CN103972391A - Composite organic rectifier diode - Google Patents
Composite organic rectifier diode Download PDFInfo
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- CN103972391A CN103972391A CN201410236826.8A CN201410236826A CN103972391A CN 103972391 A CN103972391 A CN 103972391A CN 201410236826 A CN201410236826 A CN 201410236826A CN 103972391 A CN103972391 A CN 103972391A
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- rectifier diode
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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
- H10K10/20—Organic diodes
- H10K10/26—Diodes comprising organic-organic junctions
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- 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
- H10K85/10—Organic polymers or oligomers
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- 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
- H10K85/20—Carbon compounds, e.g. carbon nanotubes or fullerenes
- H10K85/211—Fullerenes, e.g. C60
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- 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
- H10K85/60—Organic compounds having low molecular weight
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Abstract
The invention discloses an organic rectifier diode, relates to the field of organic semiconductor electronic devices, and particularly relates to a composite organic rectifier diode compounded on an organic/organic p-n heterojunction interface on the basis of a charge carrier. The composite organic rectifier diode disclosed by the invention comprises a base, a bottom electrode, a p-type material layer, an n-type material layer, a charge buffer layer and a top electrode. The composite organic rectifier diode is characterized in that m-MTDATA, 2T-NATA, CuPc, TPD, NPB, TAPC, TCTA, CBP or Rubrene is used as the p-type material layer; C60 is used as the n-type material layer. The composite organic rectifier diode disclosed by the invention has the advantages that the composite organic rectifier diode is high in material selectivity, and the common p-type organic material can be selected with high flexibility; due to the complex mechanism, the rectified current can be supplied by compounding electrons and holes at the p-n heterojunction interface, and the composite organic rectifier diode is low in interface impedance and high in rectification ratio; the composite organic rectifier diode is simple in process and high in apparatus repeatability, is not doped with the p-type material and the n-type material, and is low in demands on fabrication processes and equipments of apparatuses.
Description
Technical field
The present invention relates to organic semiconductor field of electronic devices, especially a kind of based on electric charge carrier at the compound organic rectifier diode of organic/organic p-n heterojunction boundary.
Background technology
Organic semiconductor has boundless business application.For example: the application of Organic Light Emitting Diode aspect flat-panel monitor and solid-state illumination, the application of organic solar batteries aspect regenerative resource.In addition, organic semiconductor also has a very potential application, and that is exactly that organic rectifier diode is in RFID(RFID tag) on application.
The development of organic rectifier diode mainly based on metal/organic and inorganic/organic and p-i-n is organic/organic semiconductor heterojunction, and organic rectifier diode device based on organic/organic p-n heterojunction was not also in the news.
The carrier transport mechanism of heterojunction generally can simply be divided into following two kinds of models: 1) diffusion model, electronics is along the minimum track that do not occupy of organic material LUMO() (or conduction band) or hole be along HOMO(highest occupied molecular orbital) (or valence band) transmission; 2) composite model, electronics and hole are compound at p-n heterojunction boundary.Compound p-n heterojunction is very general in inorganic semiconductor field, and has obtained very deep research.But in organic semiconductor field, compound p-n heterojunction is exploited up till now not yet.This be because the HOMO of organic material all lower than-5.0 eV (electron-volt), and its LUMO is higher than-4.0 eV, be that the HOMO of p-type material and the LUMO of N-shaped material at least exist the energy gap that is greater than 1.0 eV, it is compound that large energy gap like this is difficult at organic/organic heterojunction interface electronics and hole.
Owing to being subject to the restriction of organic material energy level, current organic rectifier diode is mainly based on diffused heterojunction, the obstruction that this is serious the development of organic rectifier diode.Therefore, for the further developing and reach the application on RFID of organic rectifier diode, find organic/organic p-n heterojunction with interface charge multiple mechanism, realize the compound organic rectifier diode with high rectification characteristic and be very important.
Summary of the invention
To be solved by this invention is exactly the problem that organic rectifier diode device only limits to diffused heterojunction, propose a kind of based on electric charge carrier at the compound compound organic rectifier diode of organic/organic p-n heterojunction boundary.
Compound organic rectifier diode of the present invention, comprise substrate, hearth electrode, p-type organic material layer, N-shaped organic material layer, charge buffer layer and top electrode, it is characterized in that p-type material layer selects m-MTDATA, 2T-NATA, CuPc, TPD, NPB, TAPC, TCTA, CBP or Rubrene; N-shaped material layer is selected C
60.
The substrate of described organic rectifier diode is substrate of glass.
Described hearth electrode is selected ITO, Al, Ag, Au, Cu or Ni.
Described charge buffer layer is selected BCP, LiF, Liq, Libpp or Cs
2cO
3.
Described top electrode is selected Al, Ag, Mg, Li or Ca.
On described hearth electrode, modifying interface layer can be set, whether the setting of modifying interface layer is determined according to the potential barrier between hearth electrode and p-type material.This modifying interface layer material is selected MoO
-3, HAT-CN or C
60.
The physical mechanism that compound organic rectifier diode of the present invention is realized high rectification characteristic is: compound at organic/organic p-n heterojunction boundary of electronics and hole under forward bias, p-type and N-shaped material layer stopping electronics and hole respectively under reverse biased.
Larger energy level difference between p-type material and the N-shaped material of the compound organic rectifier diode in the present invention, this energy level difference makes electronics can not be delivered to from the LUMO of N-shaped material the LUMO of p-type material, and hole is also difficult to be delivered to from the HOMO of p-type material the HOMO of N-shaped material.Under External Electrical Field, assemble at p-n heterojunction boundary from electrode injection in electronics and hole.But, between the HOMO of p-type material and the LUMO of N-shaped material, still there is the energy gap that is greater than 1.0 eV.
Can there is compound physical mechanism at the p-n heterojunction boundary with 1.0 eV energy gaps and be in the electronics in the compound organic rectifier diode in the present invention and hole: the special energy level between p-type material and N-shaped material interface is arranged.Measure discovery by UV photoelectron spectroscopy, p-type material has very consistent vacuum level with the interface of N-shaped material, and Presence of an interface dipole does not reduce interface potential barrier, and makes electronics or hole cross potential barrier transmission.But p-type material and N-shaped material interface present band curvature, show that electric charge, at p-n interface, redistribution has occurred, electric charge shifts.Band curvature direction further shows, the electronics on N-shaped material LUMO can be transferred to the HOMO of p-type material.Although it is very faint that this electric charge shifts, but under forward bias, a large amount of electronics is gathered on the LUMO of N-shaped material, this electric charge is shifted and become highly beneficial, it is upper to be that a large amount of radiationless transition process of passing through of electronics on N-shaped material LUMO transits to the HOMO of p-type material, and occurs compound with the upper hole of assembling of HOMO of p-type material.This electron-hole recombination process makes diode component under low-voltage, obtain very high electric current just.In other words, NPB/C
60all electric charge carriers have been caught at interface, have played with ohmic contact and have similarly acted on.Therefore, the rectified current-voltage characteristic of diode component depends primarily on ITO/NPB contact.
Compound organic rectifier diode tool of the present invention has the following advantages: 1) material selectivity is high, comparatively flexible for the selection of p-type material, can select the organic material of common p-type; 2) multiple mechanism, high electric current derives from electronics and hole is compound at p-n heterojunction boundary, and interface impedance is lower, and rectification ratio is high; 3) technique repeatability simple, device is high, and p-type material and N-shaped material be not doping all, and the manufacture craft to device and instrument require lower.
Brief description of the drawings
Fig. 1 is that compound organic rectifier diode of the present invention is without interface decorative layer device architecture schematic diagram.
Fig. 2 is that compound organic rectifier diode of the present invention is for there being interface decorative layer device architecture schematic diagram.
Fig. 3 is that compound organic rectifier diode of the present invention is without the energy diagram under electric field action.
Fig. 4 is compound organic rectifier diode of the present invention energy diagram under forward bias, and the compound schematic diagram in electron-hole interface.
Fig. 5 is compound organic rectifier diode of the present invention energy diagram under reverse biased.
Fig. 6 is based on NPB/C in the present invention
60the energy level Pareto diagram of the p/n heterojunction boundary of the organic composite type rectifier diode of heterojunction.
Fig. 7 is based on NPB/C in the present invention
60the rectification characteristic curve figure of the compound organic rectifier diode device of heterojunction.
Embodiment
Embodiment 1: a kind of compound organic rectifier diode device, each layer of this device is arranged according to following order from the bottom up: substrate, hearth electrode, p-type material layer, N-shaped material layer, charge buffer layer, top electrode.Wherein:
Substrate is the good glass of flatness;
Hearth electrode is that photoetching is at suprabasil ITO;
P-type material layer depositions on hearth electrode, material selection NPB, m-MTDATA, 2T-NATA, CuPc, TPD, TAPC or Rubrene, its thickness is 30nm;
N-shaped material layer is the C being deposited on p-type material layer
60, thickness is 60 nm;
Resilient coating is the BCP being deposited on N-shaped material layer, and thickness is 7 nm;
Top electrode is the metal A l being deposited on resilient coating, and thickness is 100 nm.
Embodiment 2: a kind of compound organic rectifier diode device, each layer of this device is arranged according to following order from the bottom up: substrate, hearth electrode, modifying interface layer, p-type material layer, N-shaped material layer, charge buffer layer and top electrode, wherein:
Substrate is the good glass of flatness;
Hearth electrode is that photoetching is at suprabasil ITO;
Modifying interface layer is the MoO being deposited on hearth electrode
3, thickness is 1 nm;
P-type material layer is TCTA or the CBP being deposited on modifying interface layer, and thickness is 30 nm;
N-shaped material layer is the C being deposited on p-type material layer
60, thickness is 60 nm;
Charge buffer layer is the BCP being deposited on N-shaped material layer, and thickness is 7 nm;
Top electrode is the metal A l being deposited on resilient coating, and thickness is 100 nm.
Embodiment 3: a kind of compound organic rectifier diode device, each layer of this device is arranged according to following order from the bottom up: substrate, hearth electrode, modifying interface layer, p-type material layer, N-shaped material layer, charge buffer layer and top electrode, wherein:
Substrate is the good glass of flatness;
Hearth electrode is for being deposited on suprabasil Al, and thickness is 50 nm;
Modifying interface layer is the MoO being deposited on hearth electrode
3, thickness is 3 nm;
P-type material layer is NPB, m-MTDATA, 2T-NATA, CuPc, TPD, TAPC, TCTA, CBP or the Rubrene being deposited on modifying interface layer, and thickness is 30 nm;
N-shaped material layer is the C being deposited on p-type material layer
60, thickness is 60 nm;
Charge buffer layer is the BCP being deposited on N-shaped material layer, and thickness is 7 nm;
Top electrode is the metal A l being deposited on resilient coating, and thickness is 100 nm.
Claims (9)
1. compound organic rectifier diode, comprise substrate, hearth electrode, p-type material layer, N-shaped material layer, charge buffer layer and top electrode, it is characterized in that p-type material layer selects m-MTDATA, 2T-NATA, CuPc, TPD, NPB, TAPC, TCTA, CBP or Rubrene; N-shaped material layer is selected C
60.
2. compound organic rectifier diode as claimed in claim 1, is characterized in that substrate is substrate of glass.
3. compound organic rectifier diode as claimed in claim 1, the hearth electrode described in it is characterized in that is selected ITO, Al, Ag, Au, Cu or Ni.
4. compound organic rectifier diode as claimed in claim 1, is characterized in that described charge buffer layer selects BCP, LiF, Liq, Libpp or Cs
2cO
3.
5. compound organic rectifier diode as claimed in claim 1, the top electrode described in it is characterized in that is selected Al, Ag, Mg, Li or Ca.
6. compound organic rectifier diode as claimed in claim 1, is characterized in that, on described hearth electrode, modifying interface layer to be set, and this modifying interface layer material is selected MoO-
3, HAT-CN or C
60.
7. compound organic rectifier diode as claimed in claim 1, is characterized in that this diode is organic/organic p-n heterojunction based on pure.
8. compound organic rectifier diode as claimed in claim 1, is characterized in that compound at organic/organic p-n heterojunction boundary of electronics and hole under forward bias, p-type and N-shaped material layer stopping electronics and hole respectively under reverse biased.
9. electron-hole as claimed in claim 8 interface multiple mechanism, is characterized in that energy level potential barrier and charge transfer mechanism between N-shaped material and p-type material.
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|---|---|---|---|
| CN201410236826.8A CN103972391A (en) | 2014-05-30 | 2014-05-30 | Composite organic rectifier diode |
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|---|---|---|---|
| CN201410236826.8A CN103972391A (en) | 2014-05-30 | 2014-05-30 | Composite organic rectifier diode |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105987662A (en) * | 2015-02-02 | 2016-10-05 | 北京大学 | Method and system for measurement of organic semiconductor heterojunction physical properties |
Citations (5)
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| CN101288188A (en) * | 2005-08-22 | 2008-10-15 | 普林斯顿大学理事会 | Organic photosensitive devices with increased open circuit voltage |
| CN102057499A (en) * | 2008-05-01 | 2011-05-11 | 密执安州立大学董事会 | Improved polymer wrapped carbon nanotube near-infrared photoactive devices |
| CN102334209A (en) * | 2009-01-12 | 2012-01-25 | 密歇根大学董事会 | Enhancing the open-circuit voltage of organic photovoltaic cells using electron/hole-blocking exciton-blocking layers |
| WO2012051337A2 (en) * | 2010-10-12 | 2012-04-19 | The Regents Of The University Of Michigan | Photoactive devices including porphyrinoids coordinating additives |
| CN103038906A (en) * | 2010-05-05 | 2013-04-10 | 密歇根大学董事会 | Method of improving exciton dissociation at organic donor-acceptor heterojunctions |
-
2014
- 2014-05-30 CN CN201410236826.8A patent/CN103972391A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101288188A (en) * | 2005-08-22 | 2008-10-15 | 普林斯顿大学理事会 | Organic photosensitive devices with increased open circuit voltage |
| CN102057499A (en) * | 2008-05-01 | 2011-05-11 | 密执安州立大学董事会 | Improved polymer wrapped carbon nanotube near-infrared photoactive devices |
| CN102334209A (en) * | 2009-01-12 | 2012-01-25 | 密歇根大学董事会 | Enhancing the open-circuit voltage of organic photovoltaic cells using electron/hole-blocking exciton-blocking layers |
| CN103038906A (en) * | 2010-05-05 | 2013-04-10 | 密歇根大学董事会 | Method of improving exciton dissociation at organic donor-acceptor heterojunctions |
| WO2012051337A2 (en) * | 2010-10-12 | 2012-04-19 | The Regents Of The University Of Michigan | Photoactive devices including porphyrinoids coordinating additives |
Non-Patent Citations (1)
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| QIUJIAN SUN, ET AL.: "《Dark current and photovoltage models on the formation of depletion region in C60/NPB organic heterojunctions》", 《ORGANIC ELECTRONICS》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105987662A (en) * | 2015-02-02 | 2016-10-05 | 北京大学 | Method and system for measurement of organic semiconductor heterojunction physical properties |
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Application publication date: 20140806 |