosslinked metalloporphyrin the nanocrystalline purposes preparing in the organic photo-detector of bottom gate type.The making method of this bottom gate type photo-detector, comprise substrate, optical detection layer, grid and source, drain electrode, the making step of described optical detection layer is that metal porphyrins is fully dissolved in and in organic solvent, forms mixing solutions, described mixing solutions is transferred on dash receiver, and it is nanocrystalline that anneal forms crosslinked metalloporphyrin.
Wherein, in described mixing solutions, the concentration of metal porphyrins is 0.05～10mg/mL.
Wherein, described anneal is to control 50～150 ℃ of temperature, keeps 10～60 minutes.
Wherein, described organic solvent comprises at least one in chloroform, chlorobenzene, dimethylbenzene, orthodichlorobenzene, 1-Methoxy-2-propyl acetate, glycol methyl ether acetate, octane.
Further, the central metal element of described metal porphyrins is zinc, cobalt, nickel, indium, copper, magnesium or platinum.
Further, described transfer method comprises spin coating, drips the one in film, immersion, roller coat, Electrospun, aerosol spray printing, ink jet printing, intaglio printing or silk screen printing.
Further, described dash receiver is at least one in insulation layer or source, drain electrode.
Beneficial effect:
The preparation method of photo-detector provided by the present invention, utilizes the netted or branched structure of the crosslinked nanocrystalline one dimension having of metalloporphyrin, is prepared with organic detecting layer of good photoelectric characteristic.The making method of this organic detecting layer is easy to operate, with low cost, not high to environmental requirement.The photo-detector of preparing has can solubilisate preparation, flexibility, high sensitivity, low cost, be easy to big area the feature such as prepares, and therefore in the preparation of flexibility, big area, low cost, the organic photo-detector of high sensitivity, has important using value.
Accompanying drawing explanation
Fig. 1 is the crosslinked nanocrystalline optical microscopy map of zinc porphyrin of the embodiment of the present invention 1.
Fig. 2 is the photoelectric characteristic test pattern of the embodiment of the present invention 1 organic detecting layer.
Embodiment
With reference to the accompanying drawings, in conjunction with specific embodiments, the present invention is described in more detail.
The invention provides a kind of crosslinked metalloporphyrin nanocrystalline, as shown in Figure 1, every described metalloporphyrin is nanocrystalline is wire, and is cross-linked with each other into the netted or branched structure of one dimension.Above-mentioned crosslinking structure forms by metal porphyrins Intermolecular Forces.By selecting solvent of different nature and adjusting the concentration of metal porphyrins, can produce size difference, crosslinking degree difference, crosslinked metalloporphyrin that performance is different is nanocrystalline.
The invention provides the brilliant diameter of this crosslinked metalloporphyrin and derivates nanometer thereof is 10～2000nm; Length is 5～1000 μ m.This metalloporphyrin and derivates nanometer crystalline substance thereof can be applied in the making of organic optical detection layer.
The making method of this crosslinked metal porphyrins, is that metalloporphyrin or derivatives thereof and organic solvent are fully dissolved each other, and the mixing solutions of formation is transferred in substrate, then carries out anneal; In described mixing solutions, the concentration of metal porphyrins is 0.05～10mg/mL.Wherein, metalloporphyrin or derivatives thereof should fully be dissolved in organic solvent, like this this metalloporphyrin of guarantee or its derivative can dispersion in solution, forms nano wire and reticulated structure with Intermolecular Forces.
In conjunction with the making embodiment of photo-detector, introduce this crosslinked metalloporphyrin and derivates nanometer crystalline substance thereof the making method as organic detecting layer below.
Embodiment 1
The photo-detector of the present embodiment is bottom gate-top contact type, and its making method is as follows:
Step 1 prepares by the method for sputter the gate electrode that one deck 100nm is thick in substrate, and this gate electrode is made up of Si.Wherein, the making method of substrate is that PEI will be served as substrate, uses successively acetone, ethanol, pure water ultrasonic 40 minutes, then uses N 2air-blowing is dry, puts into 100 ° of C vacuum drying ovens and places 10 minutes, forms substrate.
Step 2, on gate electrode, utilizes the method for thermooxidizing to plate the SiO that one deck 300nm is thick 2as insulation layer.
Step 3, on insulation layer, the crosslinked metalloporphyrin of preparation is nanocrystalline, and wherein insulation layer is as dash receiver.
Step 4, substrate and crosslinked metalloporphyrin nanocrystalline on thermal evaporation for source electrode and the drain electrode of a layer thickness 100nm gold material.The width of source, drain electrode is 20 μ m, and length is 200 μ m, and the distance between two electrodes is 20 μ m.
Wherein, in step 3, adopt the crosslinked nanocrystalline making method as organic detecting layer of metalloporphyrin as follows:
Zinc porphyrin is mixed and is made into mixing solutions with chloroform, octane, and wherein porphyrin zinc concentration is 3mg/mL.Then by the method for dripping film, described mixing solutions is transferred on gate electrode and insulation layer, placed 40 minutes.Through 100 ° of C thermal anneal process 10 minutes, obtain by crosslinked nanocrystalline the formed organic detecting layer of zinc porphyrin of one dimension.
Adopt aforesaid method to obtain being cross-linked the nanocrystalline photo-detector as organic detecting layer of one dimension zinc porphyrin.
Above-mentioned organic photo-detector is carried out to photoelectric characteristic test, the results are shown in Fig. 2.In figure, can draw the susceptibility that the prepared organic photo-detector of the present embodiment has had, and repeated preferably.
Embodiment 2
The photo-detector of the present embodiment is bottom gate-top contact type, and its making method is as follows:
Step 1 prepares by the method for thermal evaporation the gate electrode that one deck 100nm is thick in substrate, and this gate electrode is made up of gold.Wherein, the preparation method of substrate as described in Example 1.
Step 2, on gate electrode, utilizes the method for revolving Tu to plate insulating film that one deck 500nm is thick if polyvinylpyrrolidone (PVP) is as insulation layer.
Step 3, on insulation layer, the crosslinked metalloporphyrin of preparation is nanocrystalline, and wherein insulation layer is as dash receiver.
Step 4, in substrate and the crosslinked metalloporphyrin of one dimension nanocrystalline on the method for thermal evaporation for one deck 100nm gold formation source electrode and drain electrode.Wherein, the parameter of source-drain electrode as described in Example 1.
Wherein, in step 3, adopt the crosslinked nanocrystalline making method as organic detecting layer of metalloporphyrin as follows:
8 methyl porphyrin cobalt is mixed and is made into mixing solutions with chlorobenzene, and wherein the concentration of 8 methyl porphyrin cobalt is 10mg/mL.Then by the method for spin coating, described mixing solutions is transferred on gate electrode and insulation layer, placed 40 minutes.Through 130 ° of C thermal anneal process 20 minutes.Organic detecting layer that the crosslinked 8 methyl porphyrin cobalt nanocrystal of one dimension that the present embodiment obtains forms, the structure nanocrystalline to the zinc porphyrin of embodiment 1 is similar with performance.
Embodiment 3
The photo-detector of the present embodiment is bottom gate-end contact-type, and its making method is as follows:
Step 1 prepares by the method for thermal evaporation the gate electrode that one deck 200nm is thick in substrate, and this gate electrode is made up of silver.Wherein, the preparation method of substrate as described in Example 1.
Step 2, on gate electrode, utilizes the method for atomic shell to plate the thick aluminum oxide of one deck 100nm as insulation layer.
Step 3 utilizes the method for thermal evaporation to prepare silver that one deck 100nm is thick as source, drain electrode on substrate, gate electrode and insulation layer.Wherein, the parameter of source-drain electrode as described in Example 1.
Step 4, using insulation layer and source, drain electrode is as receiver sheet, utilizes the method for aerosol spray printing to prepare the crosslinked metalloporphyrin of one dimension nanocrystalline.
Wherein, in step 4, adopt the crosslinked nanocrystalline making method as organic detecting layer of metalloporphyrin as follows:
Eight hydroxyl Porphyrin Nickels are mixed and are made into mixing solutions with chlorobenzene and 1-Methoxy-2-propyl acetate, and wherein the concentration of eight hydroxyl Porphyrin Nickels is 3mg/mL.Then the method by aerosol spray printing is transferred to described mixing solutions on substrate and source, drain electrode, places 30 minutes.Through 50 ° of C thermal anneal process 60 minutes.Crosslinked nanocrystalline the formed organic detecting layer of eight hydroxyl Porphyrin Nickels of one dimension that the present embodiment obtains, the structure nanocrystalline to the zinc porphyrin of embodiment 1 is similar with performance.
Embodiment 4
The photo-detector of the present embodiment is bottom gate-end contact-type, and its making method is as follows:
Step 1 prepares by the method for magnetron sputtering the gate electrode that one deck 80nm is thick in substrate, and this gate electrode is made up of Ta.Wherein, the preparation method of substrate as described in Example 1.The condition of magnetron sputtering is: base vacuum 2 × 10 -3pa; Passing into Ar gas makes the vacuum of sputter reach 1Pa; Sputtering power 500W; 100 ° of C of underlayer temperature.
Step 2, on substrate and gate electrode, utilizes the method for magnetically controlled DC sputtering to plate one deck TiO 2as insulation layer.The condition of reactive sputtering is: base vacuum is 2 × 10 -3pa; Pass into O 2gas makes sputter vacuum reach 1Pa; Sputtering power 500W; 100 ° of C of underlayer temperature.
Step 3, on substrate, gate electrode and insulation layer, on utilize the method for thermal evaporation to prepare gold that one deck 60nm is thick as source, drain electrode.Wherein the parameter of source, drain electrode is referring to shown in embodiment 1.
Step 4, using insulation layer and source, drain electrode is as receiver sheet, utilizes the method for ink jet printing to prepare the crosslinked metalloporphyrin of one dimension nanocrystalline.
Wherein, in step 4, the nanocrystalline making method of the crosslinked metalloporphyrin of one dimension is as follows:
Octaethylporphyrin platinum and toluene, chloroform, octane are mixed into mixing solutions, and wherein the concentration of octaethylporphyrin platinum is 0.05mg/mL.Adding on the one hand of octane can dissolution of metals porphyrin platinum, can regulate again the volatility of solvent simultaneously, and consumption generally accounts for the 1/5-1/2 of total solvent.Method by ink jet printing shifts above-mentioned mixing solutions on source electrode and drain electrode, places 20 minutes.Then through 150 ℃ of thermal anneal process 10 minutes.Organic detecting layer that the crosslinked octaethylporphyrin Pt nanocrystal of one dimension that the present embodiment obtains forms, the structure nanocrystalline to the zinc porphyrin of embodiment 1 is similar with performance.
Wherein, material and the preparation method of gate electrode, source electrode and drain electrode comprise above embodiment, but are not limited to above embodiment.
Wherein the nanocrystalline dash receiver method of transferring to of the crosslinked metalloporphyrin of one dimension not only can realize reality according to methods such as the spin coating of use respectively in embodiment 1 to 4, droplet film, aerosol spray printing and ink jet printings, also can realize by the method for immersion, intaglio printing, silk screen printing, roller coat and Electrospun, and anneal can be also the anneal in atmosphere of inert gases.Metal porphyrins can also be the compound of the Porphyrin and its derivative of indium, copper, magnesium or other metals in addition to the implementation.Organic solvent used is also not limited to described in the present embodiment, and those skilled in the art should know, and can be conducive to dissolve dispersed metal porphyrin chemical combination, and the organic solvent of the volatilization that is easy to be heated is all applicable.The concentration of controlling metal porphyrins in described mixing solutions is 0.05～10mg/mL, and described anneal is to control 50～150 ℃ of temperature, keeps 10～60 minutes, all can reach similar implementation result.In addition, metal porphyrins can also adopt with substituting group metal porphyrin derivative replace, substituting group, except above-described embodiment relates to, can also be ester group, hydroxyl, short-chain alkyl etc.
Organic photo-detector that the present invention is prepared, to be that the metalloporphyrin that is cross-linked by one dimension is nanocrystalline form its organic detecting layer.Based on transistorized device architecture, the diode structure that gate electrode voltage is zero also can adopt the inventive method to make, within should being included in the present invention.The preparation method of organic photo-detector provided by the present invention has can solubilisate preparation, flexibility, high sensitivity, low cost, be easy to big area the feature such as prepares, and therefore in the preparation of flexibility, big area, low cost, the organic photo-detector of high sensitivity, has important using value.

Claims (16)

1. a crosslinked metalloporphyrin nanocrystalline structure, is characterized in that, metalloporphyrin nano wire is cross-linked with each other into the netted or branched structure of one dimension.
2. crosslinked metalloporphyrin is nanocrystalline according to claim 1, it is characterized in that, described metalloporphyrin nanowire diameter is 10 ~ 2000nm; Length is 5 ~ 1000 μ m.
3. the crosslinked nanocrystalline making method of metalloporphyrin as claimed in claim 1 or 2, is characterized in that, comprises the steps: metal porphyrins to be fully dissolved in and in organic solvent, to form mixing solutions; Described mixing solutions is transferred on dash receiver, then carried out anneal; In described mixing solutions, the concentration of metal porphyrins is 0.05 ~ 10mg/mL.
4. be cross-linked according to claim 3 the nanocrystalline making method of metalloporphyrin, it is characterized in that, described anneal is to control 50 ~ 150 ℃ of temperature, keeps 10 ~ 60 minutes.
5. be cross-linked according to claim 3 the nanocrystalline making method of metalloporphyrin, it is characterized in that, described organic solvent comprises at least one in chloroform, chlorobenzene, dimethylbenzene, orthodichlorobenzene, 1-Methoxy-2-propyl acetate, glycol methyl ether acetate, octane.
6. be cross-linked according to claim 3 the nanocrystalline making method of metalloporphyrin, it is characterized in that, the central metal element of described metal porphyrins is zinc, cobalt, nickel, indium, copper, magnesium or platinum.
7. be cross-linked according to claim 3 the nanocrystalline making method of metalloporphyrin, it is characterized in that, described transfer method comprises spin coating, drips the one in film, immersion, roller coat, Electrospun, aerosol spray printing, ink jet printing, intaglio printing or silk screen printing.
8. the crosslinked nanocrystalline making method of metalloporphyrin as described in claim 3-7 any one, is characterized in that, described metal porphyrins is used on porphyrin ring and replaces with substituent metal porphyrin derivative.
9. the nanocrystalline making method of described crosslinked metalloporphyrin according to claim 8, is characterized in that, described substituting group be ester group, hydroxyl or the alkyl that is no more than 4 carbon atoms at least one.
10. the making method of a bottom gate type photo-detector, comprise substrate, optical detection layer, grid and source, drain electrode, it is characterized in that, the making step of described optical detection layer is that metal porphyrins is fully dissolved in and in organic solvent, forms mixing solutions, described mixing solutions is transferred on dash receiver, and it is nanocrystalline that anneal forms crosslinked metalloporphyrin.
11. making methods of photo-detector according to claim 10, is characterized in that, in described mixing solutions, the concentration of metal porphyrins is 0.05 ~ 10mg/mL.
12. making methods of photo-detector according to claim 10, is characterized in that, described anneal is to control 50 ~ 150 ℃ of temperature, keeps 10 ~ 60 minutes.
13. making methods of photo-detector according to claim 10, is characterized in that, described organic solvent comprises at least one in chloroform, chlorobenzene, dimethylbenzene, orthodichlorobenzene, 1-Methoxy-2-propyl acetate, glycol methyl ether acetate, octane.
14. making methods of photo-detector according to claim 10, is characterized in that, the central metal element of described metal porphyrins is zinc, cobalt, nickel, indium, copper, magnesium or platinum.
15. making methods of photo-detector according to claim 10, is characterized in that, described transfer method comprises spin coating, drips the one in film, immersion, roller coat, Electrospun, aerosol spray printing, ink jet printing, intaglio printing or silk screen printing.
16. making methods of photo-detector according to claim 10, is characterized in that, described dash receiver is at least one in insulation layer or source, drain electrode.
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