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CN-121985615-A - TCO film and preparation process thereof

CN121985615ACN 121985615 ACN121985615 ACN 121985615ACN-121985615-A

Abstract

The invention belongs to the field of photoelectric devices, and particularly discloses a TCO film and a preparation process thereof, wherein the preparation process comprises the steps of depositing a TCO layer after substrate pretreatment to obtain an intermediate product, and carrying out three-stage annealing treatment on the intermediate product, wherein the first stage is annealed under a hydrogen-argon mixed atmosphere; the second stage is annealing under the metal ion steam environment, the third stage is annealing under the vacuum atmosphere, then spin coating zinc oxide sol on the surface of the annealed intermediate product, and annealing again, thus obtaining the TCO film. The preparation process provided by the invention can reduce the surface roughness of the TCO film, effectively reduce light scattering, remarkably improve the transmission efficiency of light in the film, improve the optical performance of the photoelectric device, improve the carrier mobility of the TCO film to be more than 30cm 2 /V.s, remarkably improve the conductivity of the film, and strengthen the interface binding force of the TCO film and other materials, and improve the stability and the service life of the photoelectric device.

Inventors

  • HE KAI
  • Huang Nengzhou
  • ZHOU ZICHAO

Assignees

  • 广东先导稀材股份有限公司

Dates

Publication Date
20260505
Application Date
20251224

Claims (10)

  1. 1. The preparation process of the TCO film is characterized by comprising the following steps of: step 1, after the substrate is pretreated, depositing a TCO layer on the upper surface of the substrate to obtain an intermediate product; step 2, annealing the intermediate product, wherein the annealing comprises three stages, namely, annealing in a hydrogen-argon mixed atmosphere in the first stage, annealing in a metal ion steam environment in the second stage, and annealing in a vacuum atmosphere in the third stage; And step 3, spin-coating zinc oxide sol on the surface of the intermediate product prepared in the step 2, and annealing again to obtain the TCO film.
  2. 2. The process for preparing a TCO film according to claim 1, wherein in step 1, oxygen and argon are simultaneously introduced, the flow rate of the oxygen is 2-12 sccm, the flow rate of the argon is 388-398 sccm, the deposition temperature is 25-100 ℃, the deposition pressure is 0.45-0.65 Pa, the radio frequency power is 3.5-4.5 kW, and the deposition rate is 3.8-4.5 nm/s.
  3. 3. The process for preparing a TCO film according to claim 1, wherein in the step 2, during annealing, argon is 90vt% -95 vt% in the first stage, the balance is hydrogen, the concentration of metal ions in the metal ion vapor is 4.95×10 15 ~5.05×10 15 atoms/cm 3 in the second stage, and the vacuum degree is 1-10 Pa in the third stage.
  4. 4. A process for preparing a TCO film as claimed in claim 3 where the concentration of zinc ions in the metal ion vapor is 2.5×10 15 ~3.5×10 15 atoms/cm 3 and the concentration of aluminum ions in the metal ion vapor is 1.5×10 15 ~2.55×10 15 atoms/cm 3 when the metal ions in the metal ion vapor include zinc ions and aluminum ions.
  5. 5. The process for preparing a TCO film according to claim 1, wherein in the step 2, the annealing temperatures of the three stages are 500-550 ℃ and the annealing times are 5-30min.
  6. 6. The process for preparing a TCO film according to claim 1, wherein in the step 3, the annealing temperature is 180-230 ℃ and the annealing time is 10-35 min.
  7. 7. The process for preparing a TCO film according to claim 1, wherein in step 1, when the TCO is deposited, the TCO target used is an indium oxide target doped with tin, and the doping amount of tin is 9.8 to 10.2wt% based on the indium oxide target.
  8. 8. The preparation process of the TCO film according to claim 1, wherein in the step 1, the substrate is pretreated by sequentially placing the substrate in acetone, absolute ethyl alcohol and deionized water for ultrasonic cleaning for 20-40 min, then placing the substrate in a low-temperature drying oven, and drying for 30-60 min at 80-100 ℃; In the step 1, before the TCO layer is deposited, sputtering a TCO target material in a pure argon atmosphere by adopting magnetron sputtering, and sputtering the target material for 30-120 min by adopting sputtering power of 3-5 kW; And (2) before the step (2) after the step (1), placing the intermediate product in a chemical cleaning solution and performing ultrasonic treatment, wherein the chemical cleaning solution comprises ammonium citrate and Triton X-114, the concentration of the ammonium citrate in the chemical cleaning solution is 1.45-1.5 g/L, and the concentration of the Triton X-114 is 1-1.1 g/L.
  9. 9. A TCO film made by the process of any one of claims 1 to 8, where the TCO film includes a substrate, a TCO layer and a zinc oxide modification layer, the TCO layer is disposed on an upper surface of the substrate, and the zinc oxide modification layer is disposed on an upper surface of the TCO layer.
  10. 10. The TCO film according to claim 9, wherein the substrate is any one of glass, quartz and plastic, the thickness of the TCO layer is 95-105 nm, and the thickness of the zinc oxide modification layer is 4-10 nm.

Description

TCO film and preparation process thereof Technical Field The invention belongs to the field of photoelectric devices, relates to a film material for preparing the photoelectric devices, and in particular relates to a TCO film and a preparation process thereof. Background In the field of photovoltaic device fabrication, TCO (transparent conductive oxide TRANSPARENT CONDUCTIVE OXIDE) is widely used in photovoltaic devices such as solar cells, liquid crystal displays, and organic light emitting diode displays, and the surface quality of the TCO film plays a key role in the performance of the photovoltaic device. The surface roughness can seriously affect the transmission and absorption of light and the electron transport within the device. For example, in a solar cell, surface roughness greatly reduces photoelectric conversion efficiency, and in a display device, sharpness and stability are affected. The conventional method for reducing the surface roughness of the TCO film has a plurality of defects that although the wet etching process can remove superfluous materials on the surface, the wet etching process is difficult to control accurately, and thin film damage can be caused by slight carelessness, so that the performance is reduced. The complicated physical treatment method (dry etching) requires expensive equipment and has high process cost, which makes mass production face the problem of excessive cost. Disclosure of Invention In order to overcome the defects and shortcomings of the prior art, the invention provides a preparation process of a TCO film, and in a second aspect, the invention provides the TCO film. In a first aspect, the present invention provides a process for preparing a TCO film, including the steps of: step 1, after the substrate is pretreated, depositing a TCO layer on the upper surface of the substrate to obtain an intermediate product; step 2, annealing the intermediate product, wherein the annealing comprises three stages, namely, annealing in a hydrogen-argon mixed atmosphere in the first stage, annealing in a metal ion steam environment in the second stage, and annealing in a vacuum atmosphere in the third stage; And step 3, spin-coating zinc oxide sol on the surface of the intermediate product prepared in the step 2, and annealing again to obtain the TCO film. Preferably, in the step 1, the substrate is pretreated by sequentially placing the substrate in acetone, absolute ethyl alcohol and deionized water for ultrasonic cleaning for 20-40 min, then placing the substrate in a low-temperature drying oven, and drying for 30-60 min at 80-100 ℃. Preferably, in step 1, when depositing TCO, the TCO target used is an indium oxide target doped with tin, and the doping amount of tin is 9.8-10.2 wt% based on the indium oxide target. Preferably, in the step 1, oxygen and argon are simultaneously introduced when TCO is deposited, the flow of the oxygen is 2-12 sccm, the flow of the argon is 388-398 sccm, the deposition temperature is 25-100 ℃, the deposition pressure is 0.45-0.65 Pa, the radio frequency power is 3.5-4.5 kW, and the deposition rate is 3.8-4.5 nm/s. Preferably, after step 1 and before step 2, the intermediate product is placed in a chemical wash comprising ammonium citrate and triton x-114 and sonicated. Preferably, in the chemical cleaning solution, the concentration of ammonium citrate is 1.45-1.5 g/L, and the concentration of Triton X-114 is 1-1.1 g/L. Preferably, during ultrasonic treatment, the frequency of the ultrasonic tank is 35-40 kHz, the frequency of the megasonic generator is 900-950 KkHz, and the cleaning time is 18-20 minutes. Preferably, in the step 2, during annealing, the argon gas is 90-95 vt% in the first stage, the rest is hydrogen gas, the concentration of metal ions in the metal ion steam is 4.95×10 15~5.05×1015atoms/cm3 in the second stage, and the vacuum degree is 1-10 Pa in the third stage. Preferably, the metal ions in the metal ion vapor are any one or more than two of zinc ions and aluminum ions. Further preferably, when the metal ions in the metal ion vapor include zinc ions and aluminum ions, the concentration of zinc ions is 2.5×10 15~3.5×1015atoms/cm3, and the concentration of aluminum ions in the metal ion vapor is 1.5×10 15~2.55×1015atoms/cm3. Preferably, in the step 2, the annealing temperatures of the three stages are 500-550 ℃ and the annealing time is 5-30 min. Preferably, in the step 3, the annealing temperature is 180-230 ℃ and the annealing time is 10-35 min. In a second aspect, the present invention provides a TCO film including a substrate, a TCO layer disposed on an upper surface of the substrate, and a zinc oxide modification layer disposed on an upper surface of the TCO layer. Preferably, the substrate is any one of glass, quartz and plastic. Preferably, the thickness of the TCO layer is 95-105 nm. Preferably, the thickness of the zinc oxide modification layer is 4-10 nm. Compared with the prior art, the invention has the followin