CN100505365C - Method for realizing low voltage operating organic field effect transistor - Google Patents
Method for realizing low voltage operating organic field effect transistor Download PDFInfo
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- CN100505365C CN100505365C CNB2006101137219A CN200610113721A CN100505365C CN 100505365 C CN100505365 C CN 100505365C CN B2006101137219 A CNB2006101137219 A CN B2006101137219A CN 200610113721 A CN200610113721 A CN 200610113721A CN 100505365 C CN100505365 C CN 100505365C
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Abstract
A low operating voltage organic field effect transistor comprises a substrate, a grid electrode, an insulation layer, a decorative semiconductor layer, a main body semiconductor layer, a source electrode and a leakage electrode; an organic semiconductor channel consists of the decorative semiconductor layer and the organic main body semiconductor layer, and has the structure that the underside is the decorative semiconductor layer and the upside is the organic main body semiconductor layer. The preparation method is as follows: the grid metal is deposited; at least one layer of insulation layer is deposited on the grid electrode by the insulation layer film forming mode; a decorative semiconductor layer is deposited on the substrate which is deposited with the insulation layer; then the main body organic semiconductor layer is achieved by the organism film forming method; finally the source electrode and the leakage electrode are deposited to achieve finished products. The part structure provided by the invention can achieve the saturation of the field effect transistor in a lower voltage; the operating voltage of the field effect transistor is reduced through the saturation of the low voltage.
Description
Technical field
The invention belongs to the organic field effect tube technical field, particularly a kind of realization low operating voltage organic field effect tube.
The invention still further relates to the preparation method of above-mentioned organic field effect tube.
Background technology
(Tsumura since the report of first organic field effect tube, A., Koezuka, H., Ando, T.Appl.Phys.Lett.49,1210,1986), organic field effect tube is because it is in Active Matrix LCD At, the organic integration circuit, the potential using value of aspects such as electronic trademark has obtained people's extensive concern.Compare with inorganic transistors, organic field effect tube has low cost, and is in light weight, and pliability is good, is easy to characteristics such as mass preparation.In recent years, organic field effect tube has been obtained significant progress, and the trial (B.Crone, A.Dodabalapur, the Y.Y.Lin that are applied to integrated circuit have been arranged, R.W.Filas, Z.Bao, A.LaDuca, R.Sarpeshkar, H.E.Katz, andW.Li, Nature, 403,521-523,2000).The operating voltage height to tens of organic field effect tube volt even volt up to a hundred have limited them and have moved towards the possibility of practical application but generally speaking.
The organic field effect tube of low operating voltage is the necessary unit of realizing low operating voltage organic integration circuit.At present, people realize this purpose by several different methods, the ultra-thin (S.Y.Yang of current topmost employing, S.H.Kim, K.Shin, H.Jeon, and C.E.Park, Appl.Phys.Lett.88,173507,2006.) or monomolecular insulating barrier (M.Halik, H.Klauk, U.Zschieschang, G.Schmid, C.Dehm, M.Schutz, S.Maisch, F.Effenberger, M.Brunnbauer, and F.Stellacci, Nature, 431,963-966,2004), perhaps adopt high dielectric constant materials as insulating barrier (C.D.Dimitrakopoulos, S.Purushothaman, J.Kymissis, A.Callegari, and J.M.Shaw, Science, 283,822-824,1999.), perhaps adopt the device architecture of vertical-channel.Also there is report to adopt the organic field effect tube (M.J.Panzer, C.R.Newman, and C.D.Frisbie, AppliedPhysics Letters, 86,103503,2005) of polymer dielectric recently as the low operating voltage of grid.But up to now, the method for the field-effect transistor of above-mentioned several realization low operating voltages and conventional semiconductor technological process are not exclusively compatible.Particularly ultra-thin insulating barrier, unimolecule insulating barrier or the bigger problem of high-k insulating layer ubiquity leakage current.This has just caused huge obstacle to constructing low operating voltage organic effect logical circuit.
Summary of the invention
In order to solve the too high problem of conventional organic field effect tube operating voltage, the object of the present invention is to provide a kind of low operating voltage (organic field effect tube of 10V～20V) of realizing.
Another purpose of the present invention is to provide the method for the above-mentioned low operating voltage organic field effect tube of preparation.
Low operating voltage organic field effect tube provided by the invention be a kind of by two-layer or two-layer above different semiconductors as raceway groove to form heterojunction device.Above-mentioned device architecture can realize that organic field effect tube is saturated under lower voltage, by the operating voltage of the saturated reduction organic field effect tube of low-voltage.
To achieve these goals, low operating voltage organic field effect tube provided by the invention, comprise substrate, gate electrode, insulating barrier, modifying semiconductor layer, bulk semiconductor layer, source electrode and drain electrode, form the organic semiconductor raceway groove by modifying semiconductor layer and organic main body semiconductor layer, its structure of organic semiconductor raceway groove is the modifying semiconductor layer below being, is the organic main body semiconductor layer above; Wherein:
Substrate, intercalation electrode lead-in wire on substrate;
Gate electrode, this gate electrode is produced on the one side of substrate, promptly deposits and pattern gate electrode gate electrode and contact conductor conducting on substrate;
Insulating barrier, this insulating barrier is produced on the another side of gate electrode;
The modifying semiconductor layer, this modifying semiconductor layer is produced on the another side of insulating barrier;
The bulk semiconductor layer, this bulk semiconductor layer is produced on the another side of modifying semiconductor layer;
Drain electrode and source electrode, drain electrode and source electrode are produced on the another side of bulk semiconductor layer.
Described low operating voltage organic field effect tube, wherein, described substrate be glass, pottery, polymer, silicon chip one of them.
Described low operating voltage organic field effect tube, wherein, described modifying semiconductor layer is as the key-course that reduces operating voltage, and its thickness is 0.5～50 nanometer.
Described low operating voltage organic field effect tube, wherein, described main body organic semiconductor is individual layer or bilayer, thickness is 20～200 nanometers.
Described low operating voltage organic field effect tube, wherein, the thickness of described drain electrode and source electrode metal layer is 30 nanometers～300 nanometers; Described channel length is 0.2 micron～150 microns.
The method of the above-mentioned low operating voltage organic field effect tube of preparation provided by the invention may further comprise the steps:
The first step, the deposition of gate metal:
On substrate, deposit layer of metal at least, obtain gate electrode;
Second step, the deposition of insulating barrier:
On gate electrode, adopt the insulating barrier thin film-forming method to deposit one deck insulating barrier at least;
The 3rd step, the deposition of the deposition of modifying semiconductor layer and organic main body semi-conducting material:
Depositing on the substrate of insulating barrier, deposition one deck modifying semiconductor layer adopts the organic substance film build method to obtain the main body organic semiconductor layer then, gets finished product.
Described preparation method, wherein, described substrate be glass, pottery, polymer, silicon chip one of them, earlier with ethanol, acetone ultrasonic cleaning, deionized water rinsing, through nitrogen dry up with oven for drying after deposition obtain gate electrode.
Described preparation method, wherein, described gate electrode, source electrode and electric leakage very have low-resistance material gold, silver, aluminium, copper metal and alloy material, metal conductive oxide material and/or conducing composite material.
Described preparation method, wherein, described deposition process is the various deposition processs of chemical vapour deposition (CVD), silk screen printing, coating of vacuum thermal evaporation, magnetron sputtering, plasma enhancing.
Described preparation method, wherein, described insulating layer material is silicon dioxide, silicon nitride, titanium dioxide, tantalum pentoxide, polymethyl methacrylate and/or the polyvinyl alcohol with good dielectric property; Chemical vapour deposition (CVD), the thermal oxidation that the film forming using plasma of insulating barrier strengthens, get rid of film or vacuum evaporation.
Described preparation method, wherein, described modifying semiconductor layer is to have the material of accepting or providing electronic capability, comprises that inorganic body and acceptor material, dye molecule, organic body and acceptor molecule, the macromolecule given given give body and acceptor material and their derivative or their mixture; The film forming of modifying semiconductor layer adopts vacuum evaporation, gets rid of film, drips film or printing.
Described preparation method, wherein, described main body organic semiconductor is the organic material with field effect behavior, comprises organic small molecule material, macromolecule polymer material or their mixtures; Main body adopts vacuum evaporation in the semi-conductive film forming of machine, gets rid of film, drips film or printing.
The present invention has and has following characteristics and advantage:
1, the organic field effect tube of the present invention's preparation can be controlled the character of conducting channel by the thickness of control modifying semiconductor layer, can realize the low voltage operating of organic field effect tube.
2, method disclosed by the invention is compared with other method, can utilize same prepared to obtain the organic field effect tube of controllable doped semiconductor channel.
3, method disclosed by the invention, semiconductor channel comprises two-layer at least, can change the composition of modifying semiconductor layer and organic main body semiconductor layer arbitrarily, is easy to prepare construct the low operating voltage field-effect transistor that is made of homojunction or heterojunction.In the controlled preparation of organic effect transistor and low-voltage organic semiconductor gate and integrated circuit, using value is arranged.
4, the invention has the advantages that, can on very thick insulating barrier (400 nanometers～500 nanometers), realize the low voltage operating of organic field effect tube, can accomplish with conventional semiconductor preparation technology compatible fully like this.
Description of drawings
Figure 1A, B, C and D are the organic material molecular formula of field-effect transistor of the present invention.
Fig. 2 is the structural representation of low-voltage organic field effect tube of the present invention.
Fig. 3 a and b are respectively based on CuPc (a) and F
16The curve of output of the high operation voltage organic field effect tube of CuPc (b) is as the contrast of low operating voltage organic field effect tube curve of output of the present invention.
Fig. 4 is the curve of output that the present invention is based on the low operating voltage organic field effect tube of TCNE and CuPc.
Fig. 5 is for the present invention is based on TCNE and F
16The curve of output of the low operating voltage organic field effect tube of CuPc.
Fig. 6 is the curve of output that the present invention is based on the low operating voltage organic field effect tube of BEDT TTF and CuPc.
Fig. 7 is for the present invention is based on BEDT TTF and F
16The curve of output of the low operating voltage organic field effect tube of CuPc.
Embodiment
Below in conjunction with accompanying drawing the present invention is described in detail, be to be noted that described embodiment only is intended to be convenient to the understanding of the present invention, and it is not played any qualification effect.
As Fig. 2 is the structural representation of low operating voltage organic field effect tube of the present invention: be followed successively by gate electrode 1, insulating barrier 2, modifying semiconductor layer 3, bulk semiconductor layer 4, source electrode 5 and drain electrode 6 from the bottom up.
Technical scheme of the present invention is to increase a raceway groove and be called the modifying semiconductor layer extra between insulating barrier 2 and the main body organic semiconductor layer 4 or between source electrode 5, drain electrode 6 and the bulk semiconductor layer 4, as the key-course that reduces operating voltage.The structure of this device comprises substrate, gate electrode 1, insulating barrier 2, modifying semiconductor layer 3, bulk semiconductor layer 4, source electrode 5 and drain electrode 6; It constructs insulating barrier 2, modifying semiconductor layer 3, bulk semiconductor layer 4, source electrode 5 and drain electrode 6 in turn after deposition and pattern gate electrode 1 on the substrate.
Its described substrate is that one of them is made by glass, pottery, polymer, silicon chip.
Its described gate electrode 1, source electrode 5 and drain electrode 6, be to constitute by having low-resistance material, comprise various metals and alloy materials such as gold, silver, aluminium, copper, metal oxide (as tin indium oxide) electric conducting material and conducing composite material (as gold size, elargol, carbon paste etc.), deposition process can be various deposition processs such as the chemical vapour deposition (CVD) that strengthens of vacuum thermal evaporation, magnetron sputtering, plasma, silk screen printing, coating.
Its described insulating barrier 2 materials have excellent dielectric properties, comprise inorganic insulating material such as silicon dioxide, silicon nitride, titanium dioxide, tantalum pentoxide, organic insulating material such as polymethyl methacrylate etc., polyvinyl alcohol etc., the preparation method can be the chemical vapour deposition (CVD), the thermal oxidation that strengthen of plasma, get rid of film or vacuum evaporation etc.
Described modifying semiconductor layer 3 is between insulating barrier 2 and main body organic semiconductor layer 4, as the key-course that reduces operating voltage.
Described modifying semiconductor layer 3, modifying semiconductor layer 3 is to have the material of accepting or providing electronic capability, comprises that inorganic body and acceptor material, dye molecule, organic body and acceptor molecule, the macromolecule given given give body and acceptor material and their derivative or their mixture.
Described modifying semiconductor layer 3, the film forming of modifying semiconductor layer 3 adopt vacuum evaporation, get rid of film, drip film, print the thin film-forming method preparation.Modifying semiconductor layer 3 can change the threshold voltage of device, perhaps makes organic field effect tube saturated under lower voltage, thereby realizes the reduction of organic field effect tube operating voltage.
Described main body organic semiconductor 4 adopts the organic material with field effect behavior, comprises organic small molecule material, macromolecule polymer material or their mixtures,
Described main body organic semiconductor layer 4 adopts vacuum evaporation, gets rid of film, drips film, prints thin film-forming method.
Described main body organic semiconductor layer 4 adopts individual layer or bilayer, adopts a kind of material or composite material.
The film build method of its described modifying semiconductor layer 3 and bulk semiconductor layer 4, for vacuum evaporation, get rid of film, drip film, printing; When organic substance is polymer, adopts and get rid of film, drip film, printing; During for micromolecule, adopt vacuum evaporation, get rid of film, drip film, impression, printing.
Described low operating voltage organic field effect tube is formed the organic semiconductor raceway groove by modifying semiconductor layer and organic main body semiconductor layer, and the structure of organic semiconductor raceway groove is the modifying semiconductor layer below being, is the organic main body semiconductor layer above.
Its described source electrode 5 and drain electrode 6 metal layer thickness are 30 nanometers～300 nanometers.Can select 30 nanometers or 100 nanometers or 200 nanometers or 300 nanometers as required
0.2 micron～150 microns of its described channel lengths.Can select 0.2 micron or 50 microns or 100 microns or 150 microns as required.
The present invention can make the operating voltage of organic field effect tube be reduced to 10V～30V from 60～100V under the prerequisite of not using ultra-thin or high-k insulating layer
Embodiment 1:
Shown in Figure 1 is the molecular formula that is used to prepare organic material of the present invention, is fluorine CuPc F
16CuPc (A), CuPc CuPc (B), TCNE TCNE (C) and acetylene two sulphur tetrathiafulvalene BEDT TTF (D).
Shown in Figure 2 be the structural representation of low operating voltage field-effect transistor of the present invention; Wherein: the bottom is a gate electrode 1, and its top is an insulating barrier 2, is respectively modifying semiconductor layer 3 and main body organic semiconductor layer 4 then, and its top is respectively source electrode 5 and drain electrode 6.
It is 50 microns to channel length L for example below, source electrode 5, drain electrode 6 are gold electrode, preparation based on organic field effect tube Fig. 2 of four cyano xyloquinone (TCNE) modifying semiconductor layer 3 and CuPc (CuPc) main body organic semiconductor layer 4 is illustrated, but the present invention is not limited thereto.
The preparation method of low operating voltage organic field effect tube provided by the invention comprises that following concrete step is as follows:
The first step, the preparation of gate electrode 1
After polycrystalline silicon substrate is ultrasonic through ethanol, acetone, deionized water rinsing, nitrogen dried up, oven dry realized heavily doped to form the gate electrode of conduction to substrate with diffusion technology then;
Second step, the deposition of insulating barrier 2
Silicon substrate is placed in the chemical gas-phase deposition system of plasma enhancing, deposition of silica, thickness are 450 nanometers, or 300 nanometers, or 350 nanometers, or 400 nanometers, or 500 nanometers.
The 3rd step, the deposition of modifying semiconductor layer 3
In vacuum degree is 4 * 10
-4Under the condition of Pa with
Speed evaporation TCNE, thickness is 3 nanometers, or selects 0.5 nanometer as required, or 5 nanometers, or 10 nanometers, or 20 nanometers.
The 4th step, the deposition of bulk semiconductor layer 4
In vacuum degree is 4 * 10
-4Under the condition of Pa with
Speed evaporation CuPc (CuPc), thickness is 50 nanometers, or selects 25 nanometers as required, or 75 nanometers, or 100 nanometers.
The 5th step, the preparation of source electrode 5, drain electrode 6
In vacuum degree is 1 * 10
-3Under the condition of Pa with
Speed by the template gold evaporation, thickness is 50 nanometers, obtains having the gold electrode of interdigital structure.
The 6th step, test
Utilize the HP4140B semi-conductor test instrument that device performance is tested.
Fig. 4 is 50 microns for channel length of the present invention, and source electrode 5, drain electrode 6 are the curve of output of the low operating voltage organic field effect tube of gold electrode.Can find out clearly that device is the field-effect transistor of p type from curve of output, operating voltage is reduced to about 10V, and compares (operating voltage about 80～100V volt) based on the device of individual layer CuPc among Fig. 3 a, and operating voltage has had significant reduction.
Embodiment 2:
Press the preparation of embodiment 1, unique different be that CuPc CuPc layer is replaced to fluorine CuPc F
16CuPc is deposited between TCNE modifying semiconductor layer and the gold electrode, and the device of this structure also presents the low voltage operating characteristic.
Fig. 5 is 50 microns for channel length of the present invention, and source electrode 5, drain electrode 6 are the curve of output of the low operating voltage organic field effect tube of gold electrode.From curve of output, can find out clearly that device is the field-effect transistor of n type, operating voltage be reduced to about 10V～15V and Fig. 3 b in based on individual layer fluorine CuPc F
16The operating voltage of the device of CuPc (about 60～100V volt) has been compared significant reduction.
Embodiment 3:
Press the preparation of embodiment 1, unique different be that main body organic semiconductor layer 4 is phthalocyanine nickel (NiPc), be the organic field effect tube that modifying semiconductor layer 3 has prepared low operating voltage with TCNE, the operating voltage of device is about 10～15V.
Embodiment 4:
Press the preparation of embodiment 1, unique different be that the thickness of modifying semiconductor layer 3TCNE is 10 nanometers, source electrode 5, drain electrode 6 are gold electrode, the operating voltage of device is about 10V.
Embodiment 5:
Press the preparation of embodiment 1, unique difference changes modifying semiconductor layer 3 into BEDT TTF, and bulk semiconductor layer 4 remains CuPc.
Fig. 6 is 50 microns for channel length of the present invention, and source electrode 5, drain electrode 6 are the curve of output of the low operating voltage organic field effect tube of gold electrode.Can find out clearly that device is the field-effect transistor of p type from curve of output, operating voltage is reduced to about 30V, and has compared significant reduction based on the device of individual layer CuPc CuPc among Fig. 3 a.
Embodiment 6:
Press the preparation of embodiment 2, unique difference changes modifying semiconductor layer 3 into BEDT TTF, and bulk semiconductor layer 4 remains fluorine CuPc F
16CuPc.
Fig. 6 is 50 microns for channel length of the present invention, and source electrode 5, drain electrode 6 are the curve of output of the low operating voltage organic field effect tube of gold electrode.From curve of output, can find out clearly that device is the field-effect transistor of n type, operating voltage be reduced to about 20V and Fig. 3 b in based on individual layer fluorine CuPc F
16The device of CuPc has been compared significant reduction.
Describing above is to be used to realize the present invention and embodiment, and those of ordinary skills can determine multiple implementation according to actual conditions, and therefore, scope of the present invention should not described by this and limit.It should be appreciated by those skilled in the art,, all belong to claim restricted portion of the present invention in any modification or partial replacement that does not depart from the scope of the present invention.
Claims (11)
1, a kind of low operating voltage organic field effect tube, comprise substrate, gate electrode, insulating barrier, modifying semiconductor layer, bulk semiconductor layer, source electrode and drain electrode, form the organic semiconductor raceway groove by modifying semiconductor layer and organic main body semiconductor layer, its structure of organic semiconductor raceway groove is the modifying semiconductor layer below being, is the organic main body semiconductor layer above; Wherein:
Substrate, intercalation electrode lead-in wire on substrate;
Gate electrode, this gate electrode is produced on the one side of substrate, promptly deposits and pattern gate electrode gate electrode and contact conductor conducting on substrate;
Insulating barrier, this insulating barrier is produced on the another side of gate electrode;
The modifying semiconductor layer, this modifying semiconductor layer is produced on the another side of insulating barrier;
The bulk semiconductor layer, this bulk semiconductor layer is produced on the another side of modifying semiconductor layer;
Drain electrode and source electrode, drain electrode and source electrode are produced on the another side of bulk semiconductor layer;
The thickness of described drain electrode and source electrode metal layer is 30 nanometers～300 nanometers;
Described organic semiconductor channel length is 0.2 micron～150 microns.
2, low operating voltage organic field effect tube as claimed in claim 1, wherein, described substrate be glass, pottery, polymer, silicon chip one of them.
3, low operating voltage organic field effect tube as claimed in claim 1, wherein, described modifying semiconductor layer is as the key-course that reduces operating voltage, and its thickness is 0.5～50 nanometer.
4, low operating voltage organic field effect tube as claimed in claim 1, wherein, described main body organic semiconductor is individual layer or bilayer, thickness is 20～200 nanometers.
5, prepare the method for the described low operating voltage organic field effect tube of claim 1, may further comprise the steps:
The first step, the deposition of gate metal:
On substrate, deposit layer of metal at least, obtain gate electrode;
Second step, the deposition of insulating barrier:
On gate electrode, adopt the insulating barrier thin film-forming method to deposit one deck insulating barrier at least;
The 3rd step, the deposition of the deposition of modifying semiconductor layer and main body organic semiconducting materials:
Depositing on the substrate of insulating barrier, deposition one deck modifying semiconductor layer adopts the organic substance film build method to obtain the main body organic semiconductor layer then.
6, preparation method as claimed in claim 5, wherein, described substrate be glass, pottery, polymer, silicon chip one of them, earlier with ethanol, acetone ultrasonic cleaning, deionized water rinsing, through nitrogen dry up with oven for drying after deposition obtain gate electrode.
7, preparation method as claimed in claim 5, wherein, described gate electrode, source electrode and electric leakage very have low-resistance material gold, silver, aluminium, copper metal and alloy material, metal conductive oxide material and/or conducing composite material.
8, preparation method as claimed in claim 5, wherein, described deposition process is the various deposition processs of chemical vapour deposition (CVD), silk screen printing, coating of vacuum thermal evaporation, magnetron sputtering, plasma enhancing.
9, preparation method as claimed in claim 5, wherein, described insulating layer material is silicon dioxide, silicon nitride, titanium dioxide, tantalum pentoxide, polymethyl methacrylate and/or the polyvinyl alcohol with good dielectric property; Chemical vapour deposition (CVD), the thermal oxidation that the film forming using plasma of insulating barrier strengthens, get rid of film or vacuum evaporation.
10, preparation method as claimed in claim 5, wherein, described modifying semiconductor layer is to have the material of accepting or providing electronic capability, comprises that inorganic body and acceptor material, dye molecule, organic body and acceptor molecule, the macromolecule given given give body and acceptor material or their mixture; The film forming of modifying semiconductor layer adopts vacuum evaporation, gets rid of film, drips film or printing.
11, preparation method as claimed in claim 5, wherein, described main body organic semiconductor is the organic material with field effect behavior, comprises organic small molecule material, macromolecule polymer material or their mixtures; Main body organic semi-conductor film forming adopts vacuum evaporation, gets rid of film, drips film or printing.
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| CN105336860A (en) * | 2015-11-09 | 2016-02-17 | 南京邮电大学 | Flexible low-voltage organic field effect transistor and manufacturing method thereof |
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| CN102110776B (en) * | 2010-12-03 | 2012-10-03 | 中国科学院化学研究所 | High-performance Organic field effect transistor and preparation method thereof |
| CN102255046B (en) * | 2011-05-25 | 2013-04-10 | 中国科学院化学研究所 | Transparent organic polymer insulating layer, preparation method thereof and application thereof to organic field effect transistor |
| CN103399072B (en) * | 2013-08-02 | 2015-04-29 | 中国科学院化学研究所 | Gas-assisted organic field-effect transistor sensor, and preparation method and applications thereof |
| CN110095522B (en) * | 2019-03-25 | 2022-01-25 | 同济大学 | Organic transistor chemical sensor for monitoring lithium battery electrolyte and preparation method thereof |
| CN113264933B (en) * | 2021-05-17 | 2022-06-17 | 济南大学 | Semiconductor material, field effect transistor device, bipolar semiconductor and application |
| CN115132923B (en) * | 2021-08-23 | 2023-10-17 | 天津大学 | Light stable organic field effect transistor |
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| US20050287697A1 (en) * | 2003-10-09 | 2005-12-29 | Canon Kabushiki Kaisha | Organic semicounductor device, process for producing the same, and organic semiconductor apparatus |
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