CN108441833B - Multilayer transparent conductive film and preparation method thereof - Google Patents

Multilayer transparent conductive film and preparation method thereof Download PDF

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CN108441833B
CN108441833B CN201810269246.7A CN201810269246A CN108441833B CN 108441833 B CN108441833 B CN 108441833B CN 201810269246 A CN201810269246 A CN 201810269246A CN 108441833 B CN108441833 B CN 108441833B
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sputtering
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argon
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CN108441833A (en
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李兴鳌
张�杰
胡瑞媛
毛巍威
陈爱诗
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Nanjing University of Posts and Telecommunications
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Abstract

The invention provides a multilayer transparent conductive film and a preparation method thereof, wherein the multilayer transparent conductive film is prepared by a magnetron sputtering method at room temperature and comprises the steps of sputtering preparation, target pre-sputtering, bottom target radio-frequency sputtering, intermediate Ag layer direct-current sputtering and top target radio-frequency sputtering, wherein the bottom layer and the bottom layer are prepared by the radio-frequency magnetron sputtering method, the intermediate Ag layer is prepared by the direct-current magnetron sputtering method, and when the intermediate Ag layer is sputtered, a proper amount of oxygen is introduced into the sputtering gas argon as a reaction gas, the flow ratio of the oxygen and the argon is controlled by a flowmeter, and the introduced oxygen effectively improves the growth process of Ag nanoparticles, so that the Ag nanoparticles growing on the bottom layer are well-ordered and good in continuity, the appearance of the Ag layer is improved, and the absorption of the Ag layer to light is reduced; the multilayer transparent conductive film prepared by the method has reduced surface resistance and improved conductivity and light transmittance.

Description

Multilayer transparent conductive film and preparation method thereof
Technical Field
The invention relates to a conductive film, in particular to a multilayer transparent conductive film and a preparation method thereof, belonging to the field of preparation of photoelectric functional materials.
Background
The transparent conductive film is used as a semiconductor material, integrates light transmission and conductivity, and not only has high conductivity, but also has high light transmission in a visible light range. Due to the unique photoelectric characteristics, the method has attracted great attention of researchers in the field, becomes a research hotspot at present, and is widely applied to the field of photoelectric devices such as liquid crystal displays, touch screens, organic photovoltaics, solar cells, field effect transistors and the like. At present, an Indium Tin Oxide (ITO) film is a transparent conductive film which is widely applied in the field of optoelectronic devices, but the ITO preparation process is complex, the manufacturing cost is high, and indium is a rare element, is expensive and is toxic in the preparation process.
The structure of the multilayer transparent conductive film is generally dielectric layer/metal layer/dielectric layer (D/M/D), and the structure has good conductivity and can realize control of transmission spectrum by adjusting the thickness of each film layer, thus attracting great attention. Compared with ITO, the multilayer transparent conductive film is low in price, non-toxic and environment-friendly, is prepared at room temperature, does not need heating, is simple in preparation process, and gradually becomes a hot point for research in the field of photoelectric materials at home and abroad due to the advantages. At present, the light transmittance and the electrical conductivity of the multilayer transparent conductive film prepared by different methods are mainly improved by optimizing the thickness of the middle Ag layer, but research on the growth mechanism of Ag nanoparticles shows that optimizing the thickness of the Ag layer only helps to improve the continuity of the Ag layer to a certain extent, but the growth process of the Ag nanoparticles is still disordered and has poor continuity, and the prepared transparent conductive film has low light transmittance and poor electrical conductivity.
Disclosure of Invention
Aiming at the defects or improvement requirements of the prior art, the invention provides the multilayer transparent conductive film and the preparation method thereof, and a proper amount of oxygen is filled into the sputtering gas argon to be used as a reaction gas, so that the growth process of Ag nano particles is effectively improved, and the light transmittance and the conductivity of the multilayer transparent conductive film are effectively improved.
In order to achieve the purpose, the invention adopts the following technical scheme:
according to an aspect of the present invention, there is provided a method for producing a multilayer transparent conductive film, comprising the steps of:
s1), preparing sputtering, namely, placing a substrate in a magnetron sputtering reaction chamber, pumping the vacuum degree of the reaction chamber to 6X 10-4Pa, and then filling argon with the purity of 99.99% as sputtering gas;
s2) pre-sputtering the target, respectively selecting a bottom layer target, a top layer target and a middle layer Ag target with the purity of 99.9%, and respectively pre-sputtering for 5min-15 min;
s3), performing radio frequency sputtering on the bottom layer target, filling argon with the purity of 99.99% as sputtering gas in the sputtering process, controlling the pressure to be 2.0Pa and the radio frequency power to be 100W at room temperature, and performing radio frequency sputtering on the bottom layer target for 5min-10 min;
s4), performing direct current sputtering on the middle Ag layer, filling argon with the purity of 99.99% as sputtering gas in the sputtering process, and filling oxygen with the purity of 99.99% as reaction gas, wherein the volume ratio of the oxygen to the argon is 1-3: 100, controlling the direct current power of 20W at room temperature to perform direct current sputtering on the intermediate Ag layer for 40S-60S, and depositing the intermediate Ag layer on the bottom layer target material in the step S3;
s5), performing radio frequency sputtering on the top layer target, filling argon with the purity of 99.99% as sputtering gas in the sputtering process, controlling the pressure to be 2.0Pa and the radio frequency power to be 100W at room temperature, performing radio frequency sputtering on the top layer target for 5min-10min, and depositing on the middle Ag layer in the step S4.
Further, before step S1, the method further includes:
s0), pretreating the substrate, carrying out ultrasonic cleaning on the substrate in deionized water, acetone and ethanol in sequence, and then blowing dry by high-purity nitrogen.
Furthermore, the ultrasonic cleaning time is 10min-20 min.
Further, the bottom layer target and the top layer target in step S2 are Nb2O5、ZnO、CO2、SnO2NiO or V2O5。
Further, the bottom layer target material is Nb2O5And the top layer target material is ZnO.
Further, the thickness of the bottom layer target after the radio frequency sputtering in step S3 is 30nm to 50 nm.
Further, the thickness of the top layer target after the rf sputtering in step S5 is the same as the thickness of the bottom layer target after the rf sputtering in step S3.
Further, the thickness of the intermediate Ag layer after the DC sputtering in step S4 is 5nm-20 nm.
As a preferred embodiment of the method of the present invention, the method for producing the multilayer transparent conductive film comprises the steps of:
s0), pretreating the substrate, sequentially and respectively ultrasonically cleaning the substrate in deionized water, acetone and ethanol for 15min, and then blowing the substrate to dry by using high-purity nitrogen;
s1), preparing sputtering, placing the substrate in a magnetron sputtering reaction chamber, and pumping the vacuum degree of the reaction chamber to 6X 10-4Pa, then filling argon with the purity of 99.99 percent as sputtering gas;
s2) pre-sputtering the target materials, and respectively selecting bottom layer target materials Nb with the purity of 99.9 percent2O5The top layer target material ZnO and the middle layer target material Ag are respectively pre-sputtered for 10 min;
s3) bottom layer target Nb2O5Performing radio frequency sputtering, filling argon with the purity of 99.99 percent as sputtering gas in the sputtering process, controlling the pressure of 2.0Pa and the radio frequency power of 100W at room temperature, and performing Nb treatment on the bottom layer target material2O5Performing radio frequency sputtering for 8min to obtain a bottom layer target Nb2O5The thickness is 40 nm;
s4), performing direct current sputtering on the middle Ag layer, filling argon with the purity of 99.99% as sputtering gas in the sputtering process, and filling oxygen with the purity of 99.99% as reaction gas, wherein the volume ratio of the oxygen to the argon is 2:100, controlling the direct current power to be 20W at room temperature to carry out direct current sputtering on the intermediate Ag layer for 50s to obtain the target Nb which is deposited on the bottom layer and has the thickness of the intermediate Ag layer of 10nm2O5The above step (1);
s5), introducing argon with the purity of 99.99% as sputtering gas in the sputtering process, controlling the pressure at 2.0Pa and the radio frequency power at 100W at room temperature, performing radio frequency sputtering on the top layer target ZnO for 8min to obtain the top layer target ZnO with the thickness of 40nm, and depositing the top layer target ZnO on the middle Ag layer.
According to another aspect of the present invention, there is provided a multilayer transparent conductive film produced by the production method of the present invention.
Compared with the prior art, the invention has the following beneficial effects:
the invention provides a preparation method of a multilayer transparent conductive film, which is prepared by adopting a magnetron sputtering method at room temperature, wherein a bottom layer and a bottom layer are prepared by adopting a radio frequency magnetron sputtering method, an intermediate Ag layer is prepared by adopting a direct current magnetron sputtering method, a proper amount of oxygen is introduced into sputtering gas argon as reaction gas when the intermediate Ag layer is sputtered, the flow ratio of the oxygen and the argon is controlled by a flowmeter, and the introduced oxygen effectively improves the growth process of Ag nano particles, so that the Ag nano particles growing on the bottom layer are well ordered and have good continuity, the appearance of the Ag layer is improved, and the light absorption of the Ag layer is reduced; the multilayer transparent conductive film prepared by the method has reduced surface resistance and improved conductivity and light transmittance.
Drawings
FIG. 1 is a schematic structural view of an example of the present invention and a comparative example.
FIG. 2 is a Scanning Electron Micrograph (SEM) of an intermediate Ag layer in various examples of the present invention at different ratios of oxygen and argon.
FIG. 3 is a graph of transmittance analysis for various examples of the present invention at different ratios of argon oxygen.
FIG. 4 is a graph of conductivity analysis for various embodiments of the present invention at different ratios of argon oxygen.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings and specific embodiments. Examples of the embodiments are illustrated in the accompanying drawings, and specific embodiments described in the following embodiments of the invention are provided as illustrative of the embodiments of the invention only and are not intended to be limiting of the invention.
The invention provides a preparation method of a multilayer transparent conductive film, which comprises the following steps:
s1), preparing sputtering, namely, placing a substrate in a magnetron sputtering reaction chamber, pumping the vacuum degree of the reaction chamber to 6X 10-4Pa, and then filling argon with the purity of 99.99% as sputtering gas;
s2) pre-sputtering the target, respectively selecting a bottom layer target, a top layer target and a middle layer Ag target with the purity of 99.9%, and respectively pre-sputtering for 5min-15 min;
s3), performing radio frequency sputtering on the bottom layer target, filling argon with the purity of 99.99% as sputtering gas in the sputtering process, controlling the pressure to be 2.0Pa and the radio frequency power to be 100W at room temperature, and performing radio frequency sputtering on the bottom layer target for 5min-10 min;
s4), performing direct current sputtering on the middle Ag layer, filling argon with the purity of 99.99% as sputtering gas in the sputtering process, and filling oxygen with the purity of 99.99% as reaction gas, wherein the volume ratio of the oxygen to the argon is 1-3: 100, controlling the direct current power of 20W at room temperature to perform direct current sputtering on the intermediate Ag layer for 40S-60S, and depositing the intermediate Ag layer on the bottom layer target material in the step S3;
s5), performing radio frequency sputtering on the top layer target, filling argon with the purity of 99.99% as sputtering gas in the sputtering process, controlling the pressure to be 2.0Pa and the radio frequency power to be 100W at room temperature, performing radio frequency sputtering on the top layer target for 5min-10min, and depositing on the middle Ag layer in the step S4.
Further, before the step S1, the method further includes S0) pre-treating the substrate, that is, ultrasonically cleaning the substrate in deionized water, acetone and ethanol in sequence, and then drying the substrate with high-purity nitrogen. The substrate is made of glass or an organic flexible substrate, and the size of the substrate can be selected according to experimental conditions.
Furthermore, the time of ultrasonic cleaning is 10min-20min to remove particles and organic pollutants on the surface of the substrate.
Further, step S2 is to pre-sputter the bottom layer target, the top layer target and the middle layer Ag target respectively to remove impurities and contaminants on the surface of each layer of target, so as to improve the sputtering quality of each layer of target; the bottom layer target and the top layer target are Nb2O5, ZnO, CO2, SnO2, NiO or V2O5, namely the bottom layer target and the top layer target can be made of the same material or different materials.
Further, the bottom layer target is Nb2O5, and the top layer target is ZnO.
Further, the thickness of the bottom layer target after the radio frequency sputtering in step S3 is 30nm to 50 nm.
Further, the thickness of the top layer target after the rf sputtering in step S5 is the same as the thickness of the bottom layer target after the rf sputtering in step S3, i.e., the thickness of the top layer target after the rf sputtering is also 30nm to 50 nm.
Further, the thickness of the intermediate Ag layer after the DC sputtering in step S4 is 5nm-20 nm.
Comparative example a
A method for preparing a multilayer transparent conductive film, comprising the steps of:
s0) pretreating a glass substrate, namely sequentially ultrasonically cleaning the glass substrate with the size of 20mm X20 mm X1 mm in deionized water, acetone and ethanol for 15min respectively, and then drying the glass substrate by using high-purity nitrogen;
s1), preparing sputtering, namely, placing a glass substrate in a magnetron sputtering reaction chamber, pumping the vacuum degree of the reaction chamber to 6X 10-4Pa, and then filling argon with the purity of 99.99 percent as sputtering gas;
s2) pre-sputtering the target, selecting Nb2O5 with the purity of 99.9% as a bottom layer target and pre-sputtering for 10min, selecting Ag with the purity of 99.9% as an intermediate layer and pre-sputtering for 10min, and selecting ZnO with the purity of 99.9% as a top layer target and pre-sputtering for 10 min;
s3) performing radio frequency sputtering on the bottom layer target Nb2O5, filling argon with the purity of 99.99% as sputtering gas in the sputtering process, controlling the pressure to be 2.0Pa and the radio frequency power to be 100W at room temperature, and performing radio frequency sputtering on the bottom layer target Nb2O5 for 8min to obtain a bottom layer target Nb2O5 with the thickness of 40 nm;
s4), performing direct current sputtering on the intermediate Ag layer, filling argon with the purity of 99.99% in the sputtering process as sputtering gas, controlling the direct current power of 20W at room temperature to perform direct current sputtering on the intermediate Ag layer for 50S, and depositing the intermediate Ag layer with the thickness of 10nm on a bottom layer target Nb2O 5;
s5), performing radio frequency sputtering on the top layer target ZnO, filling argon with the purity of 99.99% as sputtering gas in the sputtering process, controlling the pressure at 2.0Pa and the radio frequency power at 100W at room temperature, performing radio frequency sputtering on the top layer target ZnO for 8min to obtain the top layer target ZnO with the thickness of 40nm, and depositing the top layer target ZnO on the middle Ag layer.
The morphology of the intermediate Ag layer of the Nb2O5/Ag/ZnO transparent conductive film prepared by the method is shown in figure 1 (a), and the Ag nano-particle growth process is disordered and discontinuous.
Example b
S0) pretreating a glass substrate, namely sequentially ultrasonically cleaning the glass substrate with the size of 20mm X20 mm X1 mm in deionized water, acetone and ethanol for 15min respectively, and then drying the glass substrate by using high-purity nitrogen;
s1), preparing sputtering, namely, placing a glass substrate in a magnetron sputtering reaction chamber, pumping the vacuum degree of the reaction chamber to 6X 10-4Pa, and then filling argon with the purity of 99.99 percent as sputtering gas;
s2) pre-sputtering the target, respectively selecting a bottom layer target Nb2O5, a top layer target ZnO and an intermediate layer target Ag with the purity of 99.9%, and respectively pre-sputtering for 10 min;
s3) performing radio frequency sputtering on the bottom layer target Nb2O5, filling argon with the purity of 99.99% as sputtering gas in the sputtering process, controlling the pressure to be 2.0Pa and the radio frequency power to be 100W at room temperature, and performing radio frequency sputtering on the bottom layer target Nb2O5 for 8min to obtain a bottom layer target Nb2O5 with the thickness of 40 nm;
s4), performing direct current sputtering on the middle Ag layer, filling argon with the purity of 99.99% as sputtering gas in the sputtering process, and filling oxygen with the purity of 99.99% as reaction gas, wherein the volume ratio of the oxygen to the argon is 1:100, controlling the direct current power of 20W at room temperature to perform direct current sputtering on the intermediate Ag layer for 50s to obtain an intermediate Ag layer with the thickness of 10nm, and depositing the intermediate Ag layer on a bottom layer target Nb2O 5;
s5), introducing argon with the purity of 99.99% as sputtering gas in the sputtering process, controlling the pressure at 2.0Pa and the radio frequency power at 100W at room temperature, performing radio frequency sputtering on the top layer target ZnO for 8min to obtain the top layer target ZnO with the thickness of 40nm, and depositing the top layer target ZnO on the middle Ag layer.
As shown in figure 1 (b), when the intermediate Ag layer is sputtered by direct current, a proper amount of oxygen is filled in the sputtering gas argon to serve as a reaction gas, the growth process of Ag nano particles is effectively improved due to the induction effect of the oxygen, the appearance of the Ag layer is improved, and the Ag nano particles growing on the bottom Nb2O5 are well ordered and have good continuity.
Example c
A method for producing a multilayer transparent conductive film, wherein steps S0 to S5 are the same as those of example b above, and only the volume ratio of oxygen to argon in step S4 is adjusted to 2: 100.
example d
A method for producing a multilayer transparent conductive film, wherein steps S0 to S5 are the same as those of example b above, and only the volume ratio of oxygen to argon in step S4 is adjusted to 3: 100.
scanning Nb2O5/Ag/ZnO transparent conductive films prepared under different oxygen-argon ratios by using a scanning electron microscope (S-4800, Hitachi), wherein a Scanning Electron Microscope (SEM) image of an intermediate Ag layer is detailed in figure 2, oxygen is not filled in a comparative example a as a reaction gas, Ag nanoparticles are disordered and have poor continuity; in example b, when the volume ratio of the charged oxygen gas to the argon gas was 1:100, the Ag layer gradually became continuous; in the embodiment c, the volume ratio of the oxygen to the argon is 2:100, and the Ag nano particles grow regularly and orderly and have better continuity; in example d, the volume ratio of oxygen to argon gas is 3:100, the continuity of the Ag layer is better, but the Ag nanoparticles begin to have a random tendency.
When the transparent conductive film of Nb2O5/Ag/ZnO prepared at different oxygen/argon ratios is measured by using a UV-visible spectrophotometer (Lambda 35, Perkinelmer), the analysis of light transmittance is shown in detail in FIG. 3. As can be seen from FIG. 3, comparative example a has no oxygen introduced, the volume ratio of oxygen to argon is 0, and the curve marked as "0" represents the light transmittance of comparative example a, in which the light transmittance is at most 81.5%. In the process of sputtering the Ag layer, a proper amount of oxygen is filled as a reaction gas, which is beneficial to improving the light transmittance of the multilayer film. When the volume ratio of the charged oxygen to the argon is 2:100, the light transmittance of the multilayer film is optimal, and the highest light transmittance can reach 96.7%.
The Nb2O5/Ag/ZnO transparent conductive film prepared under different oxygen-argon ratios is measured by using a four-probe (ST-2258A), the conductivity analysis is compared with the figure shown in detail in FIG. 4, as can be seen from FIG. 4, the comparative example a is not introduced with oxygen, the volume ratio of oxygen to argon is 0, and the minimum resistance of the multilayer film is 12.7 omega/sq; during the process of sputtering the Ag layer, a proper amount of oxygen is filled as reaction gas, which is beneficial to reducing the resistivity and improving the conductivity of the multilayer film. When the volume ratio of the oxygen gas to the argon gas is 2:100, the conductivity of the multilayer film is optimal, and the minimum resistance is 6.7 omega/sq.
The invention provides a multilayer transparent conductive film and a preparation method thereof. The introduced oxygen effectively improves the growth process of Ag nano particles, improves the appearance of an Ag layer, reduces the light absorption of the Ag layer, reduces the surface resistance of a multilayer film, improves the light transmittance and the conductivity of the multilayer transparent conductive film, and can effectively replace ITO (indium tin oxide) to be used as an organic light-emitting diode or solar cell transparent electrode.
It should be noted that the above-mentioned embodiments illustrate rather than limit the invention, and that those skilled in the art will be able to design alternative embodiments without departing from the scope of the appended claims. In the claims, the word "comprising" does not exclude the presence of data or steps not listed in a claim.

Claims (7)

1. A method for producing a multilayer transparent conductive film, comprising the steps of:
s1), preparing sputtering, placing the substrate in a magnetron sputtering reaction chamber, and pumping the vacuum degree of the reaction chamber to 6X 10-4Pa, then filling argon with the purity of 99.99 percent as sputtering gas;
s2) pre-sputtering the target, respectively selecting a bottom layer target, a top layer target and a middle layer Ag target with the purity of 99.9%, and respectively pre-sputtering for 5min or 15 min;
s3) performing radio frequency sputtering on the bottom layer target material, wherein the bottom layer target material is selected from CO2NiO or V2O5Argon with the purity of 99.99 percent is filled in the sputtering process to be used as sputtering gas, the pressure is controlled to be 2.0Pa and the radio frequency power is controlled to be 100W at room temperature, and the bottom layer target material is subjected to radio frequency sputtering for 5min or 10 min;
s4), performing direct current sputtering on the middle Ag layer, filling argon with the purity of 99.99% as sputtering gas in the sputtering process, and filling oxygen with the purity of 99.99% as reaction gas, wherein the volume ratio of the oxygen to the argon is 1-3: 100, controlling the direct current power of 20W at room temperature to perform direct current sputtering on the middle Ag layer for 40S-60S, and depositing on the bottom layer target material in the step S3;
s5) performing radio frequency sputtering on the top layer target material, wherein the top layer target material is selected from CO2NiO or V2O5Argon with the purity of 99.99 percent is filled in the sputtering process to be used as sputtering gas, the pressure is controlled to be 2.0Pa and the radio frequency power is controlled to be 100W at room temperature, the top layer target material is subjected to radio frequency sputtering for 5min or 10min and is deposited onOn the intermediate Ag layer of step S4.
2. The method of claim 1, further comprising, before step S1:
s0), pretreating the substrate, carrying out ultrasonic cleaning on the substrate in deionized water, acetone and ethanol in sequence, and then blowing dry by high-purity nitrogen.
3. The method of claim 2, wherein the ultrasonic cleaning is performed for 10-20 min.
4. The method of claim 1, wherein the thickness of the bottom layer target after the rf sputtering in step S3 is 30nm to 50 nm.
5. The method according to claim 4, wherein the thickness of the top target after RF sputtering in step S5 is the same as the thickness of the bottom target after RF sputtering in step S3.
6. The method of claim 1, wherein the thickness of the intermediate Ag layer after dc sputtering in step S4 is 5nm-20 nm.
7. A multilayer transparent conductive film produced according to any one of claims 1 to 6.
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