CN113707808B - Intrinsic stretchable organic parallel heterojunction phototransistor and preparation method thereof - Google Patents
Intrinsic stretchable organic parallel heterojunction phototransistor and preparation method thereof Download PDFInfo
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
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- H10K30/20—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising organic-organic junctions, e.g. donor-acceptor junctions
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Abstract
The invention discloses an intrinsic stretchable organic parallel heterojunction phototransistor and a preparation method thereof. The stretchable organic phototransistor is a bottom gate top contact structure, and the bottom gate top contact structure comprises a stretchable substrate, a stretchable gate electrode, a stretchable insulating layer, a stretchable organic semiconductor layer, a stretchable source drain electrode, a photosensitive layer and a stretchable packaging layer, wherein the photosensitive layer is made of organic micromolecular materials with high mobility and high photosensitivity. The invention adopts the parallel heterojunction formed by the electron donor stretchable organic semiconductor material and the electron acceptor micromolecular material as an active layer material system, and the prepared stretchable parallel heterojunction phototransistor has the characteristics of high mobility, low dark current, high response speed and stable photoelectric performance under high mechanical deformation. Meanwhile, the method provided by the invention has the advantages of simple process and low cost, and can be widely applied to the fields of ultrathin flexible photoelectric detection and the like.
Description
Technical Field
The invention relates to the technical field of flexible electronics, in particular to an intrinsic stretchable organic parallel heterojunction phototransistor (STOTPs) and a preparation method thereof.
Background
The flexible stretchable electronic device has the same mechanical properties as human skin, plays an important role in the fields of health monitoring, medical implantation, artificial skin, human-computer interaction and the like, can accurately monitor human signals such as pulse, blood pressure, body temperature and the like in real time, and is expected to become a functional human body 'second layer skin' (a) of Someya, T.; bao, Z.; maliaras, G.Nature 2016,540,379.; b) of chord, A.; liu, J.; bao, Z.Nature Materials 2016,15,937.; c) of Kang, S.K.; murphy, R.K.; hwang, S.W.; et al Nature 2016,530,71. The polymer semiconductor is flexible, controllable in molecular structure, high in mobility, solution processable, and suitable for stretchable electronic devices (trunk, T.Q.; lee, N.E. advanced Materials 2017,29,1603167.). However, the molecular structure of the polymer semiconductor contains a large number of thiophene rings and benzene rings, making it difficult to achieve a balance of stretchability and electrical properties. The technical proposal of the university of Stanford chemical engineering system, which teaches Bao Zhena, skillfully designs a solution coating method, limits the semiconductor polymer to the nanofiber coated by the rubber polymer, and satisfies the high elasticity and stretchability of the semiconductor film, thereby preparing the intrinsic stretchable organic field effect transistor. The stretchable transistor was found to have only a very small decrease in conductivity when stretched to twice its original length (Xu, j.; wang, s.; wang.n.; et al science 2017,355.). However, the current research is limited to stretchable organic field effect transistors, and little research is done in the field of stretchable organic type photodetectors and the like.
The organic photodetectors mainly include organic phototransistors, organic photodiodes, and organic photoconductors, depending on the device structure. Compared with the organic photodiode and the organic photoconductor, the organic phototransistor has the advantages of high sensitivity, low noise, integration of a photodetecting function and a signal amplifying function, convenience in circuit integration and the like (Chinese patent 201810746339.4). Therefore, the phototransistor is not only a preferred device prototype for studying the photoelectric characteristics of a specific material, but also is expected to realize a photosensor. Although organic phototransistors have great advantages in the fabrication of ultra-thin, lightweight, ultra-soft photodetectors, research into organic phototransistors has not received sufficient attention, and no report has been made concerning the fabrication and research of intrinsically stretchable organic phototransistors.
Disclosure of Invention
The invention aims to provide an intrinsic stretchable organic parallel heterojunction phototransistor and a preparation method thereof.
The invention provides an intrinsic stretchable organic parallel heterojunction phototransistor which is a bottom gate top contact structure and sequentially comprises a stretchable substrate (1), a stretchable gate electrode (2), a stretchable insulating layer (3), a stretchable organic semiconductor layer (4), a stretchable source electrode (5) and a stretchable drain electrode (6) which are arranged on the same plane, a photosensitive layer (7) and a stretchable packaging layer (8), wherein the photosensitive layer (7) is arranged between the stretchable source electrode (5) and the stretchable drain electrode (6).
The photosensitive layer is made of small organic molecules with high mobility and high photosensitivity, such as fullerene C60.
The thickness of the photosensitive layer may be 10 to 200nm.
In the intrinsic stretchable organic parallel heterojunction phototransistor described above, the stretchable substrate, the stretchable insulating layer, and the stretchable encapsulation layer are all made of an elastomeric polymer;
the elastomer polymer is any one of Polydimethylsiloxane (PDMS), hydrogenated styrene-butadiene block copolymer (SEBS), styrene-butadiene rubber (SBR), natural Rubber (NR), ethylene-propylene rubber (EPR), butyl rubber (IIR) and thermoplastic polyurethane elastomer (PU);
the stretchable substrate may have a thickness of 200 μm to 3mm;
the thickness of the stretchable insulating layer may be 500nm to 2 μm;
the stretchable encapsulation layer may have a thickness of 100 μm to 1mm.
In the intrinsic stretchable organic parallel heterojunction phototransistor, the stretchable organic semiconductor layer is made of a stretchable organic semiconductor blend system;
the stretchable organic semiconductor blend system is formed by mixing an elastomer polymer and a conjugated polymer;
the elastomeric polymer may be any one of hydrogenated styrene-butadiene block copolymer (SEBS), polydimethylsiloxane (PDMS), styrene-butadiene rubber (SBR), ethylene-propylene rubber (SPR), and butyl rubber (IIR);
the conjugated polymer may be any of poly (2, 5-bis (2-octyldodecyl) -3, 6-bis (thiophen-2-yl) diketopyrrolo [3,4-c ] pyrrole-1, 4-dione-alt-thiophene [3,2-b ] thiophene), poly- [2, 5-bis (7-decylnonyl) pyrrole [3,4-c ] pyrrole-1, 4- (2 h,5 h) -dione- (E) - (1, 2-bis (5- (thiophen-2-yl) selen-2-yl) ethylene), poly [2, 5-bis (4-decyltetradecyl) pyrrole [3,4-c ] pyrrole-1, 4- (2 h,5 h) -dione- (E) -1, 2-bis (2, 2' -dithiophene-5-yl) ethylene ], indole dithieno-benzothiadiazole and poly (3-hexylthiophene);
the mass ratio of elastomeric polymer to conjugated polymer in the stretchable organic semiconductor system may be (9:1) - (1:9), and specifically may be 5:5;
the stretchable organic semiconductor layer may have a thickness of 40 to 150nm.
In the intrinsic stretchable organic parallel heterojunction phototransistor, the stretchable gate electrode, the stretchable source electrode, and the stretchable drain electrode are all made of carbon nanotube materials;
the carbon nanotube material may be single-walled carbon nanotubes;
the single-walled carbon nanotubes may be any of AP-SWNTs, P2-SWNTs, P3-SWNTs, P5-SWNTs, P8-SWNTs, and P9-SWNTs.
The invention also provides a preparation method of the stretchable organic parallel heterojunction phototransistor.
The preparation method comprises the following steps:
1) Preparing the stretchable substrate, the stretchable gate electrode, the stretchable insulating layer, the stretchable organic semiconductor layer, the stretchable source electrode, the stretchable drain electrode, and the stretchable encapsulation layer on a substrate with a self-assembled molecular layer, respectively;
2) Depositing the photosensitive layer in a region between the stretchable source electrode and the stretchable drain electrode;
3) Transferring the stretchable gate electrode to the stretchable substrate by a thermal bonding method, sequentially transferring the stretchable insulating layer and the stretchable organic semiconductor layer to the stretchable gate electrode, and then transferring the stretchable source-drain electrode and the photosensitive layer which are positioned on the same plane to the stretchable organic semiconductor layer; and finally transferring the stretchable packaging layer onto the photosensitive layer to obtain the intrinsic stretchable organic parallel heterojunction phototransistor.
In the above method, the material of the substrate may be any one of silicon wafer, glass, metal, quartz and hard alloy;
the substrate with the self-assembled molecular layer is prepared by the following method: and heating the substrate by adopting silane molecules under vacuum or soaking the substrate in the solution to obtain the substrate with the self-assembled molecular layer.
The silane molecule can be any one of octadecyltrimethoxysilane, octadecyltrichlorosilane, octyl trichlorosilane and phenyl trichlorosilane;
the temperature of the heating treatment can be 90-150 ℃, specifically 120 ℃, and the time can be 1-5 hours, specifically 3 hours;
the solvent adopted in the soaking treatment is any one of cyclohexane, n-hexane, n-heptane and n-pentane;
the soaking treatment time can be 1-6 hours, and can be specifically 2 hours;
before the heating treatment or the soaking treatment in the solution, the ultrasonic cleaning and the nitrogen blow-drying are sequentially carried out on the substrate by adopting liquid detergent, tap water, secondary water, ethanol and acetone;
wherein, the ultrasonic cleaning conditions can be as follows: the ultrasonic power is 20-100 watts, and the ultrasonic time is 1-30 minutes;
in the above preparation steps, the stretchable substrate, the stretchable insulating layer, the stretchable organic semiconductor layer and the stretchable encapsulation layer may be prepared by spin coating, knife coating, drop coating, roll coating, brushing or drawing;
the solvent can be toluene, xylene, dichloromethane, chloroform, n-hexane or cyclohexane;
when preparing the stretchable substrate, the concentration of the elastomeric polymer in the dispersion employed may be 100-400 mg/mL;
when preparing the stretchable insulating layer, the concentration of the elastomeric polymer in the dispersion employed may be 40-100 mg/mL;
the concentration of the stretchable organic semiconductor blend system in the dispersion employed in the preparation of the stretchable organic semiconductor layer may be 3 to 15mg/mL.
The concentration of the elastomeric polymer in the dispersion employed in preparing the stretchable encapsulating layer may be in the range of 50 to 200mg/mL.
In the above preparation steps, the stretchable gate electrode, the stretchable source electrode and the stretchable drain electrode may be prepared by spraying;
the solvent is water, ethanol, isopropanol or a mixed solvent thereof;
the carbon nano tube material is dispersed in water, ethanol, isopropanol or a mixed solvent thereof;
the dispersion concentration of the carbon nano tube material can be 0.03-0.5 mg/mL;
the spraying conditions can be as follows: the distance between the nozzle and the substrate can be 5-20 mm, the temperature of the substrate can be 50-150 ℃, the spraying rate can be 0.5-5 mL/min, and the spraying amount can be 0.5-5 mL.
In the preparation step, the photosensitive layer can be prepared by vacuum thermal evaporation;
the evaporation conditions can be as follows: vacuum degree of 10 -5 ～10 -3 Pascal, the vapor deposition temperature is 200-400 ℃, and the vapor deposition speed is 1-10 angstrom/second;
in the preparation step, the heat bonding process is carried out in a vacuum drying oven;
the conditions of the thermal lamination may be: the vacuum degree is 0.1-10 Pa, the temperature during heating treatment can be 50-150 ℃, and the heating time can be 0.5-5 hours.
The invention has the beneficial effects that: the method for preparing the intrinsic stretchable organic parallel heterojunction phototransistor is simple in preparation process and low in cost. The prepared stretchable organic phototransistor has high mobility, high photosensitivity and high light-dark current ratio. More importantly, the stretchable organic phototransistor can also show stable photoelectric performance under high stretching deformation, and has good application prospect in the field of ultrathin flexible photosensitive semiconductor devices.
Drawings
Fig. 1 is a schematic structural diagram of an intrinsically stretchable organic parallel heterojunction phototransistor (STODTS) according to the present invention.
FIG. 2 shows the transfer characteristics of STODTs prepared according to example 1 of the invention under the effect of matt and low energy white light (1.0 mW/cm), respectively. Wherein fig. 2 (a) is in an unstretched condition; FIG. 2 (b) under 50% elongation conditions; FIG. 2 (c) shows a stretch ratio of 100%.
FIG. 3 shows the variation of the photo-dark current ratio with gate voltage for STODTs prepared according to example 1 of the invention under unstretched, 50% elongation and 100% elongation conditions.
FIG. 4 shows the change in the optical responsivity with gate voltage of STODTS prepared by example 1 according to the invention under the conditions of unstretched, 50% elongation and 100% elongation.
FIG. 5 is a graph showing the transfer characteristics of STODTS prepared by example 2 according to the invention under the influence of non-light and low-energy white light (1.0 mW/cm), respectively. Wherein fig. 5 (a) is in an unstretched condition; fig. 5 (b) is under a condition of a stretching ratio of 50%.
FIG. 6 shows the transfer characteristics of STODTs prepared according to example 3 of the invention under the effect of matt and low energy white light (1.0 mW/cm), respectively. Wherein fig. 6 (a) is in an unstretched condition; fig. 6 (b) is under a condition of a stretch ratio of 50%.
Detailed Description
The present invention will be described with reference to the following specific examples, but the present invention is not limited thereto.
The experimental methods used in the following examples are all conventional methods unless otherwise specified; the reagents, materials, etc. used in the examples described below are commercially available unless otherwise specified.
The invention provides an intrinsic stretchable organic parallel heterojunction phototransistor and a preparation method thereof, wherein the stretchable organic parallel heterojunction phototransistor is of a bottom gate top contact structure and sequentially comprises a stretchable substrate 1, a stretchable gate electrode 2, a stretchable insulating layer 3, a stretchable organic semiconductor layer 4, a stretchable source electrode 5 and a stretchable drain electrode 6 which are positioned on the same plane, a photosensitive layer 7 and a stretchable packaging layer 8 which are positioned between the stretchable source electrode and the stretchable drain electrode from bottom to top, wherein the structure is shown in figure 1; wherein the photosensitive layer is made of organic micromolecular material with high mobility and high sensitivity.
An intrinsically stretchable organic parallel heterojunction phototransistor is prepared comprising the steps of:
first, preparation of a substrate with a self-assembled molecular layer
Before use, the substrate is sequentially ultrasonically cleaned by adopting a detergent solution, tap water, deionized water, acetone and ethanol, and is dried by nitrogen. Heating the clean substrate by adopting silane molecules under vacuum or soaking the clean substrate in a solution to obtain the substrate with the self-assembled molecular layer;
second step, preparation of stretchable substrate
Obtaining a stretchable substrate 1 with a thickness of 200 mu m-3mm on the substrate with the self-assembled molecular layer by a method of dripping, knife coating or rolling coating;
third step, preparation of stretchable Gate electrode
Preparing a stretchable gate electrode 2 on the substrate with the self-assembled molecular layer by a spraying method;
fourth step, preparation of stretchable insulation layer
A stretchable insulating layer 3 with a thickness of 500nm-2 μm is obtained on the substrate with the self-assembled molecular layer by spin coating, knife coating, drop coating or roll coating;
fifth step, preparation of stretchable organic semiconductor layer
A stretchable organic semiconductor layer 4 with the thickness of 40-150 nm is obtained on the substrate with the self-assembled molecular layer by spin coating, knife coating, roll coating, film brushing or film drawing;
sixth step, preparation of stretchable source electrode and stretchable drain electrode
Preparing a stretchable source electrode 5 and a stretchable drain electrode 6 on the substrate with the self-assembled molecular layer by a spraying method;
seventh step, preparation of photosensitive layer
Preparing a photosensitive layer 7 with the thickness of 10-200 nm in a region between the stretchable source electrode and the stretchable drain electrode prepared in the sixth step by a vacuum thermal evaporation method;
eighth step, preparation of stretchable packaging layer
Obtaining a stretchable packaging layer 8 with the thickness of 100 mu m-1 mm on the substrate with the self-assembled molecular layer by a method of dripping, knife coating or rolling coating;
ninth step, preparation of intrinsic stretchable organic parallel heterojunction phototransistor
And transferring the prepared stretchable gate electrode, the stretchable insulating layer, the stretchable organic semiconductor layer, the stretchable source/drain electrode, the photosensitive layer and the stretchable substrate in sequence by using the prepared stretchable substrate through a thermal bonding method to obtain the intrinsic stretchable organic parallel heterojunction phototransistor.
For a better understanding of the present invention, the following examples are further illustrated, but are not limited to the following examples.
In the examples described below, the mechanical and optoelectronic properties of stretchable organic parallel heterojunction phototransistors were measured in both atmospheric and room temperature conditions.
The tensile organic parallel heterojunction phototransistor is subjected to basic transfer characteristic test under the dark condition, and the electrical properties such as mobility in a saturation region and the like are obtained.
The transfer characteristics were then tested under low energy white light conditions and the difference in electrical properties was compared between matt and low energy white light. The calculation is performed according to the following formula:
light sensitivity= (current under transistor illumination-current under transistor no light condition)/incident light power perceived in transistor channel
Photocurrent/dark current= (current under transistor illumination-current under transistor no light condition)/current under transistor no light condition
The light sensing sensitivity and the light dark current ratio can be obtained by the formula.
Example 1,
The steps for preparing the intrinsic stretchable parallel heterojunction phototransistor in this example are as follows:
1) And sequentially carrying out ultrasonic treatment on a silicon wafer serving as a substrate by using a detergent, deionized water, acetone and ethanol at a power of 60 watts for 5 minutes, drying by using nitrogen, carrying out ultraviolet peroxidation treatment on the clean silicon substrate for 20 minutes, placing the substrate and octadecyltrimethoxysilane in a same culture dish, heating to 120 ℃ for 3 hours under the vacuum degree of 0.1 pascal, and naturally cooling to room temperature to obtain the silicon wafer with the self-assembled molecular layer.
2) Uniformly dripping 0.8mL of toluene solution of SEBS (with the concentration of 220 mg/mL) on the silicon wafer with the self-assembled molecular layer by using a 1mL syringe, then placing the silicon wafer on a hot stage, annealing at 50 ℃ for 5 hours and then annealing at 100 ℃ for 2 hours to obtain a stretchable substrate with the thickness of 400 mu m;
3) Placing the silicon wafer with the self-assembled molecular layer on a hot stage at 50 ℃ for standing for 5 minutes, and then uniformly spraying isopropanol solution (with the concentration of 0.2 mg/mL) of single-walled carbon nanotube P3-SWNT on the silicon wafer to obtain a stretchable gate electrode; the adopted spraying conditions are as follows: the distance between the nozzle and the substrate is 6mm, the spraying speed is 1mL/min, and the spraying amount is 1.5mL;
4) Placing the silicon wafer with the self-assembled molecular layer in the center of a photoresist homogenizing machine, dripping 150 mu L of cyclohexane solution (with the concentration of 80 mg/ml) of hydrogenated styrene-butadiene block copolymer on the silicon wafer by using a 1000 mu L pipetting gun, spin-coating for 40 seconds at the speed of 1200 revolutions per minute, and finally annealing the silicon wafer at 80 ℃ for 50 minutes on a hot stage to obtain a stretchable insulating layer with the thickness of 1600 nm;
5) Placing the silicon wafer with the self-assembled molecular layer on the center of a photoresist homogenizing machine, dropwise adding 30 mu L of chlorobenzene solution of poly (2, 5-bis (2-octyldodecyl) -3, 6-bis (thiophene-2-yl) diketopyrrolopyrrole [3,4-c ] pyrrole-1, 4-diketo-alt-thiophene [3,2-b ] thiophene)/hydrogenated styrene-butadiene segmented copolymer (wherein the mass ratio of the two polymers is 5:5 and the concentration is 15 mg/ml) on the silicon wafer by using a 100 mu L pipette, spin-coating for 1 minute at the speed of 2500 rpm, and finally placing the silicon wafer on a hot stage for annealing for 20 minutes at 180 ℃ to obtain a stretchable organic semiconductor layer with the thickness of 100 nm;
6) Placing the silicon wafer with the self-assembled molecular layer on a magnet, placing a mask plate on the silicon wafer, lightly placing the magnet and the silicon wafer on a heat table at 120 ℃ for standing for 15 minutes, and finally uniformly spraying an isopropanol solution (with the concentration of 0.1 mg/mL) of the single-walled carbon nanotube P3-SWNT on the silicon wafer to obtain a patterned stretchable source electrode and a patterned stretchable drain electrode. The adopted spraying conditions are as follows: the distance between the nozzle and the substrate is 10mm, the spraying speed is 1.5mL/min, and the spraying amount is 1mL;
7) Placing the silicon wafer with the stretchable source electrode and the stretchable drain electrode in the step 6) into a vacuum coating machine, and pumping the vacuum degree to 4-6 multiplied by 10 -4 Pa, depositing a fullerene C60 molecular layer between a stretchable source electrode and a stretchable drain electrode at a speed of 0.5-1.5 angstroms per second by adopting a thermal evaporation mode to reach a thickness of 60-80nm;
8) Uniformly dripping 0.3mL of toluene solution of SEBS (with the concentration of 130 mg/mL) on the silicon wafer with the self-assembled molecular layer by using a 1mL syringe, then placing the silicon wafer on a hot stage, annealing at 70 ℃ for 2 hours, and then annealing at 120 ℃ for 30 minutes to obtain a stretchable packaging layer with the thickness of 100 mu m;
9) Transferring the stretchable substrate prepared in the step 2) from the silicon wafer by using pointed tweezers, lightly covering the stretchable substrate on the silicon wafer with the stretchable gate electrode from one side, and placing the silicon wafer in a vacuum oven at 60 ℃ for 20 minutes under the vacuum degree of 0.1 pascal, so that the stretchable gate electrode can be transferred onto the stretchable substrate; then sequentially transferring the stretchable insulating layer, the stretchable organic semiconductor layer, the stretchable source-drain electrode and the photosensitive layer which are positioned on the same plane to the stretchable gate electrode by the same steps; and finally transferring the stretchable packaging layer onto the stretchable photosensitive layer to obtain the intrinsic stretchable organic parallel heterojunction phototransistor with the structure shown in figure 1.
As can be seen from FIG. 2, the stretchable organic parallel heterojunction phototransistor prepared in example 1 has saturation mobilities of 0.29cm at 0%, 50% and 100% of the tensile deformation, respectively, when no light is applied 2 V -1 s -1 、0.35cm 2 V -1 s -1 And 0.16cm 2 V -1 s -1 Explaining that the stretchable phototransistor isThe carrier mobility can be kept high when the material is stretched to twice the original length. Meanwhile, the switching ratio, the off-state current and the threshold voltage of the stretchable phototransistor can be kept relatively stable under different stretching deformation rates. Comparing the transfer characteristics of the non-light and low energy white light (1.0 mW/cm) in FIGS. 2 (a), 2 (b) and 2 (c), the tensile organic parallel heterojunction phototransistor prepared in example 1 exhibited low dark current and high photo-response speed under different tensile deformations. From the analysis of fig. 3 and 4, it can be seen that the stretchable organic parallel heterojunction phototransistor prepared in example 1 exhibits a higher photo-dark current ratio and photo-responsivity when no light is applied. When the stretching ratio is 0%, the photo-dark current ratio and the photo-responsivity of the phototransistor at the stretching ratio of 50% are obviously increased, and the molecular chain arrangement in the stretchable organic semiconductor is oriented in the stretching process, so that the transport of carriers is facilitated. Even if the stretching ratio reaches 100%, the photo-dark current ratio and the photo-responsivity of the phototransistor can be kept at relatively high values.
EXAMPLE 2,
According to the exactly same preparation method as in example 1, the deposition thickness of the fullerene C60 molecular layer in the step 7) is changed to 20-30nm, and the intrinsic stretchable organic parallel heterojunction phototransistor is obtained.
As can be seen from the analysis of FIG. 5, the on-state current, the off-state current and the switching ratio of the stretchable organic parallel heterojunction phototransistor prepared in example 2 can maintain relative stability under different stretching deformation rates, and the phototransistor also exhibits higher light-dark current ratio and light responsivity. Compared with the stretching ratio of 0%, the photo-dark current ratio and the photo-responsivity of the phototransistor at the stretching ratio of 50% are obviously improved, and further the stretchable organic parallel heterojunction phototransistor prepared in example 2 can maintain stable photoelectric performance under high stretching deformation.
EXAMPLE 3,
According to the exactly same preparation method as in example 1, only the stretchable organic semiconductor system in step 5) was changed to poly- [2, 5-bis (7-decylnonyl) pyrrole [3,4-c ] pyrrole-1, 4- (2H, 5H) -dione- (E) - (1, 2-bis (5- (thiophen-2-yl) selen-2-yl) ethylene)/hydrogenated styrene-butadiene block copolymer (the mass ratio of both was also 5:5, the concentration was also 15 mg/ml), and the other conditions were kept unchanged, to obtain an intrinsic stretchable organic parallel heterojunction phototransistor.
As can be seen from the analysis of FIG. 6, the on-state current, the off-state current and the switching ratio of the stretchable organic parallel heterojunction phototransistor prepared in example 3 can maintain relative stability under different stretching deformation rates, and the phototransistor also exhibits higher light-dark current ratio and light responsivity. The method for preparing the stretchable organic parallel heterojunction phototransistor is applicable to various organic semiconductor materials and has universality.
Claims (10)
1. An intrinsic stretchable organic parallel heterojunction phototransistor is a bottom gate top contact structure, and the structure comprises a stretchable substrate (1), a stretchable gate electrode (2), a stretchable insulating layer (3), a stretchable organic semiconductor layer (4), a stretchable source electrode (5) and a stretchable drain electrode (6) which are arranged on the same plane, a photosensitive layer (7) and a stretchable encapsulation layer (8) which are positioned between the stretchable source electrode (5) and the stretchable drain electrode (6) from bottom to top in sequence;
the photosensitive layer is made of organic small molecules with high mobility and high photosensitive sensitivity, and the organic small molecules are fullerene C60;
in the intrinsically stretchable organic parallel heterojunction phototransistor, the stretchable substrate, the stretchable insulating layer, and the stretchable encapsulation layer are all made of an elastomeric polymer one;
the first elastomer polymer is any one of polydimethylsiloxane, hydrogenated styrene-butadiene block copolymer, styrene-butadiene rubber, natural rubber, ethylene propylene rubber, butyl rubber and thermoplastic polyurethane elastomer;
the stretchable organic semiconductor layer is made of a stretchable organic semiconductor blend system;
the stretchable organic semiconductor blending system is formed by mixing an elastomer polymer II and a conjugated polymer;
the elastomer polymer II is any one of hydrogenated styrene-butadiene block copolymer, polydimethylsiloxane, styrene-butadiene rubber, ethylene propylene rubber and butyl rubber;
the conjugated polymer is any one of poly (2, 5-bis (2-octyldodecyl) -3, 6-bis (thiophen-2-yl) diketopyrrole [3,4-c ] pyrrole-1, 4-dione-alt-thiophene [3,2-b ] thiophene), poly- [2, 5-bis (7-decylnonyl) pyrrole [3,4-c ] pyrrole-1, 4- (2H, 5H) -dione- (E) - (1, 2-bis (5- (thiophen-2-yl) selen-2-yl) ethylene), poly [2, 5-bis (4-decyltetradecyl) pyrrole [3,4-c ] pyrrole-1, 4- (2H, 5H) -dione- (E) -1, 2-bis (2, 2' -dithiophene-5-yl) ethylene ], indole dithiophene benzothiadiazole and poly (3-hexylthiophene);
the stretchable gate electrode, the stretchable source electrode, and the stretchable drain electrode are all made of carbon nanotube material.
2. The intrinsically stretchable organic parallel heterojunction phototransistor of claim 1, wherein: the thickness of the photosensitive layer is 10-200 nm.
3. The intrinsically stretchable organic parallel heterojunction phototransistor as claimed in claim 1 or 2, characterized in that: the thickness of the stretchable substrate is 200 mu m-3 mm;
the thickness of the stretchable insulating layer is 500nm-2 mu m;
the thickness of the stretchable packaging layer is 100 mu m-1 mm.
4. The intrinsically stretchable organic parallel heterojunction phototransistor as claimed in claim 1 or 2, characterized in that: the mass ratio of the elastomer polymer II to the conjugated polymer in the stretchable organic semiconductor blending system is (9:1) - (1:9);
the thickness of the stretchable organic semiconductor layer is 40-150 nm.
5. The intrinsically stretchable organic parallel heterojunction phototransistor of claim 1, wherein: the carbon nanotube material is a single-walled carbon nanotube.
6. A method of making an intrinsically stretchable organic parallel heterojunction phototransistor as claimed in any of claims 1 to 5, comprising the steps of:
1) Preparing the stretchable substrate, the stretchable gate electrode, the stretchable insulating layer, the stretchable organic semiconductor layer, the stretchable source electrode, the stretchable drain electrode, and the stretchable encapsulation layer on a substrate with a self-assembled molecular layer, respectively;
2) Depositing the photosensitive layer in a region between the stretchable source electrode and the stretchable drain electrode;
3) Transferring the stretchable gate electrode to the stretchable substrate by a thermal bonding method, sequentially transferring the stretchable insulating layer and the stretchable organic semiconductor layer to the stretchable gate electrode, and then transferring the stretchable source-drain electrode and the photosensitive layer which are positioned on the same plane to the stretchable organic semiconductor layer; and finally transferring the stretchable packaging layer onto the photosensitive layer to obtain the intrinsic stretchable organic parallel heterojunction phototransistor.
7. The method according to claim 6, wherein: in the step 1), the substrate is made of any one of silicon wafer, glass, metal, quartz and hard alloy;
the substrate with the self-assembled molecular layer is prepared by the following method: heating the substrate by adopting silane molecules under vacuum or soaking the substrate in a solution to obtain a substrate with a self-assembled molecular layer;
wherein the silane molecule is any one of octadecyltrimethoxysilane, octadecyltrichlorosilane, octyl trichlorosilane and phenyl trichlorosilane;
the temperature of the heating treatment is 90-150 ℃ and the time is 1-5 hours;
the solvent adopted in the soaking treatment is any one of cyclohexane, n-hexane, n-heptane and n-pentane;
the soaking treatment time is 1-6 hours.
8. The method according to claim 6 or 7, characterized in that: the stretchable substrate, the stretchable insulating layer, the stretchable organic semiconductor layer and the stretchable packaging layer are prepared by spin coating, knife coating, drip coating, roll coating, film brushing or film drawing;
the solvent is toluene, xylene, methylene dichloride, chloroform, n-hexane or cyclohexane;
when the stretchable substrate is prepared, the concentration of the elastomer polymer I in the adopted dispersion liquid is 100-400 mg/mL;
when the stretchable insulating layer is prepared, the concentration of the elastomer polymer I in the adopted dispersion liquid is 40-100 mg/mL;
when the stretchable organic semiconductor layer is prepared, the concentration of the stretchable organic semiconductor blending system in the adopted dispersion liquid is 3-15 mg/mL;
when the stretchable packaging layer is prepared, the concentration of the elastomer polymer I in the adopted dispersion liquid is 50-200 mg/mL.
9. The method according to claim 6 or 7, characterized in that: the stretchable gate electrode, the stretchable source electrode and the stretchable drain electrode are all prepared by spraying;
the solvent is water, ethanol, isopropanol or a mixed solvent thereof;
the carbon nano tube material is dispersed in water, ethanol, isopropanol or a mixed solvent thereof;
the dispersion concentration of the carbon nanotube material is 0.03-0.5 mg/mL;
the spraying conditions are as follows: the distance between the nozzle and the substrate is 5-20 mm, the temperature of the substrate is 50-150 ℃, the spraying speed is 0.5-5 mL/min, and the spraying amount is 0.5-5 mL.
10. The method according to claim 6 or 7, characterized in that: the photosensitive layer is prepared by vacuum thermal evaporation;
the evaporation conditions are as follows: vacuum degree of 10 -5 ~10 -3 Pascal, the evaporation temperature is 200-400 ℃, and the evaporation speed is 1-10 angstroms/second;
the conditions of the thermal lamination are as follows: the vacuum degree is 0.1-10 Pa, the temperature during heating treatment is 50-150 ℃, and the heating time is 0.5-5 hours.
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