CN115322423A - Egg white thin film and preparation method of degradable organic-inorganic thin film transistor - Google Patents
Egg white thin film and preparation method of degradable organic-inorganic thin film transistor Download PDFInfo
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Abstract
The invention relates to an egg white thin film and a preparation method of a degradable organic-inorganic thin film transistor. The preparation of the egg white film comprises the preparation of egg white precursor liquid; cleaning and surface activating a substrate; preparing an egg white film. The preparation of the degradable organic-inorganic thin film transistor comprises the preparation of an alcohol-based high-k oxide precursor solution and a water-based TMOS precursor solution; activating the surface of the egg white film; preparing an alcohol-based high-k oxide film; activating the surface of the alcohol-based high-k oxide film; preparing a water-based TMOS film; and preparing a source electrode and a drain electrode. According to the invention, on one hand, a large-area uniform high-k egg white film is obtained, on the other hand, the preparation compatibility between the egg white film and the water-based TMOS film is improved by virtue of the alcohol-based high-k oxide film, and the preparation of the full-solution degradable organic-inorganic thin film transistor based on the egg white film-high-k oxide film-TMOS film is realized.
Description
Technical Field
The invention belongs to the technical field of semiconductors, and particularly relates to an egg white thin film and a preparation method of a degradable organic-inorganic thin film transistor.
Background
With the rapid development of information technology, in order to meet the increasingly rich consumption experience of consumers, the updating frequency of consumer electronics is accelerated continuously, so that the consumer electronics market is promoted to expand rapidly, and a large amount of waste electronic products are generated. However, electronic waste (E-waste) formed by improper recycling of waste electronic products wastes rare earth elements and precious metal resources, and also causes a certain environmental burden, thereby restricting the strategic goal of sustainable development to a certain extent. In view of the characteristics of biodegradability and environmental friendliness of the biological material, the biological material is introduced into an electronic functional device as a functional layer, so that the recycling difficulty of waste electronic products is greatly reduced, and the problems of resource waste and environmental pollution caused by electronic wastes are solved. Therefore, the application of a new generation of green, environment-friendly and biocompatible electronic functional device prepared based on biodegradable and environment-friendly biomaterials in consumer electronics products has attracted extensive attention of researchers.
Display devices, as "windows" for man-machine interaction in most consumer electronics products, have become an important component of many consumer electronics products, such as mobile phones, vehicle displays, wearable devices, luxury goods, VR/AR, and so on. The Thin Film Transistor (TFT) is used as a common basic technology of various display devices, and the low-temperature preparation of the TFT by the all-solution method has important significance for constructing a printing TFT array technology system and realizing the combination of printing display and flexible display technologies. The channel layer and the gate insulating layer are key functional layers of the TFT, wherein a metal oxide semiconductor (TMOS) becomes one of the best channel layer materials which realize high carrier mobility and are suitable for preparing a flexible display device by virtue of the advantages of high electron mobility, high transmittance of a visible light region and large-area performance uniformity; the egg white film as a biodegradable film has the characteristics of easy acquisition, high transmittance, simple process, low price, environmental friendliness, large relative dielectric constant (k) and the like, and is a promising degradable gate insulating layer material.
The egg white contains a large amount of thick protein, which is a fibrous colloidal substance mainly composed of ovomucin and ovomucoid, and has high viscosity. In the prior art, the egg white thin film is directly deposited by adopting an egg white stock solution, the uniformity of the thin film is poor after the thin film is formed, and the egg white thin film is composed of a large number of amino acid side chains, has obvious hydrophobicity, is not beneficial to the solution method deposition of a subsequent thin film, and is particularly not beneficial to the deposition of the subsequent thin film based on a water-based solution method. In view of the above factors, in the prior art, when electronic devices such as a TFT and a memristor based on an egg white film are manufactured, a vacuum coating technology is mostly adopted to deposit a subsequent film, which is not favorable for the construction of a printing TMOS-TFT array technology system. Therefore, a method for guaranteeing the uniformity of the egg white thin film and improving the compatibility of the egg white thin film and a TMOS thin film deposited by a subsequent solution method is sought, and the method is particularly important for low-temperature preparation of a full-solution degradable organic-inorganic thin film transistor.
Disclosure of Invention
In view of the above, the invention provides a preparation method of an egg white film and a degradable organic-inorganic thin film transistor, so as to solve the problems that in the prior art, the uniformity and wettability of the egg white film after film formation are poor, and the subsequent film solution deposition is not facilitated.
In order to achieve the purpose, the invention provides the following technical scheme: a preparation method of an egg white film comprises the following steps:
a1, preparing an egg white precursor solution;
a2, substrate cleaning and surface activation: cleaning and surface activating the substrate to obtain the substrate after the surface activating treatment;
a3, preparation of an egg white film: firstly, enabling the egg white precursor solution to form an egg white wet film on a substrate; and then annealing the egg white wet film to obtain an egg white film.
Further, the specific steps of step A1 include:
(1) Separating egg white from egg yolk, and collecting egg white;
(2) Filtering the collected egg white by adopting a single-layer sterile gauze;
(3) Carrying out vacuum filtration on the filtered egg white by using a plurality of layers of sterile gauze;
(4) Diluting according to the volume ratio of egg white to deionized water of 1 to 0 to 1, and treating the diluted solution for 1-60min by using an ultrasonic cell disruption instrument to obtain a uniform egg white solution;
(5) Putting the egg white solution into a centrifuge tube, centrifuging at 3000-12000 r for 1-60min, and collecting supernatant to obtain egg white precursor solution.
Further, the specific steps of step A3 include:
(1) Forming an egg white wet film on the substrate by adopting any one of spin coating, bar coating, lifting, drop coating and ink-jet printing;
(2) And (3) putting the wet egg white film on a heating table or a drying box, and carrying out one-step annealing treatment for 0-120min at 25-200 ℃, or carrying out multi-step gradient annealing treatment for 0-120min at 25-200 ℃ to obtain an egg white film.
Based on the egg white film, the invention also provides a preparation method of the degradable organic-inorganic thin film transistor, which comprises the following steps:
s1, preparing an alcohol-based high-k oxide precursor solution and a water-based TMOS precursor solution;
s2, activating the surface of an egg white film, wherein the egg white film is prepared by adopting the steps A1-A3 of the preparation method of the egg white film, and a substrate used in the preparation of the egg white film is one of a highly-doped silicon wafer, ITO glass or an ITO flexible polymer substrate;
s3, preparing an alcohol-based high-k oxide film;
s4, activating the surface of the alcohol-based high-k oxide film;
s5, preparing a water-based TMOS film;
s6, preparation of a source electrode and a drain electrode: and preparing a source electrode and a drain electrode on the water-based TMOS thin film so as to obtain the degradable organic-inorganic thin film transistor.
Further, in the step S1, the alcohol-based high-k oxide precursor solution includes Al 2 O 3 Precursor liquid, zrO 2 Precursor solution, hfO 2 Any one or combination of a plurality of precursor solutions of MgO, srO and the like. (ii) a
Further, in the step S1, the water-based TMOS precursor solution includes In 2 O 3 Precursor solution, znO precursor solution, unit element doped In 2 O 3 Precursor solution, single-element doped ZnO precursor solution and multi-element doped In 2 O 3 Any one or a combination of a plurality of precursor solutions and multi-element doped ZnO precursor solutions. (ii) a
Further, in the step S3, firstly, the alcohol-based high-k oxide precursor solution is dripped on the egg white film after surface activation, and an alcohol-based high-k oxide wet film is formed on the egg white film by a spin coating method; then placing the wet film of the alcohol-based high-k oxide on a heating table, and carrying out annealing treatment at 40-200 ℃ for 0-120min to obtain the alcohol-based high-k oxide film.
Further, in the step S2 and the step S4, the surface activation adopts the plasma treatment technology, the egg white film and the alcohol group high-k oxide film are respectively placed in a plasma cleaning machine, and the plasma treatment temperature and the O temperature are 20-100 DEG C 2 、Ar、N 2 In any gas plasma environment, performing plasma treatment for 1-30min to obtain surface activated egg white film and alcohol group high k oxide film.
Further, the specific step of step S5 includes:
(1) Dripping water-based TMOS precursor liquid on the alcohol-based high-k oxide film with the activated surface, and forming a TMOS wet film on the alcohol-based high-k oxide film by adopting a spin-coating method;
(2) Placing the TMOS wet film on a heating table or a drying box, and carrying out annealing treatment for 0-120min at 40-200 ℃ to obtain a pre-annealed TMOS film;
(3) N-performing on the preannealed TMOS film 2 Plasma treatment to obtain low temperature activated TMOS films, where N 2 The plasma treatment process adopts high-purity N 2 Or ultrapure N 2 As a plasma gas source, the gas flow is 10-700sccm, the plasma treatment power is 10-200W, the plasma treatment temperature is 25-250 ℃, the plasma treatment time is 30s-60min, and the plasma treatment pressure is 500-1500mTorr;
(4) Performing post-annealing on the TMOS film activated at the low temperature to obtain the TMOS film, wherein the post-annealing environment is N 2 Environment, O 2 One of an environment and an Ar environment, wherein the annealing temperature is 25-250 ℃, and the annealing time is 0-12h.
Further, in step S6, the source electrode and the drain electrode are made of one or more of Al, au, ag, cu, ni, mo, ITO, and AZO; the thickness of the source electrode and the drain electrode is 10-200nm; the channel width-length ratio of the source electrode to the drain electrode is 1; the degradable organic-inorganic thin film transistor is of a bottom-gate-top contact type structure, wherein highly-doped silicon in a highly-doped silicon wafer or an ITO film in ITO glass and an ITO flexible polymer substrate are used as a gate electrode of the degradable organic-inorganic thin film transistor, a laminated film formed by an egg white film and an alcohol-based high-k oxide film is used as a gate insulating layer of the degradable organic-inorganic thin film transistor, and a TMOS film is used as a channel layer of the degradable organic-inorganic thin film transistor.
Compared with the prior art, the invention has the following beneficial effects:
1) The egg white film provided by the invention is derived from egg white protein, belongs to biological materials, has wide sources and low price, does not need artificial synthesis and is easy to obtain; however, the viscosity and molecular weight of the concentrated protein in the egg white are high, and the egg white solution filtered by gauze or diluted by water is difficult to obtain a large-area uniform egg white film. According to the invention, on the basis of filtering and removing umbilical cord blocks, broken eggshells and other macroscopic impurities in egg white by gauze, the egg white is further treated, firstly, multiple layers of sterile gauze are adopted to carry out vacuum filtration on the egg white, and part of thick protein in the egg white is removed; then, diluting the egg white with deionized water in different proportions to obtain egg white diluents with different concentrations so as to adjust the thickness of the egg white film, wherein insoluble substances are separated out in the process of diluting the egg white, and the separated insoluble substances can seriously weaken the dielectric property of the egg white film; then processing egg white diluents with different proportions by adopting an ultrasonic cell disruption instrument, reducing the viscosity of the solution by disrupting thick protein in the solution, and simultaneously, disrupting insoluble substances precipitated in the solution to promote redissolution of the insoluble substances; and finally, centrifuging the solution at a high speed, separating a clear egg white solution from trace insoluble substances in the solution, and taking supernatant as an egg white precursor solution. In view of the fact that the large-area uniformity of the egg white film is directly determined by the quality of the egg white precursor liquid, the egg white precursor liquid prepared by the method has moderate viscosity and less impurities compared with the egg white stock liquid obtained by filtering or the egg white diluent obtained by diluting with water, so that the problem that the film is uneven or the surface roughness of the film is large can be effectively solved by the egg white film prepared by the egg white precursor liquid provided by the method, and the large-area uniform egg white film can be effectively obtained.
2) According to the invention, the egg white film is used as a gate insulating layer, and the organic-inorganic thin film transistor prepared by the method becomes an excellent green degradable functional device by virtue of the rapid degradation characteristics of the egg white film obtained by different crosslinking or denaturation reactions in one or more of deionized water, glycerol, trypsin solution and the like.
3) The method combines the improvement effect of the surface of the egg white film after plasma treatment on the wettability of the alcohol-based precursor solution, effectively solves the wettability problem between the water-based TMOS precursor solution and the egg white film by adding the alcohol-based high-k oxide transition layer, and improves the compatibility between the egg white film and the TMOS film deposited by a subsequent water-based solution method.
4) The insoluble substances precipitated in the solution are crushed while the viscosity of the solution is reduced by crushing the thick protein in the solution by using an ultrasonic cell crusher, so that the redissolution of the insoluble substances is promoted, and the protein component with high dielectric property is reserved in the egg white solution, so that the egg white film prepared at low temperature has large-area uniformity and high dielectric constant (namely high k).
5) The TMOS film is prepared by adopting a plasma low-temperature activation technology, and the egg white film and the high-k oxide laminated film are prepared by adopting a low-temperature method, so that the low-voltage driven degradable organic-inorganic thin film transistor is obtained at the low temperature of less than 200 ℃, and the thin film transistor has the characteristics of biocompatibility, degradability, low-cost, low-temperature preparation, low-voltage driving and low power consumption.
Drawings
FIGS. 1 (a) and (b) are respectively p + + silicon/egg white/Al and p + + silicon/egg white/ZrO 2 A structure diagram of a Metal-Insulator-Semiconductor (MIS) capacitor of Al structure;
FIGS. 2 (a), (b) and (c) are optical photographs of the MIS capacitor of p + + silicon/egg white/Al structure in examples 1, 2 and 3, respectively;
FIG. 3 shows P + + Si/albumen/Al and P + + Si/albumen/ZrO in examples 1 and 4 2 Breakdown characteristic curve of MIS capacitor with Al structure;
FIG. 4 is a breakdown characteristic curve of the p + + silicon/egg white/Al structure MIS capacitor in example 2;
FIG. 5 is a breakdown characteristic curve of the p + + silicon/egg white/Al structure MIS capacitor in example 3;
FIGS. 6 (a) and (b) are optical photographs of the p + + silicon/albumen/Al structure MIS capacitor in comparative example 1 and comparative example 2, respectively;
FIG. 7 shows that egg white-ZrO can be degraded by a bottom grid top contact type full solution method 2 -In 2 O 3 -a structural diagram of a TFT;
FIGS. 8 (a) and (b) are respectively p + + Si/albumen/ZrO in example 4 2 /In 2 O 3 the/Al structure is similar to that of p + + silicon/egg white/In comparative example 3 2 O 3 Optical photographs of/Al structure MIS capacitors;
FIG. 9 shows degradable egg white-ZrO in example 4 2 -In 2 O 3 -a transfer characteristic curve of the TFT;
FIG. 10 shows degradable egg white-ZrO in example 5 2 -In 2 O 3 -a transfer characteristic curve of the TFT;
FIG. 11 is a pairProportion 3 degradable egg white-In 2 O 3 -transfer characteristic curve of the TFT.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments.
Example 1:
in order to further characterize the dielectric properties of the egg white film, the embodiment provides a preparation method of the egg white film, wherein an electrode is plated on the obtained egg white film to obtain an MIS capacitor, and the preparation method comprises the following specific steps:
step 1: the preparation method of the egg white precursor liquid comprises the following specific steps:
(1) Selecting commercially available sterile eggs, breaking the eggs, separating yolk from egg white by using a stainless steel mesh spoon, and putting the obtained egg white into a beaker which is cleaned and disinfected;
(2) Filtering the collected egg white by adopting single-layer sterile gauze, and removing umbilical cord blocks, broken egg shells and partial thick protein in the egg white;
(3) Adopting multiple layers of sterile gauze for the filtered egg white, matching with vacuum filtration, further filtering the egg white, and putting the filtered egg white into a vacuum filtration bottle;
(4) Placing the egg white solution after vacuum filtration in an ultrasonic cell disruptor, and treating for 30min;
(5) And (3) putting the processed egg white solution into a centrifugal tube, centrifuging for 30min at the rotating speed of 12000 r, and taking supernatant to obtain an egg white precursor solution for later use.
Step 2: substrate cleaning and surface activation:
a commercially available highly doped p-type silicon wafer (p + + silicon wafer) is selected as a substrate, a 4-inch p + + silicon wafer is cut according to the size of 20 x 20mm by using a laser cutting machine, and then the cut p + + silicon wafer is placed on a cleaning frame and is sequentially subjected to ultrasonic cleaning in deionized water, acetone, isopropanol and deionized water for 10min. Taking out the substrate, drying the substrate by nitrogen and then placing the substrate in a plasma cleaning machine. Under vacuum conditions at room temperature, using O 2 Performing plasma treatment for 10min with the process parameters of 100W and 50sccm to remove the organic substances on the surface of the substrateAnd residual to activate the surface of the substrate and improve the surface wettability.
And step 3: preparing an egg white film:
firstly, dropwise adding an egg white precursor solution on a p + + silicon wafer adsorbed on a rotary table of a spin coater by using a liquid transfer gun, and spin-coating for 60s at a rotating speed of 3000 r/min to obtain an egg white wet film. Then placing the wet egg white film on a heating plate, and annealing for 10min at the temperature of 30 ℃, 50 ℃ and 70 ℃ in sequence to obtain the egg white film.
And 4, step 4: preparation of top electrode of MIS capacitor:
an Al film with a thickness of 100nm was plated on p + + silicon/egg white using a round hole mask having a diameter of 1000 μm to obtain an MIS capacitor, a schematic view of which is shown in FIG. 1 (a), and a corresponding optical photograph is shown in FIG. 2 (a).
And 5: I-V characteristic test:
and (4) carrying out an I-V characteristic test on the MIS capacitor obtained in the step (4), wherein the breakdown characteristic of the MIS capacitor is shown as an egg white curve in fig. 3.
Example 2:
in order to further characterize the dielectric properties of the egg white film, the embodiment provides a preparation method of the egg white film, wherein an electrode is plated on the obtained egg white film to obtain an MIS capacitor, and the preparation method comprises the following specific steps:
step 1: the preparation method of the egg white precursor liquid comprises the following specific steps:
(1) Selecting commercially available sterile eggs, breaking the eggs, separating yolk from egg white by using a stainless steel mesh spoon, and putting the obtained egg white into a beaker which is cleaned and disinfected;
(2) Filtering the collected egg white by adopting single-layer sterile gauze, and removing umbilical cord blocks, broken egg shells and partial thick protein in the egg white;
(3) Adopting multiple layers of sterile gauze for the filtered egg white, matching with vacuum filtration, further filtering the egg white, and putting the filtered egg white into a vacuum filtration bottle;
(4) And (3) carrying out vacuum filtration on the egg white according to the ratio of the egg white: the volume ratio of the deionized water is 1:1, diluting, and placing the mixed solution in an ultrasonic cell disruption instrument for treatment for 60min;
(5) And (4) putting the processed egg white solution into a centrifuge tube, and centrifuging for 30min at the rotating speed of 12000 r.
And 4, step 4: preparation of top electrode of MIS capacitor:
an Al film with a thickness of 100nm was plated on p + + silicon/egg white using a round hole mask having a diameter of 1000 μm to obtain an MIS capacitor, a schematic view of which is shown in FIG. 1 (a), and a corresponding optical photograph is shown in FIG. 2 (b).
And 5: I-V characteristic test:
the MIS capacitor obtained in step 4 was subjected to an I-V characteristic test, and the breakdown characteristic of the MIS capacitor is shown in fig. 4.
Example 3:
in order to further characterize the dielectric property of the egg white film, plating an electrode on the obtained egg white film to obtain an MIS capacitor, wherein the specific preparation steps are as follows:
step 1: the preparation method of the egg white precursor liquid comprises the following specific steps:
(1) Selecting commercially available sterile eggs, breaking the eggs, separating yolk from egg white by using a stainless steel mesh spoon, and putting the obtained egg white into a beaker which is cleaned and disinfected;
(2) Filtering the collected egg white by adopting single-layer sterile gauze, and removing umbilical cord blocks, broken egg shells and partial thick protein in the egg white;
(3) Adopting multiple layers of sterile gauze for the filtered egg white, matching with vacuum filtration, further filtering the egg white, and putting the filtered egg white into a vacuum filtration bottle;
(4) And (3) carrying out vacuum filtration on the egg white according to the ratio of the egg white: the volume ratio of the deionized water is 1:20, diluting, and placing the mixed solution in an ultrasonic cell disruption instrument for treatment for 60min;
(5) And (4) putting the processed egg white solution into a centrifuge tube, and centrifuging for 30min at the rotating speed of 12000 r.
And 4, step 4: preparation of top electrode of MIS capacitor:
an Al film with a thickness of 100nm was plated on p + + silicon/egg white using a round hole mask having a diameter of 1000 μm to obtain an MIS capacitor, a schematic view of which is shown in FIG. 1 (a), and a corresponding optical photograph is shown in FIG. 2 (c).
I-V characteristic test:
the obtained MIS capacitor was subjected to an I-V characteristic test, and the breakdown characteristic of the MIS capacitor was as shown in fig. 5.
Comparing example 1, example 2 and example 3, it can be seen from the combination of the area of the egg white thin film not covered by the Al electrode in fig. 2 that the egg white thin films prepared by the above three examples all have large area uniformity, and from the combination of the breakdown characteristics shown in fig. 3, fig. 4 and fig. 5, it can be seen that the diluted egg white thin film of 1.
Comparative example 1:
the comparative example provides a conventional egg white film preparation method, in order to further characterize the dielectric property of the egg white film, an electrode is plated on the obtained egg white film to obtain an MIS capacitor, and the specific preparation steps are as follows:
step 1: the preparation method of the egg white precursor liquid comprises the following specific steps:
(1) Selecting commercially available sterile eggs, breaking the eggs, separating yolk from egg white by using a stainless steel mesh spoon, and putting the obtained egg white into a beaker which is cleaned and disinfected;
(2) Filtering the collected egg white by adopting single-layer sterile gauze, removing umbilical cord blocks, broken egg shells and partial thick protein in the egg white, and taking the filtered collected egg white solution as an egg white precursor solution for later use;
And 4, step 4: preparation of top electrode of MIS capacitor:
an Al film with a thickness of 100nm was plated on p + + silicon/egg white using a round hole mask having a diameter of 1000 μm to obtain an MIS capacitor, a schematic view of which is shown in FIG. 1 (a), and a corresponding optical photograph is shown in FIG. 6 (a).
Comparative example 2:
the comparative example provides a conventional egg white film preparation method, in order to further characterize the dielectric property of the egg white film, an electrode is plated on the obtained egg white film to obtain an MIS capacitor, and the specific preparation steps are as follows:
step 1: the preparation method of the egg white precursor liquid comprises the following specific steps:
(1) Selecting commercially available sterile eggs, breaking the eggs, separating egg yolks from egg white by using a stainless steel mesh spoon, and filling the obtained egg white into a beaker which is cleaned and disinfected;
(2) Filtering the collected egg white by adopting single-layer sterile gauze, and removing umbilical cord blocks, broken egg shells and partial thick protein in the egg white;
(3) According to the egg white: deionized water volume ratio of 1:1, mixing and dissolving, and performing ultrasonic treatment in an ultrasonic cleaning machine for 25min to fully mix the deionized water and the egg white to obtain an egg white precursor solution for later use.
And 4, step 4: preparation of top electrode of MIS capacitor:
an Al film with a thickness of 100nm was plated on p + + silicon/egg white using a round hole mask having a diameter of 1000 μm to obtain an MIS capacitor, a schematic view of which is shown in FIG. 1 (a), and a corresponding optical photograph is shown in FIG. 6 (b).
Comparing the area of the egg white film not covered by the Al electrode in fig. 2 (a) and fig. 6 (a), it can be seen that the egg white film prepared by simply filtering the prepared egg white precursor solution has poor film forming quality and obvious wrinkles, and by the providing method of embodiment 1 of the present invention, a large area uniform and smooth egg white film can be obtained.
Comparing the area of the egg white film not covered by the Al electrode in fig. 2 (b) and fig. 6 (b), it can be seen that the egg white film prepared by simply filtering the egg white precursor solution prepared by diluting with 1:1 water has poor film forming quality and obvious cometlike appears, and by the method of embodiment 2 provided by the present invention, a large area of uniform and smooth egg white film can be obtained.
Example 4: the invention provides a preparation method of a degradable organic-inorganic thin film transistor, which comprises the following specific preparation steps:
step 1: preparing egg white film,ZrO 2 Precursor solution and In 2 O 3 Precursor solution:
(1-1) the method for preparing the egg white film is the same as the step 1-3 of the example 1;
（1-2）ZrO 2 preparing a precursor solution: firstly, quantitative ZrO (NO) 3 ) 2 Adding the mixture into a reagent bottle filled with a certain amount of dimethoxyethanol; then placing the reagent bottle on a rotary heating table, magnetically stirring for 9 hours at room temperature, standing for 24 hours to obtain clear, uniform and transparent alcohol-based ZrO 2 with concentration of 0.2 mol/L 2 A precursor solution;
（1-3）In 2 O 3 preparing a precursor solution: first, in (NO) is quantitatively determined 3 ) 3 ·xH 2 Adding O into a reagent bottle filled with quantitative deionized water; then placing the reagent bottle on a rotary heating table, magnetically stirring for 9 hours at room temperature, standing for 24 hours to obtain clear, uniform and transparent water-based In with the concentration of 0.2 mol/L 2 O 3 A precursor liquid.
Step 2: surface activation of the egg white film:
placing the p + + silicon wafer attached with the egg white film in a plasma cleaning machine, and using O under the vacuum condition at room temperature 2 And performing plasma treatment for 10min by using the process parameters of 100W and 50sccm to activate the surface of the egg white film.
And step 3: zrO (ZrO) 2 Preparation of the film:
first, zrO is sprayed using a pipette 2 Dripping the precursor solution on a p + + silicon wafer adsorbed on a rotary disc of a spin coater and attached with an egg white film, and spin-coating at a rotating speed of 3000 r/min for 30s to obtain ZrO 2 And (5) wet film forming. Then ZrO is mixed 2 Placing the wet film on a heating plate, and annealing at an annealing treatment temperature of 70 ℃ for 120min to obtain ZrO 2 A film.
And 4, step 4: zrO (ZrO) 2 Surface activation of the film:
attaching egg white film/ZrO 2 Placing the p + + silicon wafer of the laminated film in a plasma cleaning machine, and using O under the vacuum condition at room temperature 2 Performing plasma treatment for 10min with the process parameters of 100W and 50sccm to obtain ZrO 2 And (5) activating the surface of the film.
And 5: in 2 O 3 Preparation of the film:
first, in was transferred using a pipette 2 O 3 The precursor solution is dripped on a turntable adsorbed on a spin coater to be adhered with an egg white film/ZrO 2 Spin coating the p + + silicon wafer with laminated film at 4500 rpm for 30s to obtain In 2 O 3 Wet film forming; then In is added 2 O 3 Placing the wet film on a heating plate, and annealing at an annealing temperature of 70 ℃ for 10min to obtain pre-cured In 2 O 3 A film; finally pre-curing In 2 O 3 The film is placed in a plasma processing device for N 2 Plasma treating for 30min to obtain In 2 O 3 A film, wherein the plasma treatment temperature is controlled to 70 ℃, the plasma treatment power is controlled to 100W, the plasma working pressure is 1000mTorr 2 The gas flux of (2) was 400sccm.
Step 6: preparing TFT source and drain electrodes and MIS capacitor top electrode:
adopting a thermal evaporation mode, and adopting a mask plate with the width-length ratio of a channel region being 1000/100 mu m In 2 O 3 Plating an Al film with the thickness of 100nm on the film to obtain the bottom grid top contact type full solution method degradable egg white-ZrO 2 -In 2 O 3 -a TFT having a schematic structure as shown in fig. 7; adopting a round hole mask plate with the diameter of 1000 mu m on p + + silicon/egg white/ZrO 2 /In 2 O 3 An Al film with a thickness of 100nm was plated on the thin film to obtain an MIS capacitor, whose schematic view is shown in FIG. 1 (b), and the corresponding optical photograph is shown in FIG. 8 (a).
And 7: I-V characteristic test:
the obtained TFT and MIS capacitor were subjected to I-V characteristic test, the transfer characteristic curve of the TFT is shown in FIG. 9, and the breakdown characteristic of the MIS capacitor is shown in FIG. 3 2 Shown in the graph.
Example 5:
the invention provides a preparation method of a degradable organic-inorganic thin film transistor, which comprises the following specific preparation steps:
step 1: preparation of egg white film, zrO 2 Precursor solution and In 2 O 3 Precursor solution:
(1-1) preparation of egg white film the same as in 1-3 of example 2;
（1-2）ZrO 2 preparation of precursor solution and (1-3) In 2 O 3 The precursor solution was prepared as in example 4.
Step 6: preparation of TFT source and drain electrodes:
adopting a thermal evaporation mode, and adopting a mask plate with the width-length ratio of a channel region being 1000/100 mu m In 2 O 3 Plating an Al film with the thickness of 100nm on the film to obtain the bottom grid top contact type full solution method degradable egg white-ZrO 2 -In 2 O 3 A TFT, the schematic diagram of which is shown in FIG. 7.
And 7: I-V characteristic test:
the obtained TFT was subjected to an I-V characteristic test, and the transfer characteristic curve of the TFT was as shown in FIG. 10.
As can be seen from the TFT transfer characteristic curves shown in fig. 9 and 10, the TFT prepared by the method for preparing a degradable organic-inorganic thin film transistor provided by the present invention exhibits excellent TFT transfer characteristics.
Comparative example 3:
based on the above example 1, this comparative example provides a conventional TFT fabrication method as a comparative example to example 4, specifically including the following steps:
step 1: preparation of egg white film and In 2 O 3 Precursor solution:
(1-1) the method for preparing the egg white film is the same as the step 1-3 of the example 1;
（1-2）In 2 O 3 the precursor solution was prepared as in example 4.
And 3, step 3: in (In) 2 O 3 Preparing a film:
first, in was transferred using a pipette 2 O 3 Dripping the precursor solution on a p + + silicon wafer adsorbed on a rotary disc of a spin coater and attached with an egg white film, and spin-coating at 4500 rpm for 30s to obtain In 2 O 3 Wet film forming; then In is added 2 O 3 Placing the wet film on a heating plate, and annealing at 70 deg.CAnnealing at the temperature of fire treatment for 10min to obtain pre-cured In 2 O 3 A film; finally pre-curing In 2 O 3 The film is placed in a plasma processing device for N 2 Plasma treatment for 30min to obtain In 2 O 3 A film, wherein the plasma treatment temperature is controlled to be 70 ℃, the plasma treatment power is controlled to be 100W, the plasma working pressure is 1000mTorr, N is added to the film 2 The gas flux of (2) was 400sccm.
And 4, step 4: preparing TFT source and drain electrodes and MIS capacitor top electrode:
adopting a thermal evaporation mode, and adopting a mask plate with the width-length ratio of a channel region being 1000/100 mu m In 2 O 3 Plating an Al film with the thickness of 100nm on the film to obtain the bottom gate top contact type all-solution degradable egg white-In 2 O 3 -a TFT; adopting a round hole mask plate with the diameter of 1000 mu m to perform on p + + silicon/egg white/In 2 O 3 An Al film having a thickness of 100nm was formed on the thin film to obtain an MIS capacitor, and the photo photograph thereof is shown in FIG. 8 (b).
And 5: I-V characteristic test:
the obtained TFT was subjected to an I-V characteristic test, and the transfer characteristic curve of the TFT was as shown in FIG. 11.
Comparing the regions of the egg white thin film not covered with the Al electrode In fig. 8 (a) and 8 (b), it was found that the egg white thin film could not be applied to the water-based In by the plasma treatment alone 2 O 3 Precursor solution infiltration and corresponding egg white-In 2 O 3 The TFT is not turned on. As can be seen from fig. 3, 9 and 11, the method provided In embodiment 4 of the present invention is applied to the egg white thin film and the water-based In 2 O 3 Alcohol-based ZrO is added between films 2 The transition layer can effectively solve the problem of wettability between the water-based TMOS precursor liquid and the egg white film on the premise of ensuring the dielectric property of the egg white film.
Claims (10)
1. A preparation method of an egg white film is characterized by comprising the following steps:
a1, preparing an egg white precursor solution;
a2, substrate cleaning and surface activation: cleaning and surface activating the substrate to obtain the substrate after the surface activating treatment;
a3, preparation of an egg white film: firstly, enabling the egg white precursor solution to form an egg white wet film on a substrate; and then annealing the egg white wet film to obtain an egg white film.
2. The method for preparing an egg white film according to claim 1, wherein the specific steps of the step A1 comprise:
(1) Separating egg white from egg yolk, and collecting egg white;
(2) Filtering the collected egg white by adopting a single-layer sterile gauze;
(3) Carrying out vacuum filtration on the filtered egg white by using a plurality of layers of sterile gauze;
(4) Diluting according to the volume ratio of egg white to deionized water of 1 to 0 to 1;
(5) Putting the egg white solution into a centrifuge tube, centrifuging at 3000-12000 r for 1-60min, and collecting supernatant to obtain egg white precursor solution.
3. The method for preparing an egg white film according to claim 1, wherein the specific steps of the step A3 comprise:
(1) Forming an egg white wet film on the substrate by adopting any one of spin coating, bar coating, lifting, drop coating and ink-jet printing;
(2) And (3) putting the wet egg white film on a heating table or a drying box, and carrying out one-step annealing treatment for 0-120min at 25-200 ℃, or carrying out multi-step gradient annealing treatment for 0-120min at 25-200 ℃ to obtain an egg white film.
4. The method for preparing a degradable organic-inorganic thin film transistor from an egg white thin film according to claim 1, comprising the following steps:
s1, preparing an alcohol-based high-k oxide precursor solution and a water-based TMOS precursor solution;
s2, activating the surface of the egg white film, wherein the substrate used in the preparation of the egg white film is one of a highly-doped silicon wafer, ITO glass or an ITO flexible polymer substrate;
s3, preparing an alcohol-based high-k oxide film;
s4, activating the surface of the alcohol-based high-k oxide film;
s5, preparing a water-based TMOS film;
s6, preparation of a source electrode and a drain electrode: and preparing a source electrode and a drain electrode on the water-based TMOS thin film so as to obtain the degradable organic-inorganic thin film transistor.
5. The method of claim 4, wherein the method comprises the following steps: in the step S1, the alcohol-based high-k oxide precursor solution comprises Al 2 O 3 Precursor liquid, zrO 2 Precursor solution, hfO 2 Any one or combination of a plurality of precursor solutions of MgO, srO and the like.
6. The method of claim 4, wherein the method comprises the following steps: in the step S1, the water-based TMOS precursor liquid comprises In 2 O 3 Precursor solution, znO precursor solution, unit element doped In 2 O 3 Precursor solution, single-element doped ZnO precursor solution and multi-element doped In 2 O 3 Any one or a combination of a plurality of precursor solutions and multi-element doped ZnO precursor solutions.
7. The method of any one of claims 4-6, wherein the method comprises the steps of: in the step S3, firstly, the alcohol group high-k oxide precursor solution is dripped on the egg white film with the activated surface, and an alcohol group high-k oxide wet film is formed on the egg white film by adopting a spin coating method; then placing the wet film of the alcohol-based high-k oxide on a heating table, and carrying out annealing treatment at 40-200 ℃ for 0-120min to obtain the alcohol-based high-k oxide film.
8. According to claim 7The preparation method of the degradable organic-inorganic thin film transistor is characterized by comprising the following steps: in the step S2 and the step S4, the surface activation adopts a plasma treatment technology, the egg white film and the alcohol-based high-k oxide film are respectively placed in a plasma cleaning machine, and the plasma treatment temperature and the plasma treatment O are between 20 and 100 DEG C 2 、Ar、N 2 In plasma environment of any gas, performing plasma treatment for 1-30min to obtain surface activated egg white film and alcohol group high k oxide film.
9. The method of claim 8, wherein the step of preparing the degradable organic-inorganic thin film transistor comprises: the specific steps of the step S5 comprise:
(1) Dripping water-based TMOS precursor liquid on the alcohol-based high-k oxide film with the activated surface, and forming a TMOS wet film on the alcohol-based high-k oxide film by adopting a spin-coating method;
(2) Placing the TMOS wet film on a heating table or a drying box, and carrying out annealing treatment for 0-120min at 40-200 ℃ to obtain a pre-annealed TMOS film;
(3) N-performing on the pre-annealed TMOS film 2 Plasma treatment to obtain a low temperature activated TMOS film, wherein N 2 The plasma treatment process adopts high-purity N 2 Or ultrapure N 2 As a plasma gas source, the gas flow is 10-700sccm, the plasma treatment power is 10-200W, the plasma treatment temperature is 25-250 ℃, the plasma treatment time is 30s-60min, and the plasma treatment pressure is 500-1500mTorr;
(4) Performing post-annealing on the TMOS film activated at the low temperature to obtain the TMOS film, wherein the post-annealing environment is N 2 Environment, O 2 One of an environment and an Ar environment, wherein the annealing temperature is 25-250 ℃, and the annealing time is 0-12h.
10. The method of claim 9, wherein the step of preparing the degradable organic-inorganic thin film transistor comprises: in the step S6, the source electrode and the drain electrode are made of one or more of Al, au, ag, cu, ni, mo, ITO, and AZO; the thickness of the source electrode and the drain electrode is 10-200nm; the channel width-length ratio of the source electrode to the drain electrode is 1; the degradable organic-inorganic thin film transistor is of a bottom-gate-top contact type structure, wherein highly-doped silicon in a highly-doped silicon wafer or an ITO thin film in ITO glass and an ITO flexible polymer substrate is used as a gate electrode of the degradable organic-inorganic thin film transistor, a laminated thin film formed by an egg white thin film and an alcohol-based high-k oxide thin film is used as a gate insulating layer of the degradable organic-inorganic thin film transistor, and a TMOS thin film is used as a channel layer of the degradable organic-inorganic thin film transistor.
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