CN105624820A - Polystyrene/porphyrin derivative composite nano-fiber, method for preparing same and application of polystyrene/porphyrin derivative composite nano-fiber - Google Patents

Polystyrene/porphyrin derivative composite nano-fiber, method for preparing same and application of polystyrene/porphyrin derivative composite nano-fiber Download PDF

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CN105624820A
CN105624820A CN201610066234.5A CN201610066234A CN105624820A CN 105624820 A CN105624820 A CN 105624820A CN 201610066234 A CN201610066234 A CN 201610066234A CN 105624820 A CN105624820 A CN 105624820A
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polystyrene
composite nano
porphyrin
derivatives
fiber
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CN105624820B (en
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石乃恩
刘栋
仪明东
薛伟
解令海
黄维
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Nanjing Post and Telecommunication University
Nanjing University of Posts and Telecommunications
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Nanjing Post and Telecommunication University
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    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/44Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00General methods for the manufacture of artificial filaments or the like
    • D01F1/02Addition of substances to the spinning solution or to the melt
    • D01F1/10Other agents for modifying properties
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K10/00Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having potential barriers
    • H10K10/40Organic transistors
    • H10K10/46Field-effect transistors, e.g. organic thin-film transistors [OTFT]
    • H10K10/462Insulated gate field-effect transistors [IGFETs]
    • H10K10/466Lateral bottom-gate IGFETs comprising only a single gate
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10Organic polymers or oligomers
    • H10K85/111Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Textile Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Semiconductor Memories (AREA)
  • Artificial Filaments (AREA)

Abstract

The invention provides a polystyrene/porphyrin derivative composite nano-fiber, a method for preparing the same and application of the polystyrene/porphyrin derivative composite nano-fiber. The polystyrene/porphyrin derivative composite nano-fiber is made of polystyrene and porphyrin derivatives. A structural formula of the porphyrin derivatives is shown, wherein an R<1> represents one of pyridyl and phenyl, an R<2> represents one of unsaturated bonds and aromatic functional groups, and the R<1> and the R<2> are identical to each other or are different from each other. The method includes preparing the polystyrene/porphyrin derivative composite nano-fiber by the aid of electrostatic spinning processes. The polystyrene/porphyrin derivative composite nano-fiber can be used as a charge storage layer to be applied to a transistor storage. The polystyrene/porphyrin derivative composite nano-fiber, the method and the application have the advantages that the polystyrene/porphyrin derivative composite nano-fiber which is used as the charge trapping layer for the transistor storage is high in specific surface area, accordingly, storage windows of the storage can be improved, and the polystyrene/porphyrin derivative composite nano-fiber is favorable for effectively transmitting carriers among various functional layers of devices.

Description

Polystyrene/derivatives of porphyrin composite nano fiber and its preparation method and application
Technical field
The invention belongs to fiber device arts, be specifically related to a kind of polystyrene/derivatives of porphyrin composite nano fiber and its preparation method and application.
Background technology
Nanofiber refers to that diameter is Nano grade and the one-dimensional material with certain draw ratio, it not only has skin effect, small-size effect that usual nano material has etc., also there is the mechanical property of excellence, electronics and photon transmission characteristic and photoconductive property etc. so that it is in photoelectric device and sensor etc., demonstrate important using value. The method preparing nanofiber being currently known has pulling method, template synthesis method, phase separation method, self-assembly method etc., if but considering the requirements such as process controllability, equipment complexity, the scope of application, cost, productivity and fibre dimensions controllability, above method all has respective limitation. Electrostatic spinning technique is simple to operate with it, applied widely, production efficiency advantages of higher and more researcher favor.
Simultaneously, zero dimension material generally selected by existing transistorized memory, such as metal nanoparticle, polyfluorene nano-particle, fullerene etc., or two-dimensional material, such as Graphene and redox products, molybdenum bisuphide etc., storing material as carrier, but these materials are integrated into transistorized memory and there is many defects, as complicated in preparation process, cost is high, the requirement of equipment and environment is harsh etc.
Summary of the invention
Solving the technical problem that: it is an object of the invention to overcome the deficiencies in the prior art to provide a kind of polystyrene/derivatives of porphyrin composite nano fiber and its preparation method and application, this composite fibre makes the electric charge capture layer of transistorized memory can improve the memory window of memorizer.
Technical scheme:
Polystyrene/derivatives of porphyrin composite nano fiber, raw material includes polystyrene and derivatives of porphyrin, and the structural formula of described derivatives of porphyrin is:
Wherein, R1For the one of pyridine radicals or phenyl, R2For the one in unsaturated bond or aromatic functional group, R1��R2Identical or different.
Further, the diameter of described polystyrene/derivatives of porphyrin composite nano fiber is 50��800nm.
Further, the weight ratio of polystyrene and derivatives of porphyrin is 100:0.5��5.
The preparation method of described polystyrene/derivatives of porphyrin composite nano fiber, it is first derivatives of porphyrin is dissolved in DMF, adds polystyrene, heated and stirred is completely dissolved to polystyrene, finally gained solution electrostatic spinning is prepared composite nano fiber.
Further, the reception device of electrostatic spinning is two parallel metal bars, and metallic rod spacing is 0.1��5cm.
Described polystyrene/derivatives of porphyrin composite nano fiber application in transistorized memory, is the electronics trapping layer that described composite nano fiber is made transistorized memory.
The present invention adopts two parallel metal bars with same negative high voltage as the reception device of electrostatic spinning, obtains the polystyrene/derivatives of porphyrin composite nano fiber of orientation, and namely arrangement has the composite nano fiber of certain orientation. Obtaining nanofiber relative to conventional receiver mode, the nanofiber of the present invention is transferred to SiO2Method on/Si substrate is simpler fast, it is simple to ensuing memorizer is integrated. Additionally, directed nanofiber has a less roughness compared with the nanofiber of mixed and disorderly distribution, and the arrangement of nanofiber and channel vertical, does not have the parallel situation isolating raceway groove, more smooth at the epontic Benzo[b of orientated nano fibers, and then transistor field effect also can be more good. On this basis, nanofiber does electric charge capture layer, has higher specific surface area, more highdensity storage site can be formed in identical raceway groove, thus being beneficial to raising memory window, meanwhile, nanofiber surface can form higher built in field and be beneficial to the effective of carrier and transmit.
Beneficial effect:
1. polystyrene/derivatives of porphyrin composite nano fiber has higher specific surface area as the electronics trapping layer of transistorized memory than spin-coated thin film, can reach higher memory density, and then improve the memory window of memorizer in same raceway groove;
2. under same grid voltage, polystyrene/derivatives of porphyrin composite nano fiber surface can form higher built in field, is beneficial to the carrier effective transmission at each function interlayer of device;
3. when the doping content of derivatives of porphyrin is the 1% of PS weight, gained transistorized memory can reach the memory window of 33V, and device has higher reliability.
Accompanying drawing explanation
Fig. 1 be embodiment 1 use electrostatic spinning technique and nanofiber transfer schematic diagram;
Fig. 2 is the scanning electron microscope diagram of the polystyrene/derivatives of porphyrin composite nano fiber of embodiment 1 preparation;
Fig. 3 is the device architecture schematic diagram of the transistorized memory of embodiment 1 preparation;
Fig. 4 is the transfer curve of the transistorized memory of embodiment 1 preparation;
Fig. 5 is the curve of output of the transistorized memory of embodiment 1 preparation;
Fig. 6 is the drift of the transfer curve of the transistorized memory of embodiment 1 preparation;
Fig. 7 is the curve of holding time of the transistorized memory of embodiment 1 preparation;
Fig. 8 is the drift of the transfer curve of the transistorized memory of embodiment 2 preparation;
Detailed description of the invention
Following example further illustrate present disclosure, but should not be construed as limitation of the present invention. Without departing from the spirit and substance of the case in the present invention, the amendment that the inventive method, step or condition are made and replacement, belong to the scope of the present invention. If not specializing, the conventional means that technological means used in embodiment is well known to those skilled in the art.
The synthesis of Mesoporphyrin derivant of the present invention is with reference to Light-HarvestingandUltrafastEnergyMigrationinPorphyrin-B asedMetal-OrganicFrameworks, JournaloftheAmericanChemicalSociety, 2013,135 (2), pp862 869.
Embodiment 1
Weigh a certain amount of derivatives of porphyrin and be dissolved in N, in dinethylformamide, ultrasonic, add polystyrene, making polystyrene concentrations is 100mg/mL, derivatives of porphyrin: polystyrene is 1wt%, heating stirring until polymer is completely dissolved on 50 DEG C of warm tables, solution is till homogeneous, transparence. The above-mentioned solution configured is injected in the standard syringe of 2mL and carry out electrospinning, as shown in Figure 1, syringe front end connecting external diameter is that the rustless steel syringe needle of 0.6mm is as shower nozzle, and connect the positive high voltage of 15KV, place parallel metal bar that spacing is 2cm immediately below shower nozzle as receiving device, and connect the negative high voltage of-500V, shower nozzle with receive device at a distance of 15cm, arranging syringe pump fltting speed is that 0.001mm/s carries out electrospinning, obtains the polystyrene/derivatives of porphyrin composite nano fiber of orientation.
Fig. 2 is the scanning electron microscope diagram sheet of polystyrene/derivatives of porphyrin composite nano fiber, and composite nano fiber pattern is smooth as we can see from the figure, and on average, diameter is 390nm.
By SiO2/ Si sheet cuts into the substrate of 1.5 �� 1.5cm, distinguishes ultrasonic 10 minutes with acetone, ethanol, ultra-pure water, then dries up with high pressure nitrogen, then prevents from 20 minutes making it be completely dried in 120 DEG C of baking ovens. The substrate of wash clean is lain against under composite nano fiber, and ensures that composite nano fiber is vertical with substrate side, slowly lift substrate and nanofiber is successfully shifted. Being transferred in glove box by the substrate carrying nanofiber, midway can not be subject to flow perturbation, and otherwise the arrangement of nanofiber can be destroyed. Being lain against by substrate on the warm table in glove box, 200 DEG C of annealing make nanofiber soften in 1 hour and strengthen and the contacting of substrate. Next being deposited with the thick Benzo[b of 50nm at nanofiber surface, evaporation rate is lower than 0.03nm/s. Finally, mask plate is installed on Benzo[b surface, and guarantee that the raceway groove on mask plate is vertical with nanofiber, copper steam-plating source-drain electrode, obtaining the transistorized memory using directed polystyrene/derivatives of porphyrin composite nano fiber as charge storage layer, Fig. 3 is the device architecture schematic diagram of transistorized memory.
The performance of test gained transistorized memory, by SiO2Scratch, only retain grid Si for one jiao of/Si sheet, the three of semiconductor parameter instrument probes are connected source-drain electrode and grid respectively, test its transfer and curve of output, the drift of transfer curve and reliability respectively.
Fig. 4 is the transfer curve of transistorized memory,
Fig. 5 is the curve of output of transistorized memory, and as can be seen from the figure gained transistorized memory has reliable field effect.
Fig. 6 is the drift of transistorized memory transfer curve, and as can be seen from the figure the memory window of transistor is up to 33V, has stronger storage capacity.
Fig. 7 is the curve of holding time of transistorized memory, and as can be seen from the figure obvious decay does not occur the electric current of transistorized memory ON state and OFF state after the test of 10000s, and on-off ratio still has 5.2 �� 104, this memorizer has good stability.
Embodiment 2
Weigh a certain amount of derivatives of porphyrin and be dissolved in N, in dinethylformamide, ultrasonic, add polystyrene, making polystyrene concentrations is 100mg/mL, derivatives of porphyrin: polystyrene is 0.5wt%, heating stirring until polymer is completely dissolved on 50 DEG C of warm tables, solution is till homogeneous, transparence. The above-mentioned solution configured is injected in the standard syringe of 2mL and carry out electrospinning, as shown in Figure 1, syringe front end connecting external diameter is that the rustless steel syringe needle of 0.6mm is as shower nozzle, and connect the positive high voltage of 15KV, immediately below shower nozzle, placement spacing is that the parallel metal bar of 2cm is as receiving device, and connect the negative high voltage of-500V, shower nozzle and reception device are at a distance of 15cm, arranging syringe pump fltting speed is that 0.001mm/s carries out electrospinning, obtain the polystyrene/derivatives of porphyrin composite nano fiber of orientation, gained composite nano fiber pattern is smooth, and on average, diameter is 380nm.
By SiO2/ Si sheet is cut into the substrate of 1.5 �� 1.5cm, distinguishes ultrasonic 10 minutes with acetone, ethanol, ultra-pure water, then dries up with high pressure nitrogen, then places in 120 DEG C of baking ovens and makes it be completely dried in 20 minutes. Nanofiber is transferred on the substrate of wash clean, anneal 1 hour with 200 DEG C of warm tables in glove box again, then evaporation Benzo[b and copper source-drain electrode are shown at it, and guarantee that the raceway groove on mask plate is vertical with nanofiber, obtain the transistorized memory using directed polystyrene/derivatives of porphyrin composite nano fiber as charge storage layer. The three of semiconductor parameter instrument probes are connected source-drain electrode and grid, the memory property of test transistor memorizer respectively.
Fig. 8 is the drift of transistorized memory transfer curve, as can be seen from the figure the memory window of transistor is 16V, the window of transistorized memory is prepared lower than embodiment 1, this illustrates that the derivatives of porphyrin as storage site is before doping is not up to marginal value, and its content is proportional to the storage capacity of device.

Claims (6)

1. polystyrene/derivatives of porphyrin composite nano fiber, it is characterised in that: raw material includes polystyrene and derivatives of porphyrin, and the structural formula of described derivatives of porphyrin is:
Wherein, R1For the one of pyridine radicals or phenyl, R2For the one in unsaturated bond or aromatic functional group, R1��R2Identical or different.
2. polystyrene according to claim 1/derivatives of porphyrin composite nano fiber, it is characterised in that: the diameter of described polystyrene/derivatives of porphyrin composite nano fiber is 50��800nm.
3. polystyrene according to claim 1/derivatives of porphyrin composite nano fiber, it is characterised in that: the weight ratio of polystyrene and derivatives of porphyrin is 100:0.5��5.
4. the preparation method of the polystyrene described in claim 1/derivatives of porphyrin composite nano fiber, it is characterized in that: first derivatives of porphyrin is dissolved in N, dinethylformamide, add polystyrene, heated and stirred is completely dissolved to polystyrene, finally gained solution electrostatic spinning is prepared composite nano fiber.
5. the preparation method of polystyrene according to claim 4/derivatives of porphyrin composite nano fiber, it is characterised in that: the reception device of electrostatic spinning is two parallel metal bars, and metallic rod spacing is 0.1��5cm.
6. a transistorized memory, it is characterised in that: the electronics trapping layer of described transistorized memory polystyrene/derivatives of porphyrin composite nano fiber described in claim 1 is made.
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CN106442497A (en) * 2016-09-21 2017-02-22 天津工业大学 Preparation method of porphyrin/nano porous fiber membrane hydrogen chloride gas sensor
CN106433618A (en) * 2016-09-21 2017-02-22 天津工业大学 Preparation method for fluorescent colorimetric chemical sensor and application of fluorescent colorimetric chemical sensor in gas detection
CN106684244A (en) * 2016-11-03 2017-05-17 南京邮电大学 Floating gate-type flexible low-voltage organic field effect transistor memory
CN108796825A (en) * 2018-06-22 2018-11-13 南京邮电大学 Detect the porous nano-fibre film and the preparation method and application thereof of wet environment explosive vapors
CN111548683A (en) * 2020-05-13 2020-08-18 南京邮电大学 Polystyrene-porphyrin derivative nano vertical array film and preparation method and application thereof
CN113802208A (en) * 2021-10-09 2021-12-17 吉林大学 Multifunctional transparent nanofiber screen window and preparation method thereof

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Publication number Priority date Publication date Assignee Title
CN106442497A (en) * 2016-09-21 2017-02-22 天津工业大学 Preparation method of porphyrin/nano porous fiber membrane hydrogen chloride gas sensor
CN106433618A (en) * 2016-09-21 2017-02-22 天津工业大学 Preparation method for fluorescent colorimetric chemical sensor and application of fluorescent colorimetric chemical sensor in gas detection
CN106684244A (en) * 2016-11-03 2017-05-17 南京邮电大学 Floating gate-type flexible low-voltage organic field effect transistor memory
CN106684244B (en) * 2016-11-03 2019-07-09 南京邮电大学 A kind of floating gate type flexibility low-voltage organic field effect tube memory
CN108796825A (en) * 2018-06-22 2018-11-13 南京邮电大学 Detect the porous nano-fibre film and the preparation method and application thereof of wet environment explosive vapors
CN111548683A (en) * 2020-05-13 2020-08-18 南京邮电大学 Polystyrene-porphyrin derivative nano vertical array film and preparation method and application thereof
CN111548683B (en) * 2020-05-13 2021-09-28 南京邮电大学 Polystyrene-porphyrin derivative nano vertical array film and preparation method and application thereof
CN113802208A (en) * 2021-10-09 2021-12-17 吉林大学 Multifunctional transparent nanofiber screen window and preparation method thereof

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