CN108546936B

CN108546936B - method for preparing high-performance ZnO-based transparent conductive oxide film at low temperature

Info

Publication number: CN108546936B
Application number: CN201810439359.7A
Authority: CN
Inventors: 戴英; 贾倩; 裴新美; 陈文�
Original assignee: Wuhan University of Technology (WUT)
Current assignee: Wuhan University of Technology (WUT)
Priority date: 2018-05-09
Filing date: 2018-05-09
Publication date: 2020-01-31
Anticipated expiration: 2038-05-09
Also published as: CN108546936A

Abstract

The invention relates to methods for preparing high-performance ZnO-based transparent conductive oxide films at low temperature, which comprises the following steps of 1) dissolving zinc acetate dihydrate, an Al source and an Sn source into ethylene glycol monomethyl ether according to requirements, then dropwise adding a stabilizer into a zinc-containing solution, heating, stirring, filtering, and fully aging at room temperature to obtain clear and transparent sol for later use, 2) cleaning a substrate, uniformly and spirally coating the sol on the surface of the substrate by using a spin coater, then carrying out pre-heat treatment on the substrate, repeating the processes of spin coating and pre-heat treatment until a gel film is obtained, 3) carrying out annealing treatment of step on the gel film in an air atmosphere, then carrying out annealing treatment of step in a nitrogen or argon atmosphere, and cooling to room temperature to obtain the high-performance ZnO-based transparent conductive oxide films.

Description

method for preparing high-performance ZnO-based transparent conductive oxide film at low temperature

Technical Field

The invention relates to the technical field of photoelectric materials, in particular to methods for preparing a high-performance ZnO-based transparent conductive oxide film at a low temperature.

Background

In recent years, with the continuous development of semiconductor technology, flexible displays, radio frequency identification tags, and wearable electronics have been gradually put on the market. To meet the growing demand of the flexible electronic market, it is very necessary to replace hard glass with flexible polymer materials as substrates. Therefore, the development of a method for preparing the ZnO-based transparent conductive oxide thin film material by a low-temperature process which is compatible with a flexible polymer material is urgent.

At present, many scholars at home and abroad obtain ZnO-based transparent conductive oxide films with low resistivity and high transmittance through different preparation methods, and the adopted methods mainly comprise a magnetron sputtering method, a pulse laser deposition method (PLD), an atomic layer deposition method (ALD), a molecular beam epitaxy Method (MBE), a Sol-gel method (Sol-gel) and the like.

However, the ZnO-based transparent conductive oxide thin films with excellent photoelectric properties prepared by the sol-gel method all adopt high-temperature annealing, namely the annealing temperature is over 600 ℃, the prepared thin film samples have good crystallinity and excellent photoelectric properties, and the thin film samples prepared at low temperature have poor photoelectric properties. In order to enable the ZnO-based transparent conductive oxide film sample to be well applied to flexible materials, a proper method is needed to enable the prepared film sample to have good crystallinity and excellent photoelectric properties at a lower temperature.

Disclosure of Invention

The technical problem to be solved by the invention is to provide methods for preparing a high-performance ZnO-based transparent conductive oxide film at a low temperature aiming at the defects in the prior art, the method can effectively reduce the lattice energy of a reaction system, so that the ZnO-based transparent conductive oxide film is crystallized in advance at the temperature of about 450 ℃, and the prepared ZnO-based transparent conductive oxide film has good optical performance and electrical performance.

In order to solve the technical problems, the technical scheme provided by the invention is as follows:

methods for preparing high-performance ZnO-based transparent conductive oxide film at low temperature are provided, and the chemical formula of the ZnO-based transparent conductive oxide film is Sn_xAl_yZn_1-x-yO, wherein x is more than or equal to 0 and less than or equal to 0.015, y is more than or equal to 0.01 and less than or equal to 0.03, and the method comprises the following specific steps:

1) zinc acetate dihydrate (Zn (CH) according to the requirement₃COO)₂·2H₂Dissolving O) and Al source and Sn source in ethylene glycol monomethyl ether to obtain a zinc-containing solution, then dropwise adding a stabilizer into the zinc-containing solution, heating and stirring at 50-70 ℃, filtering, and fully aging the obtained clear solution at room temperature to obtain clear and transparent sol for later use;

2) cleaning a substrate to obtain a clean substrate, uniformly spin-coating the sol obtained in the step 1) on the surface of the cleaned substrate by using a spin coater, then carrying out pre-heat treatment on the substrate coated with the sol, and repeating the processes of spin coating and pre-heat treatment until a gel film is obtained;

3) and (3) firstly carrying out th annealing treatment on the gel film obtained in the step 2) in an air atmosphere, then carrying out the second annealing treatment in a nitrogen or argon atmosphere, and cooling to room temperature to obtain the high-performance ZnO-based transparent conductive oxide film.

According to the scheme, the concentration of zinc ions in the zinc-containing solution in the step 1) is 0.2-0.5 mol/L.

According to the scheme, the Al source in the step 1) is aluminum nitrate nonahydrate (Al (NO)₃)₃·9H₂O), Al source and Zn in Zn-containing solution²⁺The molar ratio of (A) is 0.01-0.04: 1.

according to the scheme, the Sn source in the step 1) is tin tetrachloride pentahydrate (SnCl)₄·5H₂O), Sn source and Zn in Zn-containing solution²⁺The molar ratio of (A) to (B) is 0-0.02: 1.

according to the scheme, the stabilizer in the step 1) is ethanolamine, and the molar ratio of the ethanolamine to metal ions in the zinc-containing solution is 0.9-1.1: 1.

according to the scheme, the substrate in the step 2) is kinds of quartz, glass and flexible glass.

According to the scheme, the rotating speed of the spin coater in the step 2) is 2000-4000 rpm, and the spin coating time is 20-30 s.

According to the scheme, the pre-heat treatment process conditions in the step 2) are as follows: heating at 150 deg.C for 5min, and then at 300 deg.C for 10 min.

According to the scheme, the annealing treatment in the th step in the step 3) is carried out under the process conditions that the temperature is increased to 400-600 ℃ at the speed of 2-5 ℃/min at room temperature, and the temperature is kept for 0.5-2 h.

According to the scheme, the process conditions of the second annealing treatment in the step 3) are as follows: raising the temperature to 400-600 ℃ at the speed of 5 ℃/min at room temperature, and preserving the temperature for 0.5-2 h.

The invention also comprisesThe ZnO-based transparent conductive oxide film prepared by the method has a chemical formula of Sn_xAl_yZn_1-x-yO, wherein x is more than or equal to 0 and less than or equal to 0.015, and y is more than or equal to 0.01 and less than or equal to 0.03.

Preferably, the thickness of the ZnO-based transparent conductive oxide film is 100-600 nm.

According to the invention, through doping modification, the lattice energy of the reaction system is effectively reduced within a proper doping proportion range, so that the film crystal is crystallized in advance at an annealing temperature of about 450 ℃, and a film sample with excellent photoelectric performance is obtained at a temperature of about 450 ℃. If the doping ratio is too high, the lattice order inside the film is reduced, and it is difficult to ensure good crystallinity of the film when annealing at low temperature. The invention can reduce the lattice energy of the reaction system under a proper doping proportion, and can lead the film to be crystallized in advance and simultaneously keep the orderliness of the crystal lattice as much as possible at the annealing temperature of about 450 ℃, so that the film has a good crystallization state and thus has excellent photoelectric performance.

The invention has the beneficial effects that: 1. the preparation method provided by the invention has the advantages of simple process, no need of expensive instruments and vacuum environment, low cost, capability of preparing a large-area film with good uniformity, no limitation on the shape of the substrate, and capability of effectively reducing the lattice energy of a reaction system and enabling the film to be crystallized in advance at about 450 ℃. 2. The ZnO-based transparent conductive oxide film prepared by the invention has the advantages of easy and accurate control of components, low heat treatment temperature, suitability for preparation on a flexible polymer substrate, high optical transmittance and excellent electrical properties.

Drawings

FIG. 1 is an XRD pattern of film samples prepared according to comparative example 1 and examples 1 and 3 of the present invention;

FIG. 2 is a TG-DSC curve of the ZnO xerogel prepared in comparative example 1;

FIG. 3 is a TG-DSC curve of the SAZO xerogel prepared in example 3;

FIG. 4 is an optical transmission spectrum of a film sample prepared in comparative example 1 and examples 1 and 3;

FIG. 5 is an XRD pattern of AZO films with different Al contents prepared in example 2;

FIG. 6 is the optical transmission spectrum of AZO films with different Al contents prepared in example 2;

FIG. 7 is an XRD pattern of SAZO films of different Sn loadings prepared in example 4;

FIG. 8 is optical transmission spectra of SAZO films with different Sn contents prepared in example 4.

Detailed Description

In order to make the technical solution of the present invention better understood, the present invention is further described in detail with reference to the attached drawings.

Comparative example 1

A method for preparing low-temperature high-performance transparent conductive oxide film, comprising the following steps:

(1) according to chemical composition Zn_1.0Stoichiometric ratio of O element 3.3259g of Zinc acetate dihydrate (Zn (CH)₃COO)₂·2H₂O), dissolving the ethanol-containing composite material in 20mL of glycol monomethyl ether solvent, dropwise adding 0.9mL of ethanolamine into the solution by using a dropper, then fixing the volume to enable the sol concentration to be 0.3M/L, heating the prepared solution to 60 ℃, stirring for 3 hours, filtering, standing the obtained clear solution at room temperature for 48 hours, and fully aging to form clear and transparent sol for later use;

(2) ultrasonically cleaning a quartz substrate in acetone, ethanol and deionized water for 20min to obtain a clean substrate, uniformly spin-coating sol on the surface of the cleaned substrate at the rotating speed of 3000rpm by using a spin coater, wherein the spin-coating time is 30s, placing a uniformly spin-coated wet film on a glue baking machine for pre-heat treatment, heating the film at the low temperature of 150 ℃ for 5min, heating the film at the high temperature of 300 ℃ for 10min, and repeating the processes of glue coating and pre-heat treatment for 10 times to obtain a gel film subjected to the pre-heat treatment;

(3) heating the gel film subjected to the pre-heat treatment to the annealing temperature at the room temperature at the speed of 2 ℃/min in the air atmosphere, annealing for 1h, and then carrying out N₂Heating to annealing temperature at 5 deg.C/min in atmosphere for annealing for 1h (annealing temperature is 450 deg.C and 600 deg.C respectively), and coolingCooling to room temperature to finally obtain an undoped pure ZnO film sample, wherein the film thickness is 230 nm.

FIGS. 1(a) and (d) are XRD patterns of pure ZnO films obtained by annealing at 450 ℃ and 600 ℃ respectively in this comparative example. As can be seen, the crystallinity of the sample is very low at 450 ℃, the crystallization is incomplete, and the crystallinity of the film sample is intact at an annealing temperature of 600 ℃.

FIG. 2 is a TG-DSC curve of the prepared ZnO xerogel measured at a temperature rise rate of 5 ℃/min in a constant air flow. As can be seen from the figure, the ZnO xerogel has two endothermic peaks and two exothermic peaks during the heat treatment. The endothermic peak at 252.6 ℃ is caused by the evaporation of ethylene glycol methyl ether in the xerogel; the 327.4 ℃ endotherm corresponds to the evaporation of the stabilizer diethanolamine. Exothermic peaks at 450.9 ℃ and 479.2 ℃ corresponding to diethanolamine and Zn in the gel²⁺Oxidation and decomposition reactions to form complexes, and nucleation growth process of ZnO.

Fig. 4(a) is an optical transmission spectrum of a thin film sample (annealed at 450 ℃) prepared in this comparative example, and it can be seen from the graph that the transmittance of the thin film sample in the visible light range is more than 85%, and the light transmittance thereof in the ultraviolet band is sharply reduced, and steep absorption edges appear around 380nm of wavelength, which is determined by the optical band gap of the ZnO material itself.

The resistivity of the undoped ZnO film sample is measured by using the resistivity of the four probes, and the resistivity of the undoped ZnO film sample is too large to be measured beyond the measuring range of an instrument.

Example 1

(1) according to chemical composition Al_0.02Zn_0.98Stoichiometric ratio of O element 3.2594g of Zinc acetate dihydrate (Zn (CH)₃COO)₂·2H₂O) and 0.1137g of aluminum nitrate nonahydrate (Al (NO)₃)₃·9H₂O), dissolving the mixture in 20mL of ethylene glycol monomethyl ether solvent, dropwise adding 0.9mL of ethanolamine with the molar ratio of the ethanolamine to metal ions into the solution by using a dropper, then fixing the volume to enable the sol concentration to be 0.3M/L, heating the prepared solution to 60 ℃, stirring for 3 hours, and filteringStanding the obtained clear solution at room temperature for 48h to fully age the solution to form clear and transparent sol for later use;

(3) heating the gel film subjected to the pre-heat treatment from room temperature to 450 ℃ at the speed of 2 ℃/min in the air atmosphere, annealing for 1h, and then carrying out N₂And (3) raising the temperature to 450 ℃ from room temperature at the speed of 5 ℃/min in the atmosphere, annealing for 1h, and finally obtaining the low-temperature high-performance AZO film sample after cooling to room temperature.

Fig. 1(b) is an XRD spectrum of the AZO film prepared in this example, and it can be seen that the diffraction peak intensity of the film sample doped with 2 at.% is significantly increased compared to the film sample doped with undoped ZnO, which indicates that the crystallinity of the film sample is significantly improved by doping Al. This is mainly because the doping of Al can effectively reduce the lattice energy of the reaction system, so that the film crystal can be crystallized in advance at a lower annealing temperature.

Fig. 4(b) shows the optical transmittance of the film sample prepared in this example, which shows that the optical transmittance of the film sample in the visible light region can reach 85% or more. Compared with an undoped pure ZnO film, the film sample has blue shift on the absorption edge in a near ultraviolet region, which shows that the optical band gap value is widened, i.e. the Burstein-Moss effect is intensified.

Example 2

(1) according to chemical composition, Al_0.01Zn_0.99O(1#)、Al_0.03Zn_0.97O (2#) and Al_0.04Zn_0.96The O (3#) element is weighed out in stoichiometric ratio and dihydrate is obtainedZinc acetate (Zn (CH)₃COO)₂·2H₂O) and aluminum nitrate nonahydrate (Al (NO)₃)₃·9H₂O), the specific dosage is shown in Table 1, the mixture is dissolved in 20mL of ethylene glycol monomethyl ether solvent, 0.9mL of ethanolamine with the same molar ratio with metal ions is added into the solution dropwise by a dropper, then the volume is fixed to enable the sol concentration to be 0.3M/L, the prepared solution is heated to 60 ℃, stirred for 3 hours and filtered, the obtained clear solution is kept stand for 48 hours at room temperature, and the clear and transparent sol is formed for standby application;

TABLE 1

Fig. 5 is an XRD spectrum of the AZO thin film with different Al contents prepared in this example, and it can be seen that the diffraction peak intensity of the thin film sample with the Al content of 1 to 3 at.% is obviously increased compared with the thin film sample with undoped ZnO, which indicates that the crystallinity of the thin film sample is obviously improved by doping Al. The main reason is that the Al doping can effectively reduce the oxidative decomposition temperature and the crystallization temperature of the reaction system, thereby reducing the lattice energy of the reaction system and leading the film crystal to be crystallized in advance at a lower temperature. When the doping amount reaches 4%, the crystallinity of the film is slightly reduced compared with that of the film sample of undoped ZnO, mainly due toIs excessive Al³⁺Substituted by Zn²⁺At the position in the crystal lattice, the original structure of the crystal is seriously damaged, so that the crystallinity of the crystal is reduced. It follows that a suitable doping ratio is critical for crystallization of the film sample.

Fig. 6 shows the optical transmittance spectra of the AZO thin films with different Al contents prepared in this example, and it can be seen from the graph that the average transmittance of all the thin film samples in the visible light region can reach above 85%. As the doping amount of Al increases, the absorption edge of all AZO film samples in a near ultraviolet region generates blue shift, which shows that the optical band gap value of the AZO film samples is widened, namely the Burstein-Moss effect is intensified. The introduction of the Al element can effectively reduce the resistivity of the film sample and improve the electrical property of the film sample. And the resistivity of the prepared AZO film is gradually reduced along with the increase of the doping value, and when the doping value is 1-3 at.%, the resistivity of the prepared AZO film is the lowest and is 6.0 multiplied by 10^-3～7×10^-3Ω·cm。

Example 3

(1) by chemical composition Sn_0.015Al_0.02Zn_0.965Stoichiometric ratio of O element 3.2095g of Zinc acetate dihydrate (Zn (CH)₃COO)₂·2H₂O), 0.1137g of aluminum nitrate nonahydrate (Al (NO)₃)₃·9H₂O)0.1137g and 0.0797g tin tetrachloride pentahydrate (SnCl)₄·5H₂O), dissolving the ethanol-containing composite material in 20mL of ethylene glycol monomethyl ether solvent, dropwise adding ethanolamine (0.9mL) with the molar ratio equal to metal ions into the solution by using a dropper, then fixing the volume to enable the sol concentration to be 0.3M/L, heating the prepared solution to 60 ℃, stirring for 3 hours, filtering, standing the obtained clear solution at room temperature for 48 hours, and fully aging to form clear and transparent sol for later use;

(3) heating the gel film subjected to the previous heat treatment from room temperature to 450 ℃ at the speed of 2 ℃/min in the air atmosphere, annealing for 1h, and then placing the gel film in N₂And (3) raising the temperature to 450 ℃ from room temperature at the speed of 5 ℃/min in the atmosphere, annealing for 1h, and finally obtaining the low-temperature high-performance SAZO film sample after cooling to room temperature.

FIG. 1(c) is an XRD spectrum of the thin film prepared in this example. As can be seen, the diffraction peak intensity of the thin film sample prepared by Sn-Al co-doping is obviously increased compared with that of FIGS. 1(a) and (b), which is mainly because: sn (tin)⁴⁺Has a radius of

With Zn²⁺Radius of (2)A little different from each other, Sn⁴⁺The doping does not cause too large deformation and lattice distortion of the film crystal, is beneficial to improving the crystallinity of the film crystal, and can reduce the crystallization temperature required by the film crystal so as to crystallize the film in advance.

FIG. 3 is a TG-DSC curve of SAZO xerogel, the two absorption peaks correspond to the evaporation process of ethylene glycol monomethyl ether and ethanolamine as the stabilizer respectively, and the exothermic peak is mainly due to Zn in the gel²⁺、Al³⁺And Sn⁴⁺Oxidation and decomposition reactions forming complexes with ethanolamine, and nucleation and growth processes of grains, it is worth to mention that³⁺And Sn⁴⁺The exothermic peak position 366.27 ℃ of the SAZO is lower than the exothermic positions 450.9 ℃ and 479.2 ℃ of pure ZnO, which shows that the introduction of doping ions can effectively reduce the lattice energy of the reaction system, so that the film crystal is crystallized in advance at a lower temperature, thereby improving the crystallization degree of the film and improving the photoelectric property of the film at a low temperature.

FIG. 4(c) is an optical transmittance spectrum of the film sample prepared at 450 ℃ in this example, which shows that the average light transmittance of the prepared film sample in the visible light region can reach 85% or more. The transmittance of the film sample is equivalent to that of the film samples in FIGS. 4(a) and (b), and the absorption edge of the film sample in the near ultraviolet region is subjected to blue shift, which shows that the optical band gap value is widened, i.e. the Burstein-Moss effect is intensified.

Example 4

(1) by chemical composition Sn_0.01Al_0.02Zn_0.97O (4#), and Sn_0.02Al_0.02Zn_0.96Weighing zinc acetate dihydrate (Zn (CH) according to the stoichiometric ratio of O (5#) element₃COO)₂·2H₂O), aluminum nitrate nonahydrate (Al (NO)₃)₃·9H₂O)0.1137g and tin tetrachloride pentahydrate (SnCl)₄·5H₂O), the specific dosage is shown in Table 2, the mixture is dissolved in 20mL of ethylene glycol monomethyl ether solvent, ethanolamine (0.9mL) with the same molar ratio with metal ions is added into the solution dropwise by a dropper, then the volume is fixed to enable the sol concentration to be 0.3M/L, the prepared solution is heated to 60 ℃, stirred for 3 hours and filtered, the obtained clear solution is kept stand for 48 hours at room temperature, and the clear and transparent sol is formed for standby application;

TABLE 2

(2) Ultrasonically cleaning a quartz substrate in acetone, ethanol and deionized water for 20min to obtain a clean substrate, uniformly spin-coating sol on the surface of the cleaned substrate at the rotating speed of 3000rpm by using a spin coater, wherein the spin-coating time is 20s, placing a uniformly spin-coated wet film on a glue baking machine for pre-heat treatment, heating the film at the low temperature of 150 ℃ for 5min, heating the film at the high temperature of 300 ℃ for 10min, and repeating the processes of glue coating and pre-heat treatment for 10 times to obtain a gel film subjected to the pre-heat treatment;

(3) heating the gel film subjected to the pre-heat treatment in an air atmosphere from room temperature to a temperature of 2 ℃/minAnnealing at 450 deg.C for 1h, and placing in N₂And (3) raising the temperature to 450 ℃ from room temperature at the speed of 5 ℃/min in the atmosphere, annealing for 1h, and finally obtaining the low-temperature high-performance SAZO film sample after cooling to room temperature.

Fig. 7 is an XRD spectrum of the SAZO films with different Sn doping amounts prepared in this example, and it can be seen that the characteristic diffraction peak intensities in all directions of the SAZO films with Sn doping amounts of 1 at.% to 1.5 at.% are increased compared to the AZO films without Sn doping element, mainly because: sn (tin)⁴⁺Has a radius of

With Zn²⁺Radius of (2)

A little different from each other, Sn⁴⁺The doping of the film does not cause too large deformation and lattice distortion of the film crystal, and is beneficial to improving the crystallinity of the film crystal. And the crystallization temperature required by the film crystal can be reduced, so that the film is crystallized in advance. However, as the doping amount of Sn is increased, the diffraction peak intensity of the film sample in each direction is decreased, and the full width at half maximum of the diffraction peak is widened, mainly because: sn (tin)⁴⁺After entering into crystal lattice, Zn in the crystal lattice is gradually replaced²⁺And become substitutional atoms, which can destroy the original crystal structure of the film sample, cause degree lattice distortion, and generate degree deformation of the crystal.

FIG. 8 is an optical transmittance spectrum of SAZO films with different Sn contents prepared in this example, which shows that the optical transmittance of all the prepared film samples in the visible light region is above 88%, and the steep absorption edge of the film sample shows a tendency to shift to the short wavelength direction with the increase of the Sn content, i.e. the so-called "blue shift" phenomenon, which is mainly caused by the increase of the burst-Moss effect.

The resistivity of the film sample is tested by using a four-probe resistivity tester, and the Sn-Al codoping can effectively reduce the resistivity of the film sample and improve the resistivity of the film sampleIn the range of , the resistivity of the prepared SAZO film gradually decreases with the increase of the Sn doping value, and when the Sn doping value is 1 at.% to 1.5 at.%, the resistivity of the prepared SAZO film is the lowest and is 5.0 x 10^-3～5.5×10^-3Ω·cm。

Claims

1, methods for preparing high-performance ZnO-based transparent conductive oxide film at low temperature, wherein the chemical formula of the ZnO-based transparent conductive oxide film is Sn_xAl_yZn_1-x-yO, wherein x is more than or equal to 0 and less than or equal to 0.015, and y is more than or equal to 0.01 and less than or equal to 0.03, and the method is characterized by comprising the following specific steps of:

3) carrying out th annealing treatment on the gel film obtained in the step 2) in an air atmosphere, then carrying out the second annealing treatment in a nitrogen or argon atmosphere, and cooling to room temperature to obtain a high-performance ZnO-based transparent conductive oxide film;

the process conditions of the th annealing treatment step are that the temperature is raised to 450 ℃ at the speed of 2-5 ℃/min at room temperature, and the temperature is kept for 0.5-2 h;

the process conditions of the second annealing treatment in the step 3) are as follows: heating to 450 ℃ at room temperature at the speed of 5 ℃/min, and keeping the temperature for 0.5-2 h.

2. The method for preparing the high-performance ZnO-based transparent conductive oxide film at the low temperature according to claim 1, wherein the concentration of zinc ions in the zinc-containing solution in the step 1) is 0.2-0.5 mol/L.

3. The method for preparing the high-performance ZnO-based transparent conductive oxide film at the low temperature according to claim 1, wherein the Al source in the step 1) is aluminum nitrate nonahydrate, and the Al source and Zn in the zinc-containing solution²⁺The molar ratio of (A) is 0.01-0.04: 1, the Sn source is tin tetrachloride pentahydrate, and the Sn source and Zn in a zinc-containing solution²⁺The molar ratio of (A) to (B) is 0-0.02: 1.

4. the method for preparing the high-performance ZnO-based transparent conductive oxide film at the low temperature according to claim 1, wherein the stabilizer in the step 1) is ethanolamine, and the molar ratio of the ethanolamine to metal ions in the zinc-containing solution is 0.9-1.1: 1.

5. the method for preparing the high-performance ZnO-based transparent conductive oxide thin film at the low temperature according to claim 1, wherein the substrates in the step 2) are kinds of quartz and glass.

6. The method for preparing the high-performance ZnO-based transparent conductive oxide film at the low temperature according to claim 1, wherein the rotation speed of the spin coater in the step 2) is 2000-4000 rpm, and the spin coating time is 20-30 s.

7. The method for preparing the high-performance ZnO-based transparent conductive oxide thin film at the low temperature according to claim 1, wherein the pre-heat treatment process conditions in the step 2) are as follows: heating at 150 deg.C for 5min, and then at 300 deg.C for 10 min.