Preparation method of P-type transparent metal conductive electrode

Abstract

The invention discloses a preparation method of a P-type transparent metal conductive electrode. The preparation method of the P-type transparent metal conductive electrode comprises the following steps: preparing a Sb target material and a SnO2 target material; placing the Sb target material and the SnO2 target material in magnetron sputtering equipment; mixed gas is introduced into the magnetron sputtering equipment, and the air pressure in the magnetron sputtering equipment is adjusted to a preset air pressure value; the substrate temperature of magnetron sputtering equipment is adjusted to the preset substrate temperature, the sputtering power of the magnetron sputtering equipment is adjusted to the preset sputtering power, the deposition time of the magnetron sputtering equipment is adjusted to the preset deposition duration, magnetron sputtering is conducted on the Sb target material and the SnO2 target material, and a deposited film is obtained; and carrying out annealing treatment on the deposited film at a preset annealing temperature, and carrying out heat preservation for a preset heat preservation time to obtain the P-type transparent metal conductive electrode. According to the invention, the mid-infrared light transmittance of the P-type transparent metal conductive electrode can be improved.

Description

Technical Field

[0001] The present application relates to the field of semiconductor technology, and in particular to a method for preparing a P-type transparent metal conductive electrode. Background Art

[0002] In recent years, transparent conductive electrodes have been widely used in optoelectronic devices, especially in the fields of solar cells, liquid crystal displays, touch screens and infrared detectors. Traditional transparent conductive materials mainly include indium-doped tin oxide (ITO) and fluorine-doped tin oxide (FTO), which show good transparency and conductivity in the visible light range. However, in infrared applications, the performance of these materials is often limited, especially in the mid-infrared region (3-5μm), where the transmittance is low and cannot meet the needs of high-performance infrared detectors. Summary of the invention

[0003] The present application aims to solve at least one of the above-mentioned technical problems by providing a method for preparing a P-type transparent metal conductive electrode, thereby improving the mid-infrared light transmittance of the P-type transparent metal conductive electrode.

[0004] On one hand, the present application provides a method for preparing a P-type transparent metal conductive electrode, the method for preparing a P-type transparent metal conductive electrode comprising:

[0005] Prepare Sb target and SnO2 target;

[0006] Placing the Sb target and the SnO2 target in a magnetron sputtering device;

[0007] Introducing a mixed gas into the magnetron sputtering device and adjusting the gas pressure in the magnetron sputtering device to a preset gas pressure value;

[0008] The substrate temperature of the magnetron sputtering device is adjusted to a preset substrate temperature, the sputtering power of the magnetron sputtering device is adjusted to a preset sputtering power, the deposition time of the magnetron sputtering device is adjusted to a preset deposition time, and the Sb target material and the SnO2 target material are magnetron sputtered to obtain the deposited film;

[0009] The deposited film is annealed at a preset annealing temperature and kept warm for a preset holding time to obtain a P-type transparent metal conductive electrode.

[0010] Optionally, the doping concentration of Sb in the deposited film is 1.0×10 19 cm -3 to 1.9×10 19 cm -3 .

[0011] Optionally, the doping concentration of Sb in the deposited film is 1.9×10 19 cm-3 .

[0012] Optionally, the mixed gas includes argon and oxygen.

[0013] Optionally, the concentration ratio of argon to oxygen in the mixed gas is 88:0.8.

[0014] Optionally, the preset air pressure value is 3.2Pa.

[0015] Optionally, the preset substrate temperature is not less than 80 degrees Celsius and not more than 150 degrees Celsius, the preset sputtering power is 150 W, and the preset deposition time is 30 minutes.

[0016] Optionally, the preset substrate temperature is 100 degrees Celsius.

[0017] Optionally, the preset annealing temperature is 300 degrees Celsius, and the preset insulation time is 1 hour.

[0018] Optionally, the step of annealing the deposited film at a preset annealing temperature and keeping the temperature for a preset holding time to obtain a P-type transparent metal conductive electrode comprises:

[0019] The deposited film is annealed at a preset annealing temperature in a nitrogen atmosphere and kept warm for a preset holding time to obtain a P-type transparent metal conductive electrode.

[0020] In the preparation method of the P-type transparent metal conductive electrode of the present application, the preparation method of the P-type transparent metal conductive electrode includes: preparing Sb target material and SnO2 target material; placing the Sb target material and SnO2 target material in a magnetron sputtering device; introducing a mixed gas into the magnetron sputtering device and adjusting the gas pressure in the magnetron sputtering device to a preset gas pressure value; adjusting the substrate temperature of the magnetron sputtering device to a preset substrate temperature, adjusting the sputtering power of the magnetron sputtering device to a preset sputtering power, adjusting the deposition time of the magnetron sputtering device to a preset deposition time, magnetron sputtering the Sb target material and the SnO2 target material to obtain a deposited film; annealing the deposited film at a preset annealing temperature and keeping it warm for a preset insulation time to obtain a P-type transparent metal conductive electrode. The present application can improve the mid-infrared light transmittance of the P-type transparent metal conductive electrode. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] Figure 1 It is a schematic flow chart of an embodiment of a method for preparing a P-type transparent metal conductive electrode provided in an embodiment of the present application;

[0022] Figure 2 This is a relationship diagram of the transmittance of the P-type transparent metal conductive electrode prepared in Example 1 of the method for preparing the P-type transparent metal conductive electrode provided in an embodiment of the present application to light of various wavelengths. DETAILED DESCRIPTION

[0023] The following will be combined with the drawings in the embodiments of the present application to clearly and completely describe the technical solutions in the embodiments of the present application. Obviously, the described embodiments are only part of the embodiments of the present application, not all of the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative work are within the scope of protection of this application.

[0024] In the description of the present application, it should be understood that the terms "center", "longitudinal", "lateral", "length", "width", "thickness", "up", "down", "front", "back", "left", "right", "vertical", "horizontal", "top", "bottom", "inside", "outside" and the like indicate positions or positional relationships based on the positions or positional relationships shown in the accompanying drawings, which are only for the convenience of describing the present application and simplifying the description, and do not indicate or imply that the device or element referred to must have a specific orientation, be constructed and operated in a specific orientation, and therefore cannot be understood as a limitation on the present application. In addition, the terms "first" and "second" are used only for descriptive purposes, and cannot be understood as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Therefore, the features defined as "first" and "second" may explicitly or implicitly include one or more features. In the description of the present application, the meaning of "multiple" is two or more, unless otherwise clearly and specifically defined.

[0025] In this application, the word "exemplary" is used to mean "used as an example, illustration, or description." Any embodiment described in this application as "exemplary" is not necessarily to be construed as being preferred or advantageous over other embodiments. The following description is given to enable any technician in the field to implement and use the present application. In the following description, details are listed for the purpose of explanation. It should be understood that a person of ordinary skill in the art can recognize that the present application can be implemented without using these specific details. In other instances, well-known structures and processes will not be elaborated in detail to avoid obscuring the description of the present application with unnecessary details. Therefore, the present application is not intended to be limited to the embodiments shown, but is consistent with the widest scope consistent with the principles and features disclosed in the present application.

[0026] The application of traditional metal oxide thin film materials in optoelectronic devices is limited by many factors, especially the lack of P-type transparent conductive electrode materials. Existing conductive materials such as indium-doped tin oxide (ITO) and fluorine-doped tin oxide (FTO) perform well in the visible light range, but have low transmittance in the mid-infrared region, and high doping concentrations cause the optical properties of the materials to decrease. For p-type conductive materials, doped SnO2 can usually only exhibit n-type conductivity, which is difficult to meet the needs of certain applications. In addition, the poor stability of existing materials in high-temperature environments limits their effective use in high-temperature applications such as infrared detectors. Therefore, the present invention aims to improve the conductivity and mid-infrared transmittance of the material by optimizing the preparation technology of Sb-doped SnO2 thin films, so as to solve the shortcomings of metal oxide films in the current technology in electrical and optical properties.

[0027] In order to solve the above problems, the present application provides a method for preparing a P-type transparent metal conductive electrode, which comprises: preparing an Sb target and a SnO2 target; placing the Sb target and the SnO2 target in a magnetron sputtering device; introducing a mixed gas into the magnetron sputtering device and adjusting the gas pressure in the magnetron sputtering device to a preset gas pressure value; adjusting the substrate temperature of the magnetron sputtering device to a preset substrate temperature, adjusting the sputtering power of the magnetron sputtering device to a preset sputtering power, adjusting the deposition time of the magnetron sputtering device to a preset deposition time, magnetron sputtering the Sb target and the SnO2 target to obtain a deposited film; annealing the deposited film at a preset annealing temperature and keeping it warm for a preset insulation time to obtain a P-type transparent metal conductive electrode. The present application can improve the mid-infrared light transmittance of the P-type transparent metal conductive electrode.

[0028] See also Figure 1 In an embodiment of the present application, a method for preparing a P-type transparent metal conductive electrode comprises:

[0029] 201. Prepare Sb target and SnO2 target.

[0030] In the embodiment of the present application, an Sb target and a SnO2 target are prepared. The SnO2 target is high-purity SnO2, the purity of which is higher than 99.99%, and the Sb target is high-purity Sb, the purity of which is higher than 99.99%.

[0031] 202. Place the Sb target and the SnO2 target in a magnetron sputtering device.

[0032] Magnetron sputtering is a type of physical vapor deposition (PVD). The general sputtering method can be used to prepare metals, semiconductors, insulators and other materials. It has the advantages of simple equipment, easy control, large coating area and strong adhesion. The magnetron sputtering method developed in the 1970s has achieved high speed, low temperature and low damage. Because high-speed sputtering is carried out under low pressure, the ionization rate of the gas must be effectively increased. Magnetron sputtering introduces a magnetic field on the surface of the target cathode and uses the magnetic field to constrain charged particles to increase the plasma density and increase the sputtering rate. The working principle of magnetron sputtering is that electrons collide with argon atoms in the process of flying to the substrate under the action of the electric field E, causing them to ionize and produce Ar positive ions and new electrons; the new electrons fly to the substrate, and the Ar ions are accelerated to fly to the cathode target under the action of the electric field, and bombard the target surface with high energy, causing the target material to sputter. In the sputtered particles, neutral target atoms or molecules are deposited on the substrate to form a thin film, and the secondary electrons generated will be affected by the electric field and magnetic field, resulting in a drift in the direction indicated by E (electric field) × B (magnetic field), referred to as E × B drift, and its motion trajectory is similar to a cycloid. If it is a circular magnetic field, the electrons will make circular motion on the target surface in an approximate cycloid form. Their motion path is not only very long, but also confined in the plasma region close to the target surface, and a large amount of Ar is ionized in this region to bombard the target material, thereby achieving a high deposition rate. As the number of collisions increases, the energy of the secondary electrons is exhausted, gradually moving away from the target surface, and finally deposited on the substrate under the action of the electric field E. Since the energy of the electron is very low, the energy transferred to the substrate is very small, resulting in a low temperature rise of the substrate. Magnetron sputtering is a collision process between the incident particle and the target. The incident particle undergoes a complex scattering process in the target, collides with the target atom, and transfers part of the momentum to the target atom. This target atom collides with other target atoms to form a cascade process. During this cascade process, some target atoms near the surface gain sufficient momentum to move outward, leaving the target and being sputtered.

[0033] 203. Introduce a mixed gas into the magnetron sputtering device and adjust the gas pressure in the magnetron sputtering device to a preset pressure value.

[0034] In the embodiment of the present application, the mixed gas includes argon and oxygen. The concentration ratio of argon to oxygen in the mixed gas is 88:0.8. The purity of argon (Ar) in the mixed gas is ≥99.999%, and the purity of oxygen (O2) in the mixed gas is ≥99.999%.

[0035] In the embodiment of the present application, the preset air pressure value is 3.2Pa.

[0036] 204. Adjust the substrate temperature of the magnetron sputtering device to a preset substrate temperature, adjust the sputtering power of the magnetron sputtering device to a preset sputtering power, adjust the deposition time of the magnetron sputtering device to a preset deposition time, perform magnetron sputtering on the Sb target material and the SnO2 target material to obtain a deposited film.

[0037] In the embodiment of the present application, the doping concentration of Sb in the deposited film is 1.0×10 19 cm -3 to 1.9×10 19 cm -3 .

[0038] In an optional embodiment, the doping concentration of Sb in the deposited film is 1.9×10 19 cm -3 .

[0039] In the embodiment of the present application, the preset substrate temperature is not less than 80 degrees Celsius and not more than 150 degrees Celsius, the preset sputtering power is 150 W, and the preset deposition time is 30 minutes.

[0040] In a preferred embodiment, the substrate temperature is preset to be 100 degrees Celsius, the sputtering power is preset to be 150 W, and the deposition time is preset to be 30 minutes, so as to ensure the uniformity and density of the deposited film.

[0041] In the embodiment of the present application, the deposition rate of the magnetron sputtering equipment on the Sb target and the SnO2 target is adjusted to ensure that the doping concentration of Sb in the deposited film is 1.9×10 19 cm -3 .

[0042] 205. Anneal the deposited film at a preset annealing temperature and keep it warm for a preset insulation time to obtain a P-type transparent metal conductive electrode.

[0043] In the embodiment of the present application, the preset annealing temperature is 300 degrees Celsius, and the preset insulation time is 1 hour.

[0044] In the embodiment of the present application, the deposited film is annealed at a preset annealing temperature and kept warm for a preset holding time to obtain a P-type transparent metal conductive electrode, including:

[0045] The deposited film is annealed at a preset annealing temperature in a nitrogen atmosphere and kept warm for a preset holding time to obtain a P-type transparent metal conductive electrode.

[0046] The present application performs a high temperature annealing treatment (eg, 300° C.) after deposition to optimize the crystal structure, reduce defect density, and improve the thermal stability of the material.

[0047] Furthermore, the optical and electrical properties of the prepared P-type transparent metal conductive electrode were tested using a transmission spectrum and Hall effect test system to verify its transmittance and conductivity in the visible light and mid-infrared bands.

[0048] The prepared P-type transparent metal conductive electrode is applied to optoelectronic devices such as infrared detectors, and actual performance tests are carried out to evaluate its stability and effectiveness in high temperature environments. The comparative experiment is as follows:

[0049] Under the same conditions, undoped Sb P-type transparent metal conductive electrodes were prepared, and the Sb doping concentration was 1.0×10 19 cm -3 The P-type transparent metal conductive electrode has a Sb doping concentration of 1.9×10 19 cm -3 The performance of the three P-type transparent metal conductive electrodes is shown in the following table. The transmittance of the undoped Sb-doped P-type transparent metal conductive electrode in the mid-infrared band is 70%. The conductivity is low, and the mobility is only 20cm 2 / V·s, and its square resistance is significantly higher than that of Sb-doped P-type transparent metal conductive electrode.

[0050]

[0051] From the above table, it can be seen that the Sb-doped P-type transparent metal conductive electrode has significantly improved mid-infrared transmittance and electrical performance compared to the non-Sb-doped P-type transparent metal conductive electrode, verifying the effectiveness and superiority of the present invention. This technical solution not only solves the problem of insufficient transmittance of existing transparent conductive electrodes in the mid-infrared region, but also provides a new type of P-type transparent conductive electrode material, laying the foundation for future applications in infrared detectors and other optoelectronic devices.

[0052] In another embodiment, a method for preparing a P-type transparent metal conductive electrode comprises:

[0053] (1) Prepare Sb target and SnO2 target.

[0054] In the embodiment of the present application, an Sb target and a SnO2 target are prepared. The SnO2 target is high-purity SnO2, the purity of which is higher than 99.99%, and the Sb target is high-purity Sb, the purity of which is higher than 99.99%.

[0055] (2) Place the Sb target and SnO2 target in a magnetron sputtering device.

[0056] (3) A mixed gas of argon and oxygen with a concentration ratio of 88:0.8 was introduced into the magnetron sputtering equipment and the gas pressure in the magnetron sputtering equipment was adjusted to 3.2 Pa.

[0057] (4) The substrate temperature of the magnetron sputtering device was adjusted to 80 degrees Celsius and not more than 150 degrees Celsius, the sputtering power of the magnetron sputtering device was adjusted to 150 W, and the deposition time of the magnetron sputtering device was adjusted to 30 minutes. The Sb target and the SnO2 target were magnetron sputtered to obtain a Sb doping concentration of 1.0×10 19 cm -3 of deposited thin films.

[0058] (5) The deposited film is annealed at 300 degrees Celsius in a nitrogen atmosphere for 1 hour to obtain a P-type transparent metal conductive electrode.

[0059] In yet another embodiment, a method for preparing a P-type transparent metal conductive electrode comprises:

[0060] (1) Prepare Sb target and SnO2 target.

[0061] In the embodiment of the present application, an Sb target and a SnO2 target are prepared. The SnO2 target is high-purity SnO2, the purity of which is higher than 99.99%, and the Sb target is high-purity Sb, the purity of which is higher than 99.99%.

[0062] (2) Place the Sb target and SnO2 target in a magnetron sputtering device.

[0063] (3) A mixed gas of argon and oxygen with a concentration ratio of 88:0.8 was introduced into the magnetron sputtering equipment and the gas pressure in the magnetron sputtering equipment was adjusted to 3.2 Pa.

[0064] (4) The substrate temperature of the magnetron sputtering device was adjusted to 80 degrees Celsius and not more than 150 degrees Celsius, the sputtering power of the magnetron sputtering device was adjusted to 150 W, and the deposition time of the magnetron sputtering device was adjusted to 30 minutes. The Sb target and the SnO2 target were magnetron sputtered to obtain a Sb doping concentration of 1.9×10 19 cm -3 of deposited thin films.

[0065] (5) The deposited film is annealed at 300 degrees Celsius in a nitrogen atmosphere for 1 hour to obtain a P-type transparent metal conductive electrode.

[0066] In yet another embodiment, a method for preparing a P-type transparent metal conductive electrode comprises:

[0067] (1) Prepare Sb target and SnO2 target.

[0068] In the embodiment of the present application, an Sb target and a SnO2 target are prepared. The SnO2 target is high-purity SnO2, the purity of which is higher than 99.99%, and the Sb target is high-purity Sb, the purity of which is higher than 99.99%.

[0069] (2) Place the Sb target and SnO2 target in a magnetron sputtering device.

[0070] (3) A mixed gas of argon and oxygen with a concentration ratio of 88:0.8 was introduced into the magnetron sputtering equipment and the gas pressure in the magnetron sputtering equipment was adjusted to 3.2 Pa.

[0071] (4) The substrate temperature of the magnetron sputtering device was adjusted to 100 degrees Celsius, the sputtering power of the magnetron sputtering device was adjusted to 150 W, and the deposition time of the magnetron sputtering device was adjusted to 30 minutes. The Sb target and the SnO2 target were magnetron sputtered to obtain a Sb doping concentration of 1.9×10 19 cm -3 of deposited thin films.

[0072] (5) The deposited film is annealed at 300 degrees Celsius in a nitrogen atmosphere for 1 hour to obtain a P-type transparent metal conductive electrode.

[0073] For further information, see Figure 2 , Figure 2 The doping concentration of Sb provided in the embodiment of the present application is 1.9×10 19 cm -3 A diagram showing the relationship between the transmittance of a P-type transparent metal conductive electrode to light of various wavelengths. Figure 2 In the figure, the horizontal axis is the wavelength in nm, and the vertical axis is the transmittance in %. The transmittance can be recorded as T%. This application effectively solves the problem of insufficient transmittance of existing transparent conductive electrodes in the mid-infrared band through the preparation of Sb-doped P-type transparent metal conductive electrodes. The optimized doping process and preparation technology enable the film to achieve a transmittance of 93% in the mid-infrared region while maintaining high conductivity. This technological advancement provides a new solution for the development of P-type transparent conductive electrodes and expands the application range of metal oxide films. In addition, through high-temperature annealing treatment, the thermal stability of the film is significantly improved, allowing it to maintain good electrical and optical properties in high temperature environments. This feature provides a guarantee for the long-term reliability of optoelectronic devices such as infrared detectors and smart windows.

[0074] In the preparation method of the P-type transparent metal conductive electrode of the present application, the preparation method of the P-type transparent metal conductive electrode includes: preparing Sb target material and SnO2 target material; placing the Sb target material and SnO2 target material in a magnetron sputtering device; introducing a mixed gas into the magnetron sputtering device and adjusting the gas pressure in the magnetron sputtering device to a preset gas pressure value; adjusting the substrate temperature of the magnetron sputtering device to a preset substrate temperature, adjusting the sputtering power of the magnetron sputtering device to a preset sputtering power, adjusting the deposition time of the magnetron sputtering device to a preset deposition time, magnetron sputtering the Sb target material and the SnO2 target material to obtain a deposited film; annealing the deposited film at a preset annealing temperature and keeping it warm for a preset insulation time to obtain a P-type transparent metal conductive electrode. The present application can improve the conductivity and mid-infrared light transmittance of the P-type transparent metal conductive electrode.

[0075] The above are only implementation methods of the present application, and are not intended to limit the patent scope of the present application. Any equivalent structure or equivalent process transformation made using the contents of the present application specification and drawings, or directly or indirectly applied in other related technical fields, are also included in the patent protection scope of the present application.

Claims

1. A method for preparing a P-type transparent metal conductive electrode, characterized in that: The method for preparing the P-type transparent metal conductive electrode comprises: Prepare Sb target and SnO2 target; Placing the Sb target and the SnO2 target in a magnetron sputtering device; Introducing a mixed gas into the magnetron sputtering device and adjusting the gas pressure in the magnetron sputtering device to a preset gas pressure value; The substrate temperature of the magnetron sputtering device is adjusted to a preset substrate temperature, the sputtering power of the magnetron sputtering device is adjusted to a preset sputtering power, the deposition time of the magnetron sputtering device is adjusted to a preset deposition time, and the Sb target material and the SnO2 target material are magnetron sputtered to obtain the deposited film; The deposited film is annealed at a preset annealing temperature and kept warm for a preset holding time to obtain a P-type transparent metal conductive electrode.

2. The method for preparing a P-type transparent metal conductive electrode according to claim 1, characterized in that: The doping concentration of Sb in the deposited film is 1.0×10 19 cm-3 to 1.9×10 19 cm-3.

3. The method for preparing a P-type transparent metal conductive electrode according to claim 2, characterized in that: The doping concentration of Sb in the deposited film is 1.9×10 19 cm-3.

4. The method for preparing a P-type transparent metal conductive electrode according to claim 1, characterized in that: The mixed gas includes argon and oxygen.

5. The method for preparing a P-type transparent metal conductive electrode according to claim 4, characterized in that: The concentration ratio of argon to oxygen in the mixed gas is 88:0.

8.

6. The method for preparing a P-type transparent metal conductive electrode according to claim 1, characterized in that: The preset air pressure value is 3.2Pa.

7. The method for preparing a P-type transparent metal conductive electrode according to claim 1, characterized in that: The preset substrate temperature is not less than 80 degrees Celsius and not more than 150 degrees Celsius, the preset sputtering power is 150W, and the preset deposition time is 30 minutes.

8. The method for preparing a P-type transparent metal conductive electrode according to claim 7, characterized in that: The preset substrate temperature is 100 degrees Celsius.

9. The method for preparing a P-type transparent metal conductive electrode according to claim 1, characterized in that: The preset annealing temperature is 300 degrees Celsius, and the preset insulation time is 1 hour.

10. The method for preparing a P-type transparent metal conductive electrode according to claim 1, characterized in that: The step of annealing the deposited film at a preset annealing temperature and keeping the film warm for a preset holding time to obtain a P-type transparent metal conductive electrode comprises: The deposited film is annealed at a preset annealing temperature in a nitrogen atmosphere and kept warm for a preset holding time to obtain a P-type transparent metal conductive electrode.

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