CN111430540A - Preparation method and application of organic-inorganic heterojunction - Google Patents
Preparation method and application of organic-inorganic heterojunction Download PDFInfo
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- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 23
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- 230000015572 biosynthetic process Effects 0.000 description 1
- JTPDXCIVXNLRFP-UHFFFAOYSA-N bis(selanylidene)platinum Chemical compound [Pt](=[Se])=[Se] JTPDXCIVXNLRFP-UHFFFAOYSA-N 0.000 description 1
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- RKNFJIIYAUSTJA-UHFFFAOYSA-N bis(sulfanylidene)platinum Chemical compound S=[Pt]=S RKNFJIIYAUSTJA-UHFFFAOYSA-N 0.000 description 1
- HITXEXPSQXNMAN-UHFFFAOYSA-N bis(tellanylidene)molybdenum Chemical compound [Te]=[Mo]=[Te] HITXEXPSQXNMAN-UHFFFAOYSA-N 0.000 description 1
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- NRJVMVHUISHHQB-UHFFFAOYSA-N hafnium(4+);disulfide Chemical compound [S-2].[S-2].[Hf+4] NRJVMVHUISHHQB-UHFFFAOYSA-N 0.000 description 1
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- MHWZQNGIEIYAQJ-UHFFFAOYSA-N molybdenum diselenide Chemical compound [Se]=[Mo]=[Se] MHWZQNGIEIYAQJ-UHFFFAOYSA-N 0.000 description 1
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- WFGOJOJMWHVMAP-UHFFFAOYSA-N tungsten(iv) telluride Chemical compound [Te]=[W]=[Te] WFGOJOJMWHVMAP-UHFFFAOYSA-N 0.000 description 1
- 230000005641 tunneling Effects 0.000 description 1
- XWPGCGMKBKONAU-UHFFFAOYSA-N zirconium(4+);disulfide Chemical compound [S-2].[S-2].[Zr+4] XWPGCGMKBKONAU-UHFFFAOYSA-N 0.000 description 1
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- 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]
- H10K10/462—Insulated gate field-effect transistors [IGFETs]
- H10K10/484—Insulated gate field-effect transistors [IGFETs] characterised by the channel regions
- H10K10/486—Insulated gate field-effect transistors [IGFETs] characterised by the channel regions the channel region comprising two or more active layers, e.g. forming pn heterojunctions
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G39/00—Compounds of molybdenum
- C01G39/06—Sulfides
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- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
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- H10K71/125—Deposition of organic active material using liquid deposition, e.g. spin coating using electrolytic deposition e.g. in-situ electropolymerisation
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- H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
- H10K85/621—Aromatic anhydride or imide compounds, e.g. perylene tetra-carboxylic dianhydride or perylene tetracarboxylic di-imide
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Abstract
The invention discloses a preparation method and application of an organic-inorganic heterojunction. The method realizes the preparation of the organic-inorganic heterojunction, the prepared organic-inorganic heterojunction is of an inorganic-organic-inorganic sandwich structure, the inorganic protective layer is arranged outside the organic layer and is not directly exposed, and when the organic-inorganic heterojunction is used for preparing an electronic device, organic micromolecules cannot be damaged. The prepared organic-inorganic heterojunction can be used as a channel material of an electronic device, can effectively reduce or eliminate a contact potential barrier with an electrode, and the device can have high electron mobility.
Description
Technical Field
The invention relates to a preparation method and application of an organic-inorganic heterojunction, and belongs to the technical field of two-dimensional material electronic devices.
Background
The integration of two-dimensional van der Waals heterojunctions provides different structures without lattice matching constraints, which are critical to the new field of creating functional devices by design.
The heterostructure prepared by the existing method is usually an inorganic heterostructure, an organic layer lacks an effective transfer mode at present, and an organic-inorganic heterojunction cannot be realized. The general heterostructure preparation method such as transfer can damage the structure of the organic material, the operation is difficult, large-area preparation is difficult, and the repeatability is poor; although the chemical vapor deposition method can obtain a high-quality organic thin film layer on the surface of an inorganic thin film to generate a high-quality heterostructure, the organic layer is exposed outside, so that when the chemical vapor deposition method is used for preparing an electronic device, the organic layer is extremely easy to damage in the process of evaporating a metal electrode by organic micromolecules, and the organic-inorganic heterojunction of the thin layer cannot be practically used in the electronic device. In addition, due to the unique property of the organic layer, the existing method can not deposit an inorganic protective layer on the surface of the organic layer, and can not realize a layer-by-layer staggered structure.
To date, the synthesis of two-dimensional organic-inorganic van der waals heterostructures with thin atoms remains a great challenge, and new methods are needed to realize the construction of organic-inorganic heterojunctions.
Disclosure of Invention
The purpose of the invention is as follows: aiming at the problem that the existing method can not realize the preparation of the organic-inorganic heterostructure, the invention provides a preparation method of an organic-inorganic heterojunction and provides an application of the organic-inorganic heterostructure prepared by the method as a channel material of an electronic device.
The technical scheme is as follows: the invention relates to a preparation method of an organic-inorganic heterojunction, which is characterized in that a two-dimensional organic molecule with optical or electrical properties is embedded into a two-dimensional inorganic crystal by adopting an electrochemical intercalation method to obtain an inorganic-organic-inorganic sandwich heterostructure.
Specifically, a two-dimensional organic molecule solution is used as an electrolyte, a two-dimensional inorganic crystal is used as a working electrode, a counter electrode and a reference electrode are added to construct an electrochemical system, and then the two-dimensional organic molecules are embedded between the two-dimensional inorganic crystal layers under the action of current.
The preparation process can comprise the following steps:
(1) dissolving two-dimensional organic molecules in an organic solvent to prepare a saturated solution of the two-dimensional organic molecules;
(2) immersing a two-dimensional inorganic crystal serving as a working electrode in the solution obtained in the step (1), inserting a counter electrode and a reference electrode into the solution, and applying voltage scanning between the two-dimensional inorganic crystal electrode and the counter electrode to enable two-dimensional organic molecules to be embedded between two-dimensional inorganic crystal layers;
(3) and after the reaction is finished, cleaning the surface of the two-dimensional inorganic crystal to obtain the two-dimensional inorganic crystal/two-dimensional organic molecule/two-dimensional inorganic crystal organic-inorganic heterostructure.
The two-dimensional inorganic crystal may be graphene or black phosphorus, and may also be a transition metal chalcogenide compound such as molybdenum disulfide, molybdenum diselenide, tungsten disulfide, tungsten diselenide, hafnium disulfide, zirconium disulfide, rhenium diselenide, platinum disulfide, platinum diselenide, molybdenum ditelluride, tungsten ditelluride, or the like. The two-dimensional organic molecule can be 3,4,9, 10-perylenetetracarboxylic dianhydride (abbreviated as "PTCDA"), pentacene, or carbon 60.
In the step (1), the organic solvent can be dimethyl sulfoxide or acetonitrile, the concentration of the prepared two-dimensional organic molecule saturated solution is generally 1-5 g/L, and sodium dodecyl benzene sulfonate can also be added into the organic solvent, so that the dissolution of two-dimensional organic molecules can be accelerated.
In the step (2), the counter electrode can be a platinum electrode or a graphite electrode, and the reference electrode can be an Ag/AgCl electrode or a calomel electrode. Preferably, the process parameters of the applied voltage sweep are as follows: applying a voltage of 0V to 2.5-3V between the two-dimensional inorganic crystal electrode and the counter electrode, wherein the scanning speed is 10-100 mV/s, and the scanning is performed for 1-6 circles. Two-dimensional organic molecules can be embedded between two-dimensional inorganic crystal layers by scanning for one circle, and the degree of intercalation is increased and the amount of intercalation is increased by increasing the number of scanning circles; generally, in a shorter scanning time, a single layer of organic molecule intercalation can be obtained, and the longer the scanning time, the more the number of layers of the intercalated organic molecule. By controlling the scanning speed and the number of scanning circles, organic-inorganic heterojunction with different layers of organic molecule intercalation can be obtained; however, too much intercalation will cause the inorganic layer to expand too much and destroy the heterostructure, so the number of scans is preferably not more than 6.
The application of the invention is to use the organic-inorganic heterostructure prepared by the method as a channel material of an electronic device.
The invention principle is as follows: the invention uses two-dimensional organic molecule solution as electrolyte, two-dimensional inorganic crystal as working electrode to construct electrochemical system, intercalation is realized in voltage scanning process, intercalation takes place at cathode potential, wherein two-dimensional inorganic crystal layer has negative charge, and a gap is opened under the action of repulsion force, two-dimensional organic molecule can enter two-dimensional inorganic crystal layer as charge buffer part to stabilize two-dimensional inorganic crystal layer with negative charge, so that interaction is formed between two-dimensional organic molecule and adjacent two-dimensional inorganic crystal layer.
Has the advantages that: compared with the prior art, the invention has the advantages that: (1) the invention realizes the embedding of two-dimensional organic molecules with optical or electrical properties in a two-dimensional inorganic crystal by an electrochemical intercalation method, and realizes the preparation of an organic-inorganic heterojunction; the organic-inorganic heterojunction prepared by the method is of an inorganic-organic-inorganic sandwich structure, the inorganic protective layer is arranged outside the organic layer, the outside is not directly exposed, and when the organic-inorganic heterojunction is used for preparing an electronic device, organic micromolecules cannot be damaged in the process of evaporating a metal electrode; (2) the preparation method is simple and easy to operate, and is suitable for application of electronic and photoelectronic devices in various forms, including field effect transistors, photoelectric transistors, tunneling transistors, storage devices and the like.
Drawings
FIG. 1 is a schematic representation of the preparation of MoS in example 12Schematic diagram of PTCDA organic-inorganic heterojunction;
FIG. 2 shows MoS obtained in example 12A scanning transmission electron microscope image and an X-ray energy spectrum element image of the PTCDA cross-section sample;
FIG. 3 shows MoS obtained in example 12 Mo 3d and S2 p spectra of X-ray photoelectron spectra of/PTCDA heterojunction;
FIG. 4 shows MoS before and after electrochemical intercalation of PTCDA in example 12(ii) a Raman spectrum of;
FIG. 5 preparation of MoS for example 22A process flow diagram for the/PTCDA transistor;
FIG. 6 is the MoS prepared in example 22Microscopic image of PTCDA organic-inorganic heterojunction;
FIG. 7 is the MoS prepared in example 22A transfer characteristic curve (a) and an output characteristic curve (b) before and after Field Effect Transistor (FET) intercalation;
FIG. 8 is the MoS prepared in example 22A transfer characteristic curve (a) and an output characteristic curve (b) of the/PTCDA heterojunction device in a temperature range of 50K-300K;
FIG. 9 is a graph of transfer characteristics of Field Effect Transistors (FETs) of different organic-inorganic combinations before and after intercalation in example 3.
Detailed Description
The technical scheme of the invention is further explained by combining the attached drawings.
The invention relates to a preparation method of an organic-inorganic heterojunction, which is characterized in that a two-dimensional organic molecule with optical or electrical properties is embedded into a two-dimensional inorganic crystal by adopting an electrochemical intercalation method to obtain an inorganic-organic-inorganic sandwich heterostructure. The method takes a two-dimensional organic molecule solution as an electrolyte and a two-dimensional inorganic crystal as a working electrode, adds a counter electrode and a reference electrode to construct an electrochemical system, and embeds two-dimensional organic molecules between two-dimensional inorganic crystal layers under the action of current. Wherein, the two-dimensional inorganic crystal can be graphene, black phosphorus or transition metal chalcogenide, and the two-dimensional organic molecule can be PTCDA, pentacene or carbon 60.
Example 1
Adding 3,4,9, 10-perylenetetracarboxylic dianhydride (PTCDA) into dimethyl sulfoxide (DMSO), stirring to dissolve completely, precipitating, taking the upper saturated solution, centrifuging at the rotating speed of 3000r for 3min, and obtaining the PTCDA/DMSO solution with the concentration of 1 g/L.
As shown in FIG. 1, a molybdenum sulfide block was held by an electrode holder and immersed in the above solution, a platinum electrode and a calomel reference electrode were inserted into the solution, a voltage of 0V to 3V was applied between the platinum electrode and the molybdenum sulfide electrode at a sweep rate of 100mV/s, and PTCDA was inserted between the molybdenum sulfide layers after one sweep. After the reaction is finished, the surface of the original molybdenum sulfide block is cleaned by isopropanol to obtain PTCDA/MoS2An organic-inorganic heterojunction.
The performance of the organic-inorganic heterojunction is characterized in the figures 2-4. Wherein, FIG. 2 is PTCDA/MoS2When the sample is cross-sectioned by a scanning transmission electron microscope image and an X-ray energy spectrum element image, it can be seen that the PTCDA layer ratio MoS is higher due to the higher atomic number of Mo and S2Dark layer and light line MoS2Molecular layer, MoS2Is at a distance from
Increase to
The increased thickness is the thickness of the intercalated PTCDA layer; in addition, the distribution of carbon element, which is the main element of PTCDA, in MoS can be proved from X-ray energy spectrum elemental images2Between the layers.
FIG. 3 is PTCDA/MoS2 Mo 3d and S2 p spectra of X-ray photoelectron spectroscopy (XPS) of heterojunctionsFIG. 3 shows that PTCDA and MoS2The charge transfer between them results in N-type doping of the material. FIG. 4 shows MoS before and after electrochemical intercalation of PTCDA2The Raman spectrum after intercalation can be seen to contain MoS2And Raman characteristic peaks of PTCDA, confirming that MoS is indeed formed2a/PTCDA heterojunction.
Example 2
The method of the invention is adopted to prepare the molybdenum sulfide/PTCDA/molybdenum sulfide heterojunction, and the organic-inorganic heterojunction is used as a channel material to prepare the molybdenum sulfide/PTCDA transistor, and the preparation process is shown in figure 5.
(1) At 275nm silicon (Si)/silicon dioxide (SiO)2) Mechanical stripping of bulk crystals for the substrate yields a few layers of n-type molybdenum disulfide (MoS)2) Spin-coating polymethyl methacrylate (PMMA) photoresist with spin-coating parameters of 600r/min, 5s +4000r/min, 60s and baking parameters of 150 ℃ for 10min, performing electrode pattern photoetching and development by using electron Beam exposure (EB L), wherein the developing solution is MIBK and IPA is 1:3, the room temperature is 45s, depositing 20nmTi/50nm Pd by using electron Beam Evaporation (EBE, E-Beam Evaporation) to obtain a contact electrode, removing the photoresist to obtain a back gate molybdenum sulfide field effect transistor, spin-coating a layer of PMMA as a protective layer to avoid electrochemical reaction on the metal electrode, the spin-coating parameters are 600r/min, 5s +4000r/min and 60s, the baking parameters are 170 ℃ for 10min, performing patterning treatment of a reaction window at the position of a molybdenum sulfide channel by using electron Beam photoetching, and performing development to obtain a reaction window exposing molybdenum sulfide, and the developing solution is MIBK and IPA is 1: 3: 45 s.
(2) The back gate molybdenum sulfide field effect transistor is immersed in a dimethyl sulfoxide (DMSO) solution filled with saturated 3,4,9, 10-perylenetetracarboxylic dianhydride (PTCDA) and Sodium Dodecyl Sulfate (SDS), and a platinum counter electrode and an Ag/AgCl reference electrode are inserted into the solution. A small constant bias voltage is applied between the source and drain of the molybdenum sulfide device. And applying a voltage varying from 0-3V between the platinum counter electrode and the molybdenum sulfide device, scanning for 3 circles, and embedding the PTCDA between the molybdenum sulfide layers in the process. After the reaction is finished, removing the photoresist to obtain MoS2The microscopic image of the/PTCDA organic-inorganic heterojunction device is shown in FIG. 6, wherein, a picture shows the deviceThe part comprises metal electrodes and organic-inorganic heterojunction regions, wherein bright regions in the part are Ti/Pd metal electrodes, and molybdenum sulfide is arranged between the two Ti/Pd metal electrodes; the image of the area where the molybdenum sulfide is located after being further enlarged is shown as a graph b in fig. 6, a window (the center of the graph b) of PMMA on the prepared molybdenum sulfide device is a position where the molybdenum sulfide is in contact with the solution, and the PTCDA is intercalated into the whole channel from the edge position of the molybdenum sulfide.
The obtained MoS2The PTCDA organic-inorganic heterojunction field effect transistor is arranged in a vacuum probe station, two probes are respectively contacted with a source electrode, a drain electrode and the two electrodes, and Si/SiO is used for passing through2Adding a back gate on the substrate, and testing to obtain a transfer curve and an output curve, as shown in FIG. 7, wherein the voltage between the fixed source and drain in the transfer curve (a) is 500mV, the gate voltage is from-40V to 40V, and the MoS after intercalation2The transfer characteristic curve of the device becomes almost not regulated by grid voltage, and the through current is increased by one order of magnitude compared with the original device, which is a typical behavior of n-type doping; the output curve (b) after PTCDA intercalation is linear behavior, which shows that the contact resistance of the metal-organic-inorganic heterojunction after PTCDA intercalation is reduced. FIG. 8 vs. MoS2The transport characteristics of the/PTCDA heterojunction device at different temperatures are researched, the temperature of a probe station is reduced from 300K to 50K, and the carrier mobility of a field effect transistor is reduced from 96cm-2V-1S-1Rise to 300cm- 2V-1S-1(ii) a The heterojunction I-V output curve is still linear at low temperature and is ohmic contact.
Example 3
Referring to the method of example 2, C60 and Pentacene (abbreviated as "Pentacene") were used instead of PTCDA, tungsten sulfide and highly oriented pyrolytic graphite (abbreviated as "HOPG") were used instead of molybdenum sulfide, and 9 organic-inorganic heterojunction field effect transistors of different materials were prepared by combining them.
The transfer characteristics of the prepared different organic-inorganic composite Field Effect Transistors (FET) before and after intercalation are shown in FIG. 9, except WS2Outside the Pentacene, the decrease of the on-off ratio can be seen from the transfer curve, an obvious N doping is seen, the current is increased, and the organic-inorganic heterostructure is realized in the prepared field effect transistor.
Claims (9)
1. A preparation method of an organic-inorganic heterojunction is characterized in that a two-dimensional organic molecule with optical or electrical properties is embedded into a two-dimensional inorganic crystal by adopting an electrochemical intercalation method to prepare an inorganic-organic-inorganic sandwich heterostructure.
2. The method according to claim 1, wherein the two-dimensional organic molecule solution is used as an electrolyte, the two-dimensional inorganic crystal is used as a working electrode, a counter electrode and a reference electrode are added to construct an electrochemical system, and the two-dimensional organic molecule is embedded between the two-dimensional inorganic crystal layers under the action of current.
3. A method of fabricating an organic-inorganic heterojunction as claimed in claim 2, wherein the fabrication process comprises the steps of:
(1) dissolving two-dimensional organic molecules in an organic solvent to prepare a saturated solution of the two-dimensional organic molecules;
(2) immersing a two-dimensional inorganic crystal serving as a working electrode in the saturated solution obtained in the step (1), inserting a counter electrode and a reference electrode, and applying voltage scanning between the two-dimensional inorganic crystal electrode and the counter electrode to enable two-dimensional organic molecules to be embedded between two-dimensional inorganic crystal layers;
(3) and after the reaction is finished, cleaning the surface of the two-dimensional inorganic crystal to obtain the two-dimensional inorganic crystal/two-dimensional organic molecule/two-dimensional inorganic crystal organic-inorganic heterostructure.
4. The method according to any one of claims 1 to 3, wherein the two-dimensional inorganic crystal is graphene, black phosphorus or a transition metal chalcogenide.
5. The method according to any one of claims 1 to 3, wherein the two-dimensional organic molecule is 3,4,9, 10-perylenetetracarboxylic dianhydride, pentacene, or carbon 60.
6. The method of claim 3, wherein in step (1), the organic solvent is dimethyl sulfoxide or acetonitrile.
7. The method of claim 3, wherein in step (2), the process parameters of the applied voltage sweep are: applying a voltage of 0V to 2.5-3V between the two-dimensional inorganic crystal electrode and the counter electrode, wherein the scanning speed is 10-100 mV/s, and the scanning is performed for 1-6 circles.
8. The method of claim 3, wherein in the step (2), the counter electrode is a platinum electrode or a graphite electrode, and the reference electrode is an Ag/AgCl electrode or a calomel electrode.
9. Use of an organic-inorganic heterostructure prepared by a process according to any of claims 1 to 3 as a channel material for electronic devices.
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