CN117580380B - Organic heterojunction vertical phototransistor and preparation method thereof - Google Patents
Organic heterojunction vertical phototransistor and preparation method thereof Download PDFInfo
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Abstract
An organic heterojunction vertical phototransistor and a method of fabricating the same, the phototransistor comprising: the device comprises a gate electrode, a dielectric layer, a silver nanowire source electrode formed on the dielectric layer, a bulk heterojunction formed on the source electrode, and a light-transmitting drain electrode formed on the bulk heterojunction, wherein the bulk heterojunction is formed by mixing a P-type polymer PDVT-10 solution with the concentration of 10g/L and an n-type micromolecule Y6 solution according to the volume ratio of 8:2; the silver nanowire source electrode was formed by spin-coating a dielectric layer with 0.5g/L silver nanowire solution. The PDVT-10:Y6 bulk heterojunction generates a large number of photo-generated excitons which are dissociated into holes and electrons and are not combined to generate photocurrent; the appropriate density of the silver nanowire source electrode ensures that the source electrode can not shield the regulation and control capability of the grid voltage to the source leakage current, forms a source electrode network and ensures the injection of carriers; the advantages of the vertical structure and the bulk heterojunction are combined, so that the light detection performance of the organic photoelectric transistor is greatly improved compared with that of the traditional structure.
Description
Technical Field
The present invention relates to the field of transistors, and more particularly, to an organic heterojunction vertical phototransistor and a method of fabricating the same.
Background
Most of the current research in the fabrication of high performance phototransistors is focused on light absorbing materials and most are based on parallel structures, but the relatively large channel length (typically on the order of microns or more) in parallel structures is an inherent disadvantage. In fact, the conventional parallel structure generally requires a high-precision photolithography process, and due to the limitation of the geometry of the device and the current technology, it is difficult to further shorten the channel of the device to the nanometer level, which results in low current density and low operation speed of the device; and the longer channel length not only leads to long transit time of photo-generated carriers, but also increases the probability of electron-hole recombination after separation, thereby reducing the photoelectric performance of the device and limiting the practical application of the photoelectric transistor in a plurality of fields. Vertical Field Effect Transistors (VFETs) have been widely studied as a new device structure in recent decades, and their channel lengths can be easily scaled down to tens of nanometers or even a single layer scale; in addition, the transport direction of carriers in the VFETs channel is parallel to the direction of an electric field generated by the grid electrode and the source electrode, so that the VFETs can provide higher current density and working frequency in principle, and the practical application of the VFETs in integrated circuits, backboard LED displays and the like is ensured.
With the continuous change of market demand, inorganic field effect transistors show defects in some scenes, such as: the silicon-based transistor needs high temperature and fine micro-nano processing technology, and needs to consume a great deal of cost; inorganic materials are often poorly ductile, brittle, and cannot be integrated on a large scale in flexible displays; for the infrared light detection region, the performance of most silicon semiconductor materials is still unsatisfactory, etc. The organic semiconductor has the characteristics of low cost, simple preparation, flexibility and the like, exactly overcomes the defects of inorganic materials, and has great application potential in the fields of flexible electronics, electronic skin, photoelectric detection and the like.
However, the use of a single organic semiconductor in a phototransistor has also been limited. First, the dielectric constant of organic semiconductors is typically low, which allows them to generate highly localized, tightly bound Frenkel excitons (electron-hole pairs) under light conditions, forming binding energies up to 0.3-1eV, resulting in lower dissociation efficiency of photogenerated excitons and lower photogenerated current of the device. In addition, the low mobility of organic semiconductors is also an important factor limiting the development of phototransistors.
Disclosure of Invention
The invention provides an organic heterojunction vertical phototransistor and a preparation method thereof, wherein an organic heterojunction is integrated into VFETs, the vertical organic phototransistor is prepared, a proper amount of Y6 is added into PDVT-10 to form a bulk heterojunction so as to prepare a high-performance vertical phototransistor, the PDVT-10:Y6 bulk heterojunction has larger LUMO and HOMO energy extremely poor, and a large amount of generated photo-generated excitons can be guaranteed to be dissociated into holes and electrons and not to be compounded, so that photocurrent is generated; meanwhile, the source electrode can not shield most of the regulation and control capability of grid voltage to source leakage current by selecting proper density of the silver nanowire source electrode, and meanwhile, a source electrode network can be formed, carrier injection is ensured, and larger on-state current density is formed; the advantages of the vertical structure and the bulk heterojunction are combined, so that the light detection performance of the organic photoelectric transistor is greatly improved compared with that of a light detector with a traditional structure.
In one aspect, the present invention provides an organic heterojunction vertical phototransistor comprising: the organic heterojunction is formed on the silver nanowire source electrode, and the light-transmitting drain electrode is formed on the organic heterojunction, wherein the organic heterojunction is formed by a P-type polymer PDVT-10 and an n-type small molecule Y6; the structural formula of the P-type polymer PDVT-10 is shown as formula I:
one (I)
The structural formula of the n-type small molecule Y6 is shown as a formula II:
two kinds of
The organic heterojunction is formed by mixing a P-type polymer PDVT-10 solution and an n-type micromolecule Y6 solution with the concentration of 10g/L according to the volume ratio of 8:2; the silver nanowire source electrode is formed by spin coating 0.5g/L silver nanowire solution on the dielectric layer.
Further, the solvent of the P-type polymer PDVT-10 solution and the n-type micromolecular Y6 solution is chlorobenzene.
Further, the solvent of the silver nanowire solution is isopropanol.
Further, the light-transmitting drain electrode is a silver nanowire electrode.
Further, the organic heterojunction thickness is 150 nm.
Since the channel length in VFETs is determined by the thickness of the semiconductor, PDVT-10: the thickness of Y6 directly affects the current level of the device, and it was found in experiments that with PDVT-10: the thickness of Y6 is continuously reduced, and the on-state current density of VOFETs is continuously increased; however, the off-state current is also increased, so that the smaller the switching ratio of the device is, which indicates that the shorter the channel length is in the VFETs, the better the shorter the channel length is, and when the channel is reduced to a certain extent, the leakage current between the source and the drain is increased, and even the short circuit between the source and the drain is caused, so that the normal operation of the device is affected. While PDVT-10: the thickness of the Y6 film is about 150nm, the device performance is optimal in this case, and the difficulty that the channel length is difficult to be reduced to the nanometer level in the conventional parallel FETs is solved.
In another aspect, the invention provides a method of making an organic heterojunction vertical phototransistor comprising:
1) Pretreating a substrate;
2) Spin-coating silver nanowire solution on the substrate and drying to form a silver nanowire source electrode;
3) Spin-coating a mixed solution of a P-type polymer PDVT-10 solution and an n-type micromolecule Y6 solution on the silver nanowire source electrode, and annealing and drying to form an organism heterojunction;
4) Preparing a light-transmitting drain electrode on the organic heterojunction;
the structural formula of the P-type polymer PDVT-10 is shown as formula I:
one (I)
The structural formula of the n-type small molecule Y6 is shown as a formula II:
two kinds of
The concentrations of the P-type polymer PDVT-10 solution and the n-type small molecule Y6 solution are 10g/L; the mixed solution is prepared from the P-type polymer PDVT-10 solution and n-type micromolecular Y6 solution according to the volume ratio of 8:2, mixing; the concentration of the silver nanowire solution is 0.5g/L.
Further, the solvent of the P-type polymer PDVT-10 solution and the n-type micromolecular Y6 solution is chlorobenzene.
Further, the solvent of the silver nanowire solution is isopropanol.
Further, the light-transmitting drain electrode is a silver nanowire electrode.
Further, the organic heterojunction thickness is 150 nm.
Compared with the prior art, the technical scheme provided by the invention has the following beneficial effects:
(1) The invention provides an organic heterojunction vertical photoelectric transistor and a preparation method thereof, and the vertical structure transistor has a shorter channel and a larger electric field under the same voltage, so that internal carrier transmission is faster, and holes generated by separation of photo-generated excitons can be injected into an electrode more quickly and effectively, thereby generating larger photo-generated current; secondly, the transmission distance of the carriers is shortened, so that the probability of electron-hole recombination after separation is smaller, and the device obtains more excellent photoelectric performance.
(2) According to the invention, a PDVT-10:Y6 bulk heterojunction structure is adopted, under the illumination condition, the source of current mainly comprises excitons generated by light absorption of the PDVT-10:Y6 bulk heterojunction besides the hot electron injection induced by a grid voltage regulation barrier, and photo-generated excitons are rapidly generated in a PDVT-10 layer, and a large amount of photo-generated excitons are dissociated into holes and electrons due to the existence of a large source-drain electric field in an extremely short channel of a vertical structure. In addition, Y6 has deeper LUMO energy level compared with PDVT-10, dissociated photo-generated electrons are transferred into Y6 from PDVT-10 along with potential barrier, and the electrons are difficult to return into PDVT-10 due to LUMO energy level difference, so that a large number of photo-generated electrons are captured at PN junction, and the recombination probability of electron holes is reduced. Similarly, the larger HOMO energy level difference between PDVT-10 and Y6 prevents holes from transferring to Y6, and under the action of a vertical electric field, the holes are effectively collected by the drain electrode, so that a large amount of photocurrent is generated, and the device performance is further improved.
(3) The silver nanowire source electrodes adopted by the invention are distributed uniformly, a good network shape is formed, a large number of stacks are not generated, the electrode is ensured not to shield most of the regulation and control capability of grid voltage to source leakage current, meanwhile, the formation of a source electrode network can be ensured, the injection of carriers is ensured, a larger on-state current density is formed, and the device performance is further optimized.
Drawings
FIG. 1 is a schematic diagram of an organic heterojunction vertical phototransistor according to example 1 of the present invention;
FIG. 2 is a graph showing the transfer characteristics of an organic heterojunction vertical phototransistor prepared in example 2 of the present invention under different light intensities of 808 and nm;
FIG. 3 is a graph showing the relationship between the light responsivity, the detection rate and the photosensitivity value of the organic heterojunction vertical phototransistor prepared in example 2 according to the present invention and the light intensity;
wherein, the reference numerals are as follows: 1-Gate electrode Si++, 2-dielectric layer SiO 2 3-silver nanowire source electrode, 4-PDVT-10: y6 organic heterojunction, 5-silver nanowire drain electrode.
Detailed Description
For a more clear description of the objects and advantages of the present invention, the present invention will be further described in detail with reference to the accompanying drawings in the embodiments of the present invention. The following specific examples are given for the purpose of illustration only and are not intended to be limiting. In addition, the technical features of the embodiments of the present invention described below may be combined with each other as long as they do not collide with each other.
Example 1
First, an organic heterojunction vertical phototransistor is provided, see fig. 1, comprising: gate electrode (si++), dielectric layer (SiO 2 ) A silver nanowire source electrode is formed on the dielectric layer, and an organic heterojunction (PDVT-10: y6), the thickness of the organism heterojunction is 150nm, a semitransparent silver nanowire drain electrode is formed on the bulk heterojunction, and the bulk heterojunction is formed by mixing a P-type polymer PDVT-10 solution and an n-type micromolecular Y6 solution with the concentration of 10g/L according to the volume ratio of 8:2; the silver nanowire source electrode is formed by spin coating 0.5g/L silver nanowire solution on the dielectric layer.
Example 2
Correspondingly, this example provides a method for fabricating an organic heterojunction vertical phototransistor, the method generally comprising the steps of:
pretreatment of a substrate:
will deposit 300 nm SiO 2 Cutting the heavily doped silicon wafer substrate into the size of 1.5 cm multiplied by 1.5 cm, sequentially soaking in water, acetone and isopropanol, ultrasonically cleaning for 5 min, then drying by argon, carrying out ozone treatment for 15 min, further cleaning the surface of the substrate, enhancing the hydrophilicity of the substrate, and facilitating the spin-coating of the subsequent solution to form a film.
Spin-coating silver nanowire solution on the pretreatment substrate and drying to form a silver nanowire source electrode:
diluting 5g/L AgNWs stock solution to 0.5g/L by isopropanol, sucking 100 mu L of solution with corresponding concentration to the pretreated substrate by a pipetting gun, spin-coating at 2000 rpm for 60s, and then placing on a hot table for annealing at 120 ℃ for 10 min to obtain a conductive AgNWs network, namely a silver nanowire source electrode.
Spin-coating a mixed solution of a P-type polymer PDVT-10 solution and an n-type small molecule Y6 solution on the silver nanowire source electrode, and annealing and drying to form a bulk heterojunction:
preparing 10g/L PDVT-10 and Y6 solution by using CB chlorobenzene solvent, and after the solution is fully dissolved, preparing the solution according to the volume ratio PDVT-10: y6=8:2 mix, heat 2 h on a hot bench at 60 ℃ to form PDVT-10: and (3) sucking 50 mu L of PDVT-10:Y6 mixed solution by using a pipette, uniformly dripping the mixed solution onto a substrate of an active electrode, rotating the mixed solution at 1000 rpm for 60s, and then placing the mixed solution on a hot table for annealing at 110 ℃ for 10 minutes to form the organic heterojunction with the thickness of 150 nm.
And preparing a light-transmitting drain electrode on the bulk heterojunction:
and (3) spraying 5g/L AgNWs stock solution network by using a spraying instrument to prepare a semitransparent silver nanowire drain electrode, wherein the spraying time is 2s.
The organic heterojunction vertical phototransistor of this example was tested at 808 and nm different illumination intensities and the transfer characteristic curve is shown in FIG. 2. It can be seen from FIG. 2 that even at 0.01 mW/cm 2 The off-state current of the device is also obviously increased under the illumination intensity of the device, and the on-voltage of the device moves towards the positive grid voltage direction. This is because the device is illuminated and the photogenerated excitons separate into electrons and holes, which rapidly increase in the channel. Thus, the device can be turned on even at a positive gate voltage. FIG. 3 further shows that the device is at V DS =-60 V，V GS The light response, detection rate and photosensitivity of the device are reduced along with the increase of the light intensity according to the change relation of the light response, detection rate and photosensitivity of the device along with the increase of the light intensity when the light response and detection rate of the device are= -5V lambda = 808 nm, the photosensitivity is increased along with the increase of the light intensity, the light response change objective rule of the device is consistent with that of a phototransistor in the prior art, the light response of the final device is 0.3A/W, and the light detection rate reaches 1.2 multiplied by 10 12 Jones, light sensitivity near 10 4 Indicating excellent optoelectronic properties of the device.
The invention has been described with particular reference to the examples which are intended to be illustrative of the invention and not limiting. Several simple deductions, modifications or substitutions may also be made by a person skilled in the art according to the idea of the invention. Such deductions, modifications or alternatives fall within the scope of the claims of the present invention.
Claims (10)
1. An organic heterojunction vertical phototransistor characterized by: the phototransistor includes: the organic heterojunction is formed on the silver nanowire source electrode, and the light-transmitting drain electrode is formed on the organic heterojunction, wherein the organic heterojunction is formed by a P-type polymer PDVT-10 and an n-type small molecule Y6; the structural formula of the P-type polymer PDVT-10 is shown as formula I:
one of the two main components is a metal-plastic composite,
the structural formula of the n-type small molecule Y6 is shown as a formula II:
a second step of, in a second step,
the organic heterojunction is formed by mixing a P-type polymer PDVT-10 solution and an n-type micromolecule Y6 solution with the concentration of 10g/L according to the volume ratio of 8:2; the silver nanowire source electrode is formed by spin coating 0.5g/L silver nanowire solution on the dielectric layer.
2. An organic heterojunction vertical phototransistor as claimed in claim 1 wherein the solvent for the P-type polymer PDVT-10 solution and the n-type small molecule Y6 solution is chlorobenzene.
3. An organic heterojunction vertical phototransistor as claimed in claim 1 wherein the solvent of the silver nanowire solution is isopropanol.
4. An organic heterojunction vertical phototransistor as claimed in claim 1 wherein said light-transmitting drain electrode is a silver nanowire electrode.
5. An organic heterojunction vertical phototransistor as claimed in claim 1 wherein said organic heterojunction has a thickness of 150 nm.
6. A method of fabricating an organic heterojunction vertical phototransistor, comprising:
1) Pretreating a substrate;
2) Spin-coating silver nanowire solution on the substrate and drying to form a silver nanowire source electrode;
3) Spin-coating a mixed solution of a P-type polymer PDVT-10 solution and an n-type micromolecule Y6 solution on the silver nanowire source electrode, and annealing and drying to form an organism heterojunction;
4) Preparing a light-transmitting drain electrode on the organic heterojunction;
the structural formula of the P-type polymer PDVT-10 is shown as formula I:
one of the two main components is a metal-plastic composite,
the structural formula of the n-type small molecule Y6 is shown as a formula II:
a second step of, in a second step,
the concentrations of the P-type polymer PDVT-10 solution and the n-type small molecule Y6 solution are 10g/L; the mixed solution is prepared from the P-type polymer PDVT-10 solution and n-type micromolecular Y6 solution according to the volume ratio of 8:2, mixing; the concentration of the silver nanowire solution is 0.5g/L.
7. The method of claim 6, wherein the solvent for the P-type polymer PDVT-10 solution and the n-type small molecule Y6 solution is chlorobenzene.
8. A method of fabricating an organic heterojunction vertical phototransistor as defined in claim 6 wherein the solvent of the silver nanowire solution is isopropanol.
9. A method of fabricating an organic heterojunction vertical phototransistor as defined in claim 6 wherein the light-transmitting drain electrode is a silver nanowire electrode.
10. A method of fabricating an organic heterojunction vertical phototransistor as defined in claim 6 wherein the organic heterojunction has a thickness of 150 nm.
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