CN110854268B - Method for eliminating photoresponse of organic field effect transistor - Google Patents
Method for eliminating photoresponse of organic field effect transistor Download PDFInfo
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- CN110854268B CN110854268B CN201911105779.2A CN201911105779A CN110854268B CN 110854268 B CN110854268 B CN 110854268B CN 201911105779 A CN201911105779 A CN 201911105779A CN 110854268 B CN110854268 B CN 110854268B
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Abstract
The invention discloses a method for eliminating photoresponse of an organic field effect transistor. The method comprises the following steps: 1) selecting an insulating layer modification material with low defect density; wherein, the modifying material is a cheap polymer insulating layer material which is widely applied at present; 2) growing or transferring the substrate treated in the step 1) with a high-crystalline-quality crystal to prepare a transistor device. The invention can be used to prepare organic functional devices such as organic light emitting diode driven by organic field effect transistor, active matrix light emitting diode array, and organic logic circuit, and can be applied to large scale integrated circuit.
Description
Technical Field
The invention belongs to the field of semiconductors, and relates to a method for eliminating photoresponse of an organic field effect transistor.
Background
The light response characteristic of the field effect transistor is considered to be an expression of the intrinsic property of the semiconductor material, and in the transistor driving organic display circuit, the shift of the threshold voltage of the field effect transistor and the change of the output current caused by the light response directly affect the brightness of the light emitting diode. In the current industrialized transistor-driven organic display circuit, especially when the transistor and the diode are connected in series in an overlapped space mode, an electrode material with the thickness of about 100nm is generally required to be introduced as a shading layer, so as to avoid the mutual influence of the diode and the transistor.
Through the development of more than thirty years, the mobility, the stability of cycle test, the storage life and the like of the organic field effect transistor are obviously improved, and the organic field effect transistor reaches the index of driving the organic light emitting diode. However, the mobility distribution of the thin film device of the organic field effect transistor is wide, and most organic semiconductor materials have certain photoresponse, which are main factors limiting the application of the organic field effect transistor in an organic display circuit.
In past research, it has been considered that the photoresponse of organic field effect transistors is an expression of the intrinsic properties of the material. However, the exciton confinement energy of the organic material is higher by one order of magnitude than that of the inorganic material, which means that the exciton is not easily separated into free electron and hole, which means that the electrical properties of the organic semiconductor material are not easily affected by light, and is contrary to the phenomenon observed in the previous experiment. Finding the causes of the photoresponse of the organic field effect transistor and eliminating the factors is crucial to the preparation of the organic field effect transistor with good photostability, and can promote the application of the organic field effect transistor in an ultra-flexible, ultra-thin and transparent organic display circuit.
Disclosure of Invention
The invention aims to provide a method for eliminating the photoresponse of an organic field effect transistor, and the universality of the method is proved so as to promote the application of the organic field effect transistor in an ultrathin, ultra-flexible and transparent organic display circuit.
The invention provides a method for eliminating photoresponse of an organic field effect transistor, which comprises the following steps:
1) cleaning and drying the gate electrode;
2) preparing a high polymer insulating layer on the gate electrode treated in the step 1);
3) preparing an active semiconductor layer on the polymer insulating layer obtained in the step 2) or transferring the prepared active semiconductor layer to the polymer insulating layer obtained in the step 2) by adopting a physical transfer method;
the active semiconductor layer is a single crystal;
4) and preparing a source electrode and a drain electrode on the active semiconductor layer to eliminate the photoresponse of the organic field effect transistor.
In the cleaning step in the step 1), the cleaning agent is at least one selected from deionized water, concentrated sulfuric acid, hydrogen peroxide and organic solvent; the organic solvent is specifically selected from at least one of acetone and isopropanol; the volume ratio of the concentrated sulfuric acid to the hydrogen peroxide is specifically 7: 3; the cleaning is to sequentially use deionized water, acetone and isopropanol for cleaning; the cleaning mode is ultrasonic cleaning;
the blow-drying is nitrogen blow-drying.
For the substrate with the gate electrode, the cleaning can be directly carried out according to the steps;
for the material without the gate, the gate electrode may be patterned by a conventional method such as vapor deposition, and then cleaned according to the above steps.
That is, the method further includes: preparing a gate electrode on a substrate before the step 1);
the method for preparing the gate electrode specifically comprises various deposition methods such as an evaporation method, magnetron sputtering, plasma enhanced chemical vapor deposition and the like.
The material of the gate electrode may be a low resistance material, and may be at least one selected from various metals and alloy materials such as gold, silver, aluminum, and copper, and a metal oxide (e.g., indium tin oxide) conductive material.
The substrate used for preparing the gate electrode can be a hard substrate or a flexible substrate; the adhesive tape can be selected from any one of glass, silicon wafers, flexible glass, adhesive tapes, PEN, PI, PMMA and PS; specifically, the silicon substrate can be silicon dioxide/silicon substrate;
in the step 2), the material for forming the polymer insulating layer is a low-defect material; specifically at least one selected from CYTOP, BCB, PMMA, PS, PSs, PI, perylene and PVA;
the step of preparing the high-molecular insulating layer comprises spin coating and annealing;
the thickness of the polymer insulating layer is 20-500 nm; specifically, the molecular weight can be 200-300nm or 60 nm; in the step 3), the material for forming the active semiconductor layer is at least one selected from the group consisting of acenes, phthalocyanines, porphyrins, benzothiophenes and perylene bisimide compounds; the acenes are specifically selected from at least one of pentacene, tetracene, rubrene, 2, 6-diphenylanthracene and 2, 6-distyrylanthracene; the phthalocyanine is specifically selected from at least one of copper phthalocyanine, perfluorinated copper phthalocyanine, zinc phthalocyanine and titanyl phthalocyanine; the porphyrin is specifically selected from at least one of benzoporphyrin, metal substituted benzoporphyrin, alkyl substituted porphyrin, aryne substituted porphyrin and zinc substituted aryne substituted porphyrin;
the method for preparing the active semiconductor layer is various conventional methods such as an evaporation method, a spin coating method, a physical vapor deposition method, or a solution method; the solution method is specifically various conventional dripping methods, pulling methods or shearing methods;
the thickness of the active semiconductor layer is 20-100 nm; specifically 25nm or 25-40nm or 40-60 nm.
The physical transfer is a conventional method, and specifically may be the transfer of a single crystal onto a target substrate by probe micromanipulation.
The above-described methods for obtaining a single-crystal active semiconductor layer are all conventional methods.
In the step 4), the source and drain electrodes may be prepared by using various conventional organic wire mask methods or gold film-attaching methods.
The invention also claims an organic field effect transistor, which sequentially comprises a substrate, a gate electrode, a high polymer insulating layer, an active semiconductor layer and a source drain electrode positioned on the active semiconductor layer from bottom to top.
In the organic field effect transistor on the market, the substrate is selected from any one of glass, silicon wafers, flexible glass, adhesive tapes, PEN, PI, PMMA and PS;
the material for forming the high polymer insulating layer is a low-defect material; specifically at least one selected from CYTOP, BCB, PMMA, PS, PSs, PI, perylene and PVA;
the thickness of the polymer insulating layer is 20-500 nm; specifically, the molecular weight can be 200-300nm or 60 nm;
the material for forming the active semiconductor layer is selected from at least one of acene compounds, phthalocyanine compounds, porphyrin compounds, benzothiophene compounds and perylene imide compounds; the acenes are specifically selected from at least one of pentacene, tetracene, rubrene, 2, 6-diphenylanthracene, 2, 6-distyrylanthracene and C8-BTBT; the phthalocyanine is specifically selected from at least one of copper phthalocyanine, perfluorinated copper phthalocyanine, zinc phthalocyanine and titanyl phthalocyanine; the porphyrin is specifically selected from at least one of benzoporphyrin, metal substituted benzoporphyrin, alkyl substituted porphyrin, aryne substituted porphyrin and zinc substituted aryne substituted porphyrin;
the thickness of the active semiconductor layer is 20-100 nm; specifically 25nm or 25-40nm or 40-60 nm.
In addition, the application of the method for eliminating the photoresponse of the organic field effect transistor in the preparation of at least one of the organic field effect transistor, the organic field effect transistor driving organic light emitting diode, the active matrix light emitting diode array, the organic logic circuit and the large scale integrated circuit, and the organic field effect transistor driving organic light emitting diode, the active matrix light emitting diode array, the organic logic circuit and the large scale integrated circuit prepared by the method also belong to the protection scope of the invention.
The organic field effect transistors are characterized by all having photostability.
The invention has the following characteristics and advantages:
1. the material used for the high-molecular insulating layer is a common polymer dielectric layer material, is cheap and easy to obtain, and is simple to prepare;
the single crystals used by the active semiconductor layer are rich in variety, the preparation method is various, and the processing is convenient;
2. the method is simple and has good universality; the mechanism has universality;
3. provides good technical support for the application of the organic field effect transistor in the organic display circuit.
Drawings
Fig. 1 is a graph showing the photoresponse characteristics of transistor devices obtained by depositing a 2, 6-Diphenylanthracene (DPA) thin film, which is an organic material, on a silica substrate at different deposition rates according to examples of the present invention.
FIG. 2 is a graph showing the photoresponse characteristics of 2, 6-Diphenylanthracene (DPA) thin films, an organic material, on various modified substrates, according to examples of the present invention.
Fig. 3 shows the photoresponse characteristics of thin film transistor devices on differently modified insulating substrates.
Fig. 4 shows the structure of the active semiconductor layer material, the structure of the device and the electric-to-light emission spectrum of the light emitting diode according to the present invention.
FIG. 5 is a graph of the photoresponse characteristics of single crystal devices on various substrates prepared in accordance with the present invention.
Fig. 6 shows that different series transistor devices prepared by the invention drive light emitting diode devices, and light output consistent with a parallel structure and a laminated structure is obtained under certain conditions.
FIG. 7 shows the photoresponse characteristics of single crystal devices of copper perfluorophthalocyanine prepared by physical vapor transport on different substrates.
FIG. 8 shows the photoresponse characteristics of single crystal devices of perfluorophthalocyanine copper on different substrates prepared by the solution dropping method.
Detailed Description
The present invention will be further illustrated with reference to the following specific examples, but the present invention is not limited to the following examples. The method is a conventional method unless otherwise specified. The starting materials are commercially available from the open literature unless otherwise specified.
The method for eliminating the photoresponse of the organic field effect transistor, provided by the invention, can be used for preparing the organic field effect transistor with good illumination stability and also can be used for preparing an organic light-emitting diode based on the drive of the organic field effect transistor, and the method for eliminating the photoresponse of the organic field effect transistor can be widely applied to a flexible display circuit. The active matrix organic light emitting diode is based on the integration of a field effect transistor and a light emitting diode. The method provided by the invention can be used for preparing the transistor device with good light stability so as to ensure stable current output, and the stable work of the transistor device serving as a driving tube also ensures the stable light intensity output of the light-emitting diode.
The organic field effect transistor comprises a substrate, a gate electrode, an insulating layer, a source electrode, a drain electrode and an organic semiconductor layer.
The organic field effect transistor driving light-emitting diode comprises a substrate, a gate electrode, an insulating layer, a source electrode, a drain electrode, an organic semiconductor layer, an interconnection lead, a substrate related to the light-emitting diode, an anode, a hole transport layer, a light-emitting layer, an electron transport layer and a cathode.
The substrate of the organic field effect transistor is made of any one of the following materials: glass, ceramic, polymer, and silicon wafers.
The gate electrode of the organic field effect transistor is made of materials with low resistance, and comprises various metals and alloy materials such as gold, silver, aluminum, copper and the like, organic conductive materials such as graphite, carbon tubes, conductive polymers and the like, and metal oxide (such as indium tin oxide) conductive materials. The method for preparing the grid electrode on the substrate can adopt various deposition methods such as vacuum thermal evaporation, magnetron sputtering, plasma enhanced chemical vapor deposition and the like.
The organic field effect transistor drives the organic light emitting diode, and the insulating layers of the organic field effect transistor are all made of insulating materials with good dielectric property and surface property. The preparation method is realized by spin coating organic polymer and the like. The active layer materials of the light emitting diode are all prepared by vacuum evaporation.
The organic semiconductor layer of the transistor part of the organic field effect transistor and the transistor driving diode is made of organic semiconductor materials with field effect performance, and the organic semiconductor layers comprise organic micromolecule materials, high polymer materials or mixtures thereof. The film forming method can be vacuum evaporation, spin coating, film dropping, printing, physical vapor deposition and other technologies.
The preparation of the source and drain electrodes in the organic field effect transistor and the gate electrode, the source electrode and the drain electrode in the organic light-emitting diode driven by the organic field effect transistor are obtained by vacuum evaporation or physical transfer, and the electrode material of the light-emitting diode part is obtained by vacuum evaporation. The electrodes of the two devices are interconnected by connecting copper wires through silver adhesive dotted lines.
The method for eliminating the photoresponse of the organic field effect transistor comprises the following steps:
the first step is as follows: cleaning of substrate with gate electrode and patterning of gate electrode thereof
For the substrate with the gate electrode, the substrate deposited with the gate electrode is subjected to ultrasonic cleaning by deionized water, acetone and isopropanol in sequence and then is dried by nitrogen.
For the material without the grid, the grid electrode is patterned by methods such as evaporation plating, and then the substrate with the patterned grid electrode is subjected to ultrasonic cleaning by deionized water, acetone and isopropanol in sequence and then is dried by nitrogen.
The second step is that: preparation and treatment of polymer insulating layer
And spin-coating a polymer solution on the gate electrode of the substrate cleaned in the first step at a certain rotating speed, and then carrying out heating annealing treatment to obtain a continuous and uniform insulating layer.
The third step: preparation of an organic semiconductor layer
1) Placing an organic semiconductor active material in a vacuum evaporation chamber, and carrying out vacuum evaporation on the active material with the thickness of 50 nm; 2) the polymer material capable of being processed by solution can adopt a spin coating method, and the proper concentration and rotating speed are adjusted to prepare an active layer with the thickness of 50 nm; 3) growing or physically transferring a single crystal of the organic small molecule material in situ on the substrate as an active layer by a physical vapor transport method. 4) The single crystal of the organic small molecule material is prepared in situ as an active layer by a solution method such as a dropping method, a shearing method, a pulling method, and the like.
The fourth step: preparation of source-drain electrode
Preparing a source electrode and a drain electrode by using a template mask method and a vacuum evaporation method for the film type active layer; and preparing the source and drain electrodes for the monocrystal active layer by adopting an organic wire mask evaporation or electrode pasting method.
The fifth step: preparation of light emitting diodes
By using a vacuum evaporation method, HATCN with the thickness of 10nm, HTL1 with the thickness of 50nm, HTL2 with the thickness of 5nm, BH with the thickness of 20 nm: BD (97:3), ET with the thickness of 30 nm: Liq (50: 50), Liq with the thickness of 1nm and aluminum electrodes with the thickness of 100nm are evaporated on ITO glass in sequence.
And a sixth step: interconnection of field effect transistors and light emitting diodes
The drain electrode of the transistor device and the anode of the light emitting diode are extended, the silver dispensing glue is connected with the copper wire, and the two electrodes are connected.
The seventh step: device testing
Driving the prepared organic field effect transistor and interconnected field effect transistor to a light emitting diode device in an atmospheric environment (10)5Pa) room temperature (298K).
In the first step, the substrate is a substrate such as ITO glass, silicon or flexible 3M adhesive tape. The organic polymer film of the insulating layer can be prepared by adopting a spin coating film forming method. In the third step, the material can be prepared by vacuum evaporation, spin coating, physical vapor transport or solution method, etc. according to different material types. The fourth step of preparing the source-drain electrode can be prepared by a method of vacuum evaporation or electrode pasting; and fifthly, obtaining each active layer by adopting a device structure of the light-emitting diode which is commercialized at present and sequentially adopting a vacuum evaporation method. And sixthly, connecting the two device structures in series through an auxiliary point silver adhesive connecting copper wire of the microscope.
The present invention will be described below with reference to specific examples, but the present invention is not limited thereto.
The experimental methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials are commercially available, unless otherwise specified.
Example 1
In this embodiment, for a silicon dioxide (300 nm)/silicon substrate having an insulating layer and a gate electrode, the selected dielectric layer modification materials are OTS (comparative modification layer), PS, PMMA and CYTOP (thickness in the range of 20-500 nm), and the semiconductor is based on a 2, 6-Diphenylanthracene (DPA) film (comparative test).
The first step is as follows: cleaning of substrate with gate electrode
For an organic field effect transistor, a two-step silicon oxide/silicon substrate with a surface oxide layer (thickness of 300nm) is sequentially treated with deionized water, concentrated sulfuric acid: hydrogen peroxide (7: 3), deionized water and isopropanol are ultrasonically cleaned, and then the nitrogen is dried.
For the organic light emitting diode, commercially available ITO glass (oxide layer 150nm) is directly subjected to ultrasonic cleaning by deionized water, acetone and isopropanol in sequence and then is subjected to nitrogen blow-drying.
The second step is that: preparation and treatment of polymer insulating layer
Vacuumizing and heating the surface of the cleaned substrate in the first step for 90 ℃, keeping the temperature for 90min, dripping a drop of OTS into a culture dish after cooling to room temperature, heating to 120 ℃ in vacuum, keeping the temperature for 120min, and cooling to room temperature. And ultrasonically washing the modified substrate by using n-hexane, trichloromethane and isopropanol in sequence to obtain the OTS modified substrate.
Spin coating 1: 3, spin-on for 50 s. Thereafter, the substrate was heated at 120 ℃ for 15min in a nitrogen atmosphere to obtain a CYTOP (200nm) modified substrate.
Preparing a PMMA chlorobenzene solution with the concentration of 80mg/mL, spin-coating for 50s at the rotating speed of 6000rmp, and then keeping the temperature at 80 ℃ in vacuum for 60min to obtain a PMMA (300nm) modified substrate.
Preparing 40mg/mL PS toluene solution, spin-coating at 8000rmp for 50s, and vacuum-coating at 80 deg.C for 60min to obtain PS (300nm) modified substrate.
Third step of preparing an organic semiconductor layer
The semiconductor active material is placed in a quartz boat and placed in a vacuum evaporation chamber. Vacuum pumping is carried out to 8 x 10-4Pa, followed by depositing the active material onto the substrate by heating and monitoring the thickness of the deposited active layer by means of a crystal oscillator plate.
The specific preparation conditions are as follows: the control of the evaporation speed is realized by controlling the current, so as to realize the control
And obtaining the semiconductor active layer with the thickness of 50nm on the bare silicon dioxide/silicon substrate at different evaporation rates. And pass through
The evaporation rate of (A) in OTS, PS, PMMA, CYTOA semiconductor active layer with a thickness of 50nm was obtained on the P substrate.
The fourth step: preparation of source-drain electrode
The source and drain electrodes are directly prepared on the semiconductor active layer by using a vacuum evaporation mode through a mask (with the length of 80 mu m and the width of 30 mu m).
The fifth step: and testing the optical response of the device.
We have found that DPA is in SiO2OFETs (a in figure 1) prepared on the dielectric layer have strong photoresponse, and b, 1c and 1d in figure 1 are transfer curves of the OFETs under different light intensity irradiation, when the incident light intensity is from 0.1mW/cm2To 0.6mW/cm2When the voltage changes, the photocurrent increases, and the threshold voltage VTThe absolute value of (a) becomes smaller. The change in photocurrent is due to the difference in the number of photogenerated carriers generated by the DPA molecules under different illumination. We found that the threshold voltage of OFETs is larger in the dark state. The shift in threshold voltage Δ V in addition to the photosensitive value (Pphotoproduction current/dark state current)TIt is also an important embodiment of the OFET optical response, and this parameter has a large influence on the output current of the field effect transistor, thereby affecting the light intensity output of the light emitting diode.
We have found that by varying the DPA evaporation rate, the photoresponse intensity changes. XRD testing of DPA films revealed the degree of crystallinity within the film, i.e., the degree of order of the molecular arrangement, as shown in FIG. 1 f, the narrower the FWHM indicates the higher the degree of order of the film, and it was observed that the relationship between the degree of order of the film at different vaporization rates, which corresponds to the relationship between the magnitude of the mobility shown in FIG. 1 e, was consistent with that at the vaporization rate shown in FIG. 1 e
The film has the highest degree of order and the smallest P and delta VT。
Furthermore, we found that there is a great difference in the OFET photo-response for the same evaporation conditions but different dielectric layers. For example, a, b, c, d in fig. 2 show that OFETs are prepared by evaporating DPA active layer under the same conditions on a substrate with different modification layers such as OTS, PS, PMMA, CYTOP, etc. Δ VTAnd P in relation to the dielectric layer interface as shown in FIG. 3It can be seen that Δ VTThe change rule of P is basically consistent with that of OFET, and the optical response intensity of OFET is reflected. The optical response of the device prepared on the OTS substrate is very strong and is 0.6mW/cm2Delta V under white light irradiationT91V is reached, and the maximum photosensitive value P reaches 9.76 multiplied by 105(ii) a The light response of the PS, PMMA and CYTOP devices is weakened and is 0.6mW/cm2Delta V under white light irradiationT6V, 16V and 10V respectively, and the maximum photosensitive value P reaches 109, 380 and 20 respectively.
We therefore conclude that a highly ordered thin film fabricated with low defect density can effectively reduce the photoresponse of field effect transistor devices. And the defects of the interface of the substrate and the semiconductor layer are reduced, and the optical response of the field effect transistor can be reduced or even eliminated by improving the order degree of the active layer.
Example 2
In this embodiment, for a silicon dioxide (300 nm)/silicon substrate having an insulating layer and a gate electrode, the selected polymer thin film layer materials are OTS (contrast modification layer), PS, PMMA and CYTOP (thickness is in the range of 20-500 nm), and the active semiconductor layer is based on 2, 6-diphenylanthracene single crystal (thickness is in the range of 20-100 nm).
The first step is as follows: cleaning of substrate with gate electrode
For an organic field effect transistor, a two-step silicon oxide/silicon substrate with a surface oxide layer (thickness of 300nm) is sequentially treated with deionized water, concentrated sulfuric acid: hydrogen peroxide (7: 3), deionized water and isopropanol are ultrasonically cleaned, and then the nitrogen is dried.
The second step is that: preparation and treatment of polymer insulating layer
Vacuumizing and heating the surface of the cleaned substrate in the first step for 90 ℃, keeping the temperature for 90min, dripping a drop of OTS into a culture dish after cooling to room temperature, heating to 120 ℃ in vacuum, keeping the temperature for 120min, and cooling to room temperature. And ultrasonically washing the modified substrate by using n-hexane, trichloromethane and isopropanol in sequence to obtain the OTS modified substrate.
Spin coating 1: 3, spin-on for 50 s. Thereafter, the substrate was heated at 120 ℃ for 15min in a nitrogen atmosphere to obtain a CYTOP (200nm) modified substrate.
Preparing a PMMA chlorobenzene solution with the concentration of 80mg/mL, spin-coating for 50s at the rotating speed of 6000rmp, and then keeping the temperature at 80 ℃ in vacuum for 60min to obtain a PMMA (300nm) modified substrate.
Preparing 40mg/mL PS toluene solution, spin-coating at 8000rmp for 50s, and vacuum-coating at 80 deg.C for 60min to obtain PS (300nm) modified substrate.
Third step of preparing an active semiconductor layer
A powder sample of 2, 6-diphenylanthracene is placed in a high-temperature zone of a tube furnace and a substrate is placed in a low-temperature deposition zone by a physical vapor transport method. Vacuumizing and introducing inert gas, wherein the vacuum degree range is 2-50 Pa; the inert gas can be argon or nitrogen; the flow rate can be 5sccm-40 sccm; the temperature of the high temperature zone is 150-200 ℃, and the holding time is 1-6 hours.
The fourth step: preparation of source-drain electrode
By using an organic wire mask mode, taking an organic wire as a sacrificial template, carrying out vacuum evaporation on 40nm gold, and then removing the organic wire to obtain a source-drain electrode pair; or two deposited gold films with the thickness of 100nm-130nm are placed on the crystal by a physical transfer method to obtain a source-drain electrode pair.
The fifth step: for the organic light emitting diode, commercially available ITO glass (oxide layer 150nm) is directly subjected to ultrasonic cleaning by deionized water, acetone and isopropanol in sequence and then is subjected to nitrogen blow-drying. Then placed in a vacuum evaporation chamber to evaporate 10nm HATCN, 50nm HTL1, 5nm HTL2, 20nm BH: BD (97:3),30nm ET: Liq (50: 50), 1nm Liq and 100nm aluminum electrodes in sequence (as shown in FIG. 4).
And a sixth step: interconnection of field effect transistors and light emitting diodes
The drain electrode of the transistor device and the anode of the light emitting diode are extended, the silver dispensing glue is connected with the copper wire, and the two electrodes are connected.
The seventh step: and testing the optical response of the device.
The molecular arrangement in the organic single crystal is long-range ordered, internal defects are few, and the insulating layer hardly influences the molecular arrangement through physical transfer, so that the organic single crystal is differentThe single crystal device of 2, 6-diphenylanthracene prepared on the insulating layer has uniform influence of the active layer on the photoresponse. Fig. 5 shows the transfer curves of 2, 6-diphenylanthracene single crystal transistor devices at different interfaces under different illumination conditions. Single crystal devices based on OTS interface, although the active layer is a highly ordered DPA single crystal, at 0.6mW cm-2P under light intensitymaxStill as high as 2.4 x 104A W-1，ΔVTReaches 19.2V (V)DSConstant pressure of-40V); whereas single-crystal devices based on polymer-insulating layers, the photoresponse of which becomes extremely weak, PmaxLess than 20 and the threshold voltage is hardly shifted. When interconnecting transistor devices with light emitting diode devices, especially when both device configurations are of the stacked type, the devices on the polymer substrate have better light stability, i.e., more stable output of luminous intensity, as shown in fig. 5.
Example 3
The method adopted in this example is the same as that of example 2, and the active semiconductor layer material used is perfluorophthalocyanine copper with a thickness of 40-60 nm.
FIG. 7 shows the dark state and 0.6mW cm of single crystal transistors of perfluorophthalocyanine copper on different substrates-2The transfer curve at light intensity shows that the optical response of the device is effectively eliminated on the polymer insulating layer.
Example 4
In this embodiment, for a silicon dioxide (300 nm)/silicon substrate having an insulating layer and a gate electrode, the selected material for the polymer thin film layer is BCB, and the active semiconductor layer is based on C8-BTBT.
The first step is as follows: cleaning of substrate with gate electrode
For an organic field effect transistor, a two-step silicon oxide/silicon substrate with a surface oxide layer (thickness of 300nm) is sequentially treated with deionized water, concentrated sulfuric acid: hydrogen peroxide (7: 3), deionized water and isopropanol are ultrasonically cleaned, and then the nitrogen is dried.
The second step is that: preparation and treatment of polymer insulating layer
In a glove box, BCB in mesitylene was spin coated onto the substrate at 2000rmp for 60 s. Then, the substrate was heated at 260 ℃ for 1 hour in a nitrogen atmosphere to obtain a BCB (thickness: 60nm) -modified substrate.
Third step of preparing an active semiconductor layer
Crystals of C8-BTBT were prepared by drop-casting at a substrate temperature of 40 degrees by a drop-casting method to a thickness in the range of 25-40 nm.
The fourth step: preparation of source-drain electrode
By using an organic wire mask mode, taking an organic wire as a sacrificial template, carrying out vacuum evaporation on 40nm gold, and then removing the organic wire to obtain a source-drain electrode pair; or two deposited gold films with the thickness of 100nm-130nm are placed on the crystal by a physical transfer method to obtain a source-drain electrode pair.
The other steps are similar to example 2.
FIG. 8 shows the prepared polymer substrate-based C8-BTBT transistor and OTS-based transistor devices in the dark state and 0.6mW cm-2The transfer curve at light intensity indicates that the optical response of the device is effectively eliminated on the polymer insulating layer.
Claims (7)
1. A method of eliminating the photoresponse of an organic field effect transistor, comprising:
1) cleaning and drying the gate electrode;
2) preparing a high polymer insulating layer on the gate electrode treated in the step 1);
in the step 2), the material for forming the polymer insulating layer is a low-defect material, and is selected from at least one of CYTOP, BCB, PMMA, PS, PSs, PI, perylene and PVA;
3) preparing an active semiconductor layer on the polymer insulating layer obtained in the step 2) or transferring the prepared active semiconductor layer to the polymer insulating layer obtained in the step 2) by adopting a physical transfer method;
the active semiconductor layer is a single crystal;
4) and preparing a source electrode and a drain electrode on the active semiconductor layer to eliminate the photoresponse of the organic field effect transistor.
2. The method of claim 1, wherein: in the cleaning step of the step 1), the cleaning agent is selected from at least one of deionized water, concentrated sulfuric acid, hydrogen peroxide and an organic solvent; the organic solvent is specifically selected from at least one of acetone and isopropanol; the cleaning is to sequentially use deionized water, acetone and isopropanol for cleaning; the cleaning mode is ultrasonic cleaning;
the blow-drying is nitrogen blow-drying.
3. The method according to claim 1 or 2, characterized in that: the method further comprises the following steps: preparing a gate electrode on the substrate before the step 1).
4. The method according to claim 1 or 2, characterized in that: in the step 2) of the said step,
the step of preparing the high-molecular insulating layer comprises spin coating and annealing;
the thickness of the polymer insulating layer is 20-500 nm.
5. The method according to claim 1 or 2, characterized in that: in the step 3), the material for forming the active semiconductor layer is at least one selected from the group consisting of acenes, phthalocyanines, porphyrins, benzothiophenes and perylene bisimide compounds;
the method for preparing the active semiconductor layer is an evaporation method, a spin coating method, a physical vapor deposition method or a solution method;
the thickness of the active semiconductor layer is 20-100 nm.
6. The method of claim 5, wherein: the acenes are selected from at least one of pentacene, tetracene, rubrene, 2, 6-diphenylanthracene and 2, 6-distyrylanthracene; the phthalocyanine is selected from at least one of copper phthalocyanine, perfluorinated copper phthalocyanine, zinc phthalocyanine and titanyl phthalocyanine; the porphyrin is selected from at least one of benzoporphyrin, metal substituted benzoporphyrin, alkyl substituted porphyrin, aryl alkynyl substituted porphyrin and zinc substituted aryl alkynyl substituted porphyrin;
the solution method is a dripping method, a pulling method or a shearing method;
the thickness of the active semiconductor layer is 25 nm.
7. Use of the method of any of claims 1-6 for preparing at least one of an organic field effect transistor having photostability, an organic field effect transistor driving organic light emitting diode, an active matrix light emitting diode array, an organic logic circuit, and a large scale integrated circuit.
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