CN114496353A - Transparent conductive film with high conductivity and high transmissivity and preparation method and application thereof - Google Patents
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Abstract
The invention belongs to the field of semiconductors, and discloses a transparent conductive film with high conductivity and high transmittance, and a preparation method and application thereof. The transparent conductive film is a CdO-based transparent conductive film, the average transmittance in the range of 400-2500nm is more than 70%, and the conductivity is more than 3000S/cm. In the process of preparing the transparent conductive film, the invention can prepare the transparent conductive oxide film with high transmissivity (average transmissivity > 70%) in the full spectrum, wherein the average transmissivity at 1000-2500nm can be > 80% and high conductivity (more than 3000S/cm) by controlling the substrate temperature, the working gas condition, regulating the concentration of impurities or alloy elements of the film, regulating the thickness of the film and carrying out proper annealing treatment, and can be applied to optoelectronic devices in the full spectrum (visible light, near infrared and even middle infrared bands) including corresponding flexible devices.
Description
Technical Field
The invention belongs to the field of semiconductors, and particularly relates to a transparent conductive film with high conductivity and high transmissivity as well as a preparation method and application thereof.
Background
Transparent Conductive Oxide (TCOs) thin film materials play an important role in the present optoelectronics industry, and are widely used as transparent conductors in optoelectronics fields such as flat panel displays, photovoltaic cells, thin film transistors, photodetectors, gas sensors, light emitting diodes, smart windows, and the like. From the first discovery in 1907 to the wide application at present, TCOs have been extensively studied and developed. Due to the new application requirements, the method has been continuously applied in recent yearsEmerging and facing several key issues, research and development on TCOs is still quite active. The application of the TCOs film at present has at least the following three problems. First, In doped with Sn2O3The (ITO) dominates the current market for transparent conductive materials, but the content of In on the earth surface is very rare, and the film is In short supply In the future, the price is increasingly expensive, and it is difficult to meet the global demand for transparent conductive films (market Research and marks published In 2017 by market regulators indicate that the global market for transparent conductive films is estimated to have an average annual growth rate of more than 9% from 2017 to 2026, and about 85 hundred million dollars are estimated In 2026). Second, the electron mobility (μ about 30 cm) of conventional commercial TCOs films2low/Vs), free carrier concentration (N about 1021/cm3) Larger, which makes the TCOs film have low transparency in the near infrared light band (due to light absorption of free electrons and plasma reflection), and limits the application of TCOs film in near infrared light electronic devices. Thirdly, the industry trend that flexible electronics represented by flexible displays, flexible solar cells and flexible wearable devices rise up is increasingly clarified, and conventional TCOs thin-film materials represented by ITO have poor mechanical flexibility and are difficult to apply to the current flexible optoelectronic devices. Therefore, there is a need in the industry and academia to develop transparent conductive materials with low cost, high transparency to near infrared light and high flexibility, so as to greatly promote the continuous development of intelligent manufacturing fields such as novel (flexible) photoelectrons. In response to the first problem, researchers developed low-cost TCOs thin film materials (e.g., Al-doped ZnO) and realized commercial applications. However, existing low-cost TCOs thin film materials (such as ZnO or SnO)2) Is not as chemically stable as ITO and has not been widely used. In response to the second problem, one generally obtains higher near infrared transmittance (e.g., In doping) by reducing the electron concentration In the TCOs thin films2O3) However, In prepared by industrial large-area production2O3Thin films, in general, have a large number of lattice defects, which make their mobility and corresponding conductivity low. For flexible TCOs films, researchers have mainly used two or more binary oxides (whose corresponding cations differ significantly in valence and size)Approaches to forming amorphous oxide alloys (e.g., amorphous In-Zn-O TCOs films) are realized. However, to obtain an amorphous In-Zn-O film with high conductivity, a higher In content (about 70%) is required. Therefore, there is a need to develop new low-cost high-mobility TCOs thin film materials that can maintain high conductivity at low carrier concentration, thereby obtaining TCOs thin film materials with high transmittance and even flexibility in the full spectrum range (from visible to near infrared).
The existing TCOs market is dominated mainly by ITO. As mentioned above, the In element In ITO has a rare earth surface content and is increasingly expensive. Further, In is doped2O3Electron mobility (in general)<40cm2Vs) and its high frequency dielectric constant are not too high, and the corresponding free electron absorption and plasma reflection result in near infrared light (wavelength)>1100nm) is low (less than 70%); if In is doped by decreasing2O3Concentration of electrons in (e.g. of)<1020cm-3) To improve the transmittance of near infrared light, it is difficult to obtain higher conductivity>3000S/cm) which greatly limits its use in near infrared light electronics. Whereas the existing In-based2O3The flexible TCOs of (a), are also not mechanically flexible enough.
Therefore, it is desirable to provide a novel transparent conductive oxide thin film which not only has a low manufacturing cost, but also has high conductivity, has a high transmittance in the full spectrum (visible light to near infrared or even mid-infrared band), and further has high electron mobility.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art described above. Therefore, the invention provides a transparent conductive film with high conductivity and high transmissivity, and a preparation method and application thereof.
The transparent conductive oxide film based on CdO has high transmissivity (average transmissivity) in the full spectrum (visible light to near infrared and even middle infrared wave band, corresponding to 400->70%, even at an average transmission of 1000->80%), high conductivity (over 300%)0S/cm, e.g., 3100->50cm2Vs, even>100cm2Vs), and excellent mechanical flexibility. Therefore, the high-performance transparent conductive oxide film based on CdO is suitable for all-spectrum (visible light to near infrared or even mid-infrared band) optoelectronic devices, including corresponding flexible devices. Furthermore, In contrast to In2O3The CdO-based Transparent Conductive Oxide (TCOs) thin film also has a significant advantage in terms of cost.
A first aspect of the present invention provides a high-conductivity, high-transmittance transparent conductive film.
Specifically, the transparent conductive film with high conductivity and high transmittance is a CdO-based transparent conductive film, and the average transmittance of the transparent conductive film in the range of 400-2500nm is more than 70%, and the conductivity is more than 3000S/cm.
Preferably, the average transmittance of the transparent conductive film in the range of 1000-.
Preferably, the conductivity of the transparent conductive film is 3100-.
Preferably, the electron mobility of the transparent conductive film>50cm2Vs; further preferably, the electron mobility of the transparent conductive film>60cm2Vs; more preferably, the electron mobility of the transparent conductive film>100cm2/Vs。
Preferably, the transparent conductive film is doped with at least one of In, Ga, V, or Ti.
Preferably, the thickness of the transparent conductive film is not more than 130 nm; further preferably, the thickness of the transparent conductive film is not more than 100nm, more preferably 20 to 50 nm.
The second aspect of the present invention provides a method for preparing the transparent conductive film with high conductivity and high transmittance.
Specifically, the preparation method of the transparent conductive film with high conductivity and high transmittance comprises the following steps:
heating the substrate to 240-320 ℃, and coating a film on the substrate by using a CdO target or a doped CdO target to prepare the transparent conductive film, wherein working gas is required to be used in the film coating process, and the working gas does not contain oxygen;
or the like, or, alternatively,
heating the substrate to 70-120 ℃, and coating a film on the substrate by using the CdO target and another oxide target to prepare the transparent conductive film, wherein working gas is required to be used in the film coating process, and the working gas does not contain oxygen.
Preferably, the substrate is heated to the temperature of 250-300 ℃, a CdO target or a doped CdO target is used for coating on the substrate, and then annealing treatment is carried out to prepare the transparent conductive film.
Preferably, the temperature of the annealing treatment is 500-600 ℃, and the time of the annealing treatment is 5-10 minutes.
Preferably, the impurity element of the doped CdO target is at least one of In, Ga, V or Ti, and the mole fraction of the impurity element is less than 5%.
Preferably, the another oxide target is In2O3Target material or Ga2O3A target material. Coating a film on a substrate by using a CdO target and another oxide target, and adjusting the power of each sputtering target gun to obtain an amorphous transparent conductive film which is an oxide alloy (such as Cd)xIn1-xO1+δ) The film, wherein the value of x is 0.1-0.55, and the value of delta is more than 0 and less than 0.5.
Preferably, the substrate is glass or a flexible plastic, such as PET (polyethylene terephthalate).
Preferably, the coating process can be performed by conventional physical or chemical vapor deposition methods, such as Metal Organic Chemical Vapor Deposition (MOCVD), Pulsed Laser Deposition (PLD), Electron Beam Evaporation (EBE), Plasma Enhanced Chemical Vapor Deposition (PECVD), misted vapor deposition (mist-CVD), low pressure vapor deposition (LPCVD).
Preferably, the working gas is argon; the pressure of the working gas is 0.1-0.5 Pa.
Preferably, the substrate is cleaned by acetone, deionization, before heating.
Preferably, the coating process is carried out under the pressure of less than 5 x 10-4And (4) plating under the vacuum degree of Pa.
A third aspect of the present invention provides the use of the above-described transparent conductive film having high conductivity and high transmittance.
The transparent conductive film with high conductivity and high transmissivity is applied to the preparation of electronic products.
Preferably, the electronic product comprises a flat panel display, a photovoltaic cell, a thin film transistor, a photodetector, a gas sensor, a light emitting diode, or a smart window.
Compared with the prior art, the invention has the following beneficial effects:
(1) the transparent conductive oxide film based on CdO has high transmissivity (average transmissivity) in the full spectrum (visible light to near infrared and even middle infrared wave band, corresponding to 400->70%, an average transmittance at 1000->80 percent), high conductivity (more than 3000S/cm, such as 3100->50cm2Vs, even>100cm2Vs), and excellent mechanical flexibility. Therefore, the high-performance transparent conductive oxide film based on CdO is suitable for all-spectrum (visible light to near infrared or even mid-infrared band) optoelectronic devices, including corresponding flexible devices. Furthermore, In contrast to In2O3The CdO-based Transparent Conductive Oxide (TCOs) thin film also has a significant advantage in terms of cost.
(2) The preparation method can prepare the transparent conductive oxide film with high transmissivity (average transmissivity is more than 70%, the average transmissivity at 1000-2500nm is more than 80%) and high conductivity (more than 3000S/cm, such as 3100-13000S/cm) in the full spectrum (the wavelength from visible light to near infrared and even mid-infrared, corresponding to 400-2500nm) by controlling the substrate temperature, the working gas condition and the target material.
Drawings
FIG. 1 is a graph of transmittance of the transparent conductive film prepared in example 1 and comparative examples 1-2 of the present invention to light wave of 400-3000 nm;
FIG. 2 is a graph of transmittance of the transparent conductive film prepared in examples 3-5 of the present invention to light waves of 400-;
FIG. 3 is a graph showing the transmittance of the transparent conductive films prepared in examples 6-7 and comparative example 3 of the present invention to light waves of 400-3000 nm.
Detailed Description
In order to make the technical solutions of the present invention more apparent to those skilled in the art, the following examples are given for illustration. It should be noted that the following examples are not intended to limit the scope of the claimed invention.
The starting materials, reagents or apparatuses used in the following examples are conventionally commercially available or can be obtained by conventionally known methods, unless otherwise specified.
Example 1: transparent conductive oxide film prepared by undoped CdO target material coating
The preparation method of the transparent conductive film with high conductivity and high transmittance comprises the following steps:
taking a glass substrate, firstly ultrasonically cleaning the glass substrate for 5 minutes by acetone, then ultrasonically cleaning the glass substrate for 5 minutes by ethanol, finally ultrasonically cleaning the glass substrate for 5 minutes by deionized water, and then, cleaning the glass substrate by N2Drying the glass substrate, and putting the cleaned glass substrate on a chamber sample table of a magnetron sputtering deposition system;
vacuumizing the magnetron sputtering deposition chamber until the pressure in the chamber is less than 5 x 10-4After Pa, introducing argon (Ar) into the magnetron sputtering deposition system through a gas path pipeline and adjusting the working pressure to be about 0.5 Pa;
heating the glass substrate to 250 ℃, firstly closing the substrate baffle, applying RF (radio frequency) to the CdO target (the working gas is pure Ar, the sputtering power density is 4W/cm)2) Pre-sputtering for 5 minutes to remove pollutants on the surface of the CdO target, then opening a substrate baffle, and coating a film on the substrate by using the CdO target (the working gas is pure Ar, no oxygen is contained in the working gas, and the sputtering power density is 4W/cm2) And starting film deposition, stopping sputtering when the thickness of the film is about 125nm, and then cooling to room temperature of 20 ℃ to obtain the transparent conductive film with the thickness of 125 nm.
Comparative example 1
In comparison with example 1, the substrate of comparative example 1 was not heated, the substrate of comparative example 1 was at room temperature of 20 ℃, and the rest of the procedure was the same as example 1.
Comparative example 2
Comparative example 2, compared to example 1, the working gas contained 1% flow fraction of oxygen during the deposition of the film on the substrate, and the rest of the process was the same as example 1.
Example 2
In example 2, the transparent conductive film prepared was further annealed at 500 c for 6 minutes in air, compared to example 1. The rest of the procedure was the same as in example 1.
Example 3: preparation of transparent conductive oxide film by using CdO-doped target material coating
In example 3, a CdO-doped target (In which the impurity element may be any one of In, Ga, V, and Ti, and the mole fraction of the impurity element is less than 5%) was used instead of the CdO target In example 1, and the thickness of the obtained transparent conductive oxide thin film was 100nm (the thickness of the transparent conductive oxide thin film can be controlled by controlling the sputtering time), as compared to example 1, and the rest of the procedure was the same as In example 1.
Example 4
Example 4 is different from example 3 in that the sputtering time is shortened such that the thickness of the transparent conductive oxide thin film produced is 50nm, and the rest of the process is the same as example 3.
Example 5
Example 5 is different from example 3 in that the sputtering time is shortened such that the thickness of the transparent conductive oxide thin film produced is 25nm, and the rest of the process is the same as example 3.
Example 6: transparent conductive oxide film prepared by coating with CdO target and another oxide target
The preparation method of the transparent conductive film with high conductivity and high transmittance comprises the following steps:
taking a glass substrate, firstly ultrasonically cleaning the glass substrate for 5 minutes by acetone, then ultrasonically cleaning the glass substrate for 5 minutes by ethanol, and finally ultrasonically cleaning the glass substrate by ethanolUltrasonic cleaning with deionized water for 5 min, and cleaning with N2Drying the glass substrate, and putting the cleaned glass substrate on a chamber sample table of a magnetron sputtering deposition system;
vacuumizing the magnetron sputtering deposition chamber until the pressure in the chamber is less than 5 x 10-4After Pa, introducing argon (Ar) into the magnetron sputtering deposition system through a gas path pipeline and adjusting the working pressure to be about 0.5 Pa;
heating the glass substrate to 100 deg.C, closing the substrate baffle, and aligning the CdO target and another oxide target (In)2O3Target) RF (radio frequency) is applied (the working gas is pure Ar, the sputtering power density is 3W/cm2) Pre-sputtering for 5 min to remove CdO target and In2O3The pollutants on the surface of the target material are removed, then a substrate baffle is opened, and the CdO target material and In are utilized2O3Co-sputtering the target material on the substrate to form a coating (the working gas is pure Ar, the working gas does not contain oxygen, and the sputtering power density is 3W/cm2) And starting film deposition, stopping sputtering when the film thickness is about 100nm, and then cooling to room temperature of 20 ℃ to obtain the transparent conductive film.
Example 7
Example 7 is different from example 6 in that the sputtering time is shortened such that the thickness of the transparent conductive oxide thin film produced is 50nm, and the rest of the process is the same as example 6.
Comparative example 3
The substrate of comparative example 3 was not heated compared to example 6, the substrate of comparative example 3 was at room temperature of 20 ℃, and the rest of the procedure was the same as example 6.
Sample Effect testing
1. The results of examples 1 to 2 and comparative examples 1 to 2 were analyzed
The transparent conductive film prepared in example 1 had a conductivity of 4210S/cm and an electron mobility of 173cm2Vs, electron concentration of 1.52X 1020cm3(ii) a The transparent conductive film obtained in example 2 had a conductivity of 3370S/cm and an electron mobility of 234cm2Vs, electron concentration 9X 1019cm3. Transparent conductive film prepared in comparative example 1Has an electrical conductivity of 2610S/cm and an electron mobility of 62cm2Vs, electron concentration of 2.6X 1020cm3(ii) a The transparent conductive film obtained in comparative example 2 had a conductivity of 560S/cm and an electron mobility of 67cm2Electron concentration of 5.2X 10/Vs19cm3
FIG. 1 is a graph of transmittance of the transparent conductive film prepared in example 1 and comparative examples 1-2 of the present invention to light wave of 400-3000 nm; as can be seen from FIG. 1 (the abscissa "wavelet" in FIG. 1 represents the Wavelength, and the ordinate "T" represents the transmittance), the transmittance of the transparent conductive film prepared in example 1 to the light wave with the Wavelength of 400-2500nm is higher than that of the comparative examples 1-2, especially in the Wavelength range of 1000-2500nm, the transmittance of the transparent conductive film prepared in example 1 to the light wave is significantly better than that of the comparative examples 1-2, and the average transmittance of the transparent conductive film prepared in example 1 to the light wave with the Wavelength of 400-2500nm is over 80%. Therefore, the substrate temperature and whether the working gas contains oxygen or not have a significant influence on the light wave transmittance of the prepared transparent conductive film.
In addition, the light wave transmittance of the transparent conductive film prepared in example 2 is improved by about 3% compared with that of example 1, and it can be seen that the annealing treatment helps to further improve the average transmittance for light waves of 400-2500 nm.
2. Analysis of the results of examples 3 to 5
The transparent conductive film obtained in example 3 had a conductivity of 13392S/cm and an electron mobility of 110cm2Vs, electron concentration of 7.6X 1020cm3A sheet resistance (Rs) of about 7.5 Ω/,; the conductivity, electron mobility and electron concentration of the transparent conductive films obtained in examples 4 to 5 were the same as those of example 3; examples 4-5 produce transparent conductive films having a sheet resistance (Rs) of about 15 omega/, 30 omega/, respectively.
FIG. 2 is a graph of transmittance of the transparent conductive film prepared in examples 3-5 of the present invention to light waves of 400-; as can be seen from FIG. 2 (the abscissa "wavelet" in FIG. 2 represents the Wavelength, and the ordinate "T" represents the transmittance), the transparent conductive film of example 5 is relatively thin, the average transmittance for light waves of 400-2500nm is the highest, and the transmittance for light waves of 1000-2500nm is close to 90%. Therefore, the thickness of the film has an important influence on the light wave transmittance of the transparent conductive film.
3. The results of examples 6 to 7 and comparative example 3 were analyzed
The transparent conductive film obtained in example 6 had a conductivity of 3114S/cm and an electron mobility of 54cm2Vs, electron concentration 3.6X 1020cm3A sheet resistance (Rs) of about 32 Ω/,; the transparent conductive film obtained in example 7 had a conductivity of 3114S/cm and an electron mobility of 54cm2Vs, electron concentration 3.6X 1020cm3The sheet resistance (Rs) is about 64 omega/, ch. The transparent conductive film obtained in comparative example 3 had a conductivity of 2950S/cm and an electron mobility of 42cm2Vs, electron concentration of 4.38X 1020cm3The sheet resistance (Rs) is about 34 omega/, ch.
FIG. 3 is a graph showing the transmittance of the transparent conductive films prepared in examples 6-7 and comparative example 3 of the present invention to light waves of 400-3000nm, and it can be seen from FIG. 3 (the abscissa "wavelet" in FIG. 3 represents the Wavelength, and the ordinate "T" represents the transmittance) that the average transmittance of the transparent conductive film prepared in example 6 to light waves of 400-2500nm is greater than 70%, and the average transmittance of the transparent conductive film prepared in example 6 to light waves of 400-2500nm is greater than 80%.
If the glass substrate in example 6 is replaced with a PET substrate, the photoelectric properties of the prepared transparent conductive film are the same as those of example 6, and the transparent conductive film also has the characteristic of flexibility.
Application example
A photodetector comprising the transparent conductive film prepared in example 1.
In addition, it should be noted that the transparent conductive film with similar effect can be obtained by changing some process parameters, such as the heating temperature of the substrate, within the scope of the claimed invention.
Claims (10)
1. The transparent conductive film is characterized in that the transparent conductive film is a CdO-based transparent conductive film, the average transmittance of the transparent conductive film in the range of 400-2500nm is more than 70%, and the conductivity of the transparent conductive film is more than 3000S/cm.
2. The transparent conductive film as claimed in claim 1, wherein the transparent conductive film has an average transmittance of more than 80% in the range of 1000-2500 nm.
3. The transparent conductive film as claimed in claim 1, wherein the conductivity of the transparent conductive film is 3100-.
4. The transparent conductive film according to claim 1, wherein the transparent conductive film has an electron mobility>50cm2/Vs。
5. The transparent conductive film according to claim 1, wherein the transparent conductive film is doped with at least one of In, Ga, V, or Ti.
6. The transparent conductive film according to claim 1, wherein the thickness of the transparent conductive film is not more than 130 nm.
7. The method for preparing a transparent conductive film according to any one of claims 1 to 6, comprising the steps of:
heating the substrate to 240-320 ℃, and coating a film on the substrate by using a CdO target or a doped CdO target to prepare the transparent conductive film, wherein working gas is required to be used in the film coating process, and oxygen is not contained in the working gas;
or the like, or, alternatively,
heating the substrate to 70-120 ℃, and coating a film on the substrate by using the CdO target and another oxide target to prepare the transparent conductive film, wherein working gas is required to be used in the film coating process, and the working gas does not contain oxygen.
8. The method as claimed in claim 7, wherein the substrate is heated to 300 ℃ and then coated with CdO target or CdO-doped target, followed by annealing to obtain the transparent conductive film.
9. The method as claimed in claim 8, wherein the temperature of the annealing treatment is 500-600 ℃, and the time of the annealing treatment is 5-10 minutes; the impurity element of the doped CdO target material is at least one of In, Ga, V or Ti.
10. Use of the transparent conductive film of any one of claims 1-6 for the preparation of electronic products.
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