Manganese cobalt oxide and zirconium oxide composite plasma developing material

Abstract

The invention discloses a manganese cobalt oxide and zirconium oxide composite plasma developing material, and belongs to the field of plasma process detection and visual developing materials. In order to solve the problems that an existing plasma indicating material is high in reversibility, unstable in color development, not resistant to high temperature and prone to generating organic pollution, the invention provides a full-inorganic composite color development system which is resistant to high temperature and irreversible in color development. The material is formed by compounding manganese oxide (MnO), cobalt oxide (CoO) and zirconium oxide (ZrO), the molar ratio of Mn to Co is (3-7): 1, and the content of ZrO is 10-40 wt%. Under the action of plasmas, synergistic valence transition from Mn to Mn and from Co to Co occurs in the material, and zirconium oxide is used as a lattice stable phase and an oxygen vacancy buffer phase, so that the high-temperature structural stability and the color development retentivity are remarkably improved. The material still keeps stable color development under the condition of 300-400 DEG C, the color development contrast delta E is larger than or equal to 30, and the material can be prepared through a sol-gel or physical vapor deposition (PVD) method. According to the invention, a high-contrast, irreversible, pollution-free and long-term stable plasma developing indication function is realized, and the device is suitable for visual detection and verification of semiconductors, medical sterilization and high-cleanliness processes.

Description

Technical Field

[0001] This invention belongs to the field of plasma processing and visualization detection materials technology, specifically relating to an all-inorganic plasma colorimetric material formed by manganese (Mn) and cobalt (Co) oxides and zirconium oxide (ZrO2) and its preparation method. Background Technology

[0002] Currently, colorimetric materials used for plasma process indication mainly include organic colorimetric systems and inorganic systems based on molybdenum (Mo), tungsten (W), and vanadium (V) oxides. These existing materials generally exhibit strong reversibility during the color development process, and the color development results are easily affected by factors such as temperature, atmosphere, and time, making it difficult to maintain long-term stability. Furthermore, organic colorimetric materials are prone to decomposition or releasing organic gases in high-temperature or vacuum environments, potentially causing contamination of equipment cavities and affecting the cleanliness requirements of semiconductor and medical device processes. Although some Mo / W / V oxide systems possess certain heat resistance, the color development reaction is mostly a reversible process, making it difficult to achieve one-time process traceability and long-term recording. Therefore, current technology lacks a novel plasma colorimetric material that is entirely inorganic, high-temperature resistant (300–400℃), stable in performance, and exhibits irreversible color development. This invention uses manganese (Mn) and cobalt (Co) oxides as the main colorimetric components and introduces zirconium oxide (ZrO2) as a lattice-stabilizing phase. Through valence state coordination and oxygen vacancy regulation mechanisms, controllable and long-term stable color development is achieved. The present invention aims to overcome the above-mentioned technical problems and provide a plasma colorimetric material that is stable, irreversible, heat resistant and free of organic pollution. Summary of the Invention

[0003] This invention fundamentally improves colorimetric stability and high-temperature resistance by constructing a manganese (Mn)-cobalt (Co) synergistic valence system and introducing a zirconium oxide (ZrO2) lattice-stabilizing phase. This invention aims to overcome the shortcomings of existing technologies and provide a composite plasma colorimetric material of manganese (Mn)-cobalt (Co) oxide and zirconium oxide (ZrO2) to solve the following technical problems: 1. Existing color-developing materials have unstable color development and are prone to fading; 2. Existing colorimetric materials undergo structural degradation or decomposition under high temperature or vacuum conditions, and organic colorimetric systems are prone to releasing pollutants; 3. Existing inorganic systems exhibit reversible color development, making it difficult to achieve permanent recording; Further verification showed that when the Mn:Co molar ratio was between 3:1 and 7:1 and the ZrO2 content was between 10 and 40 wt%, the ΔE of the color development layer reached over 30, and the structure was stable with irreversible color development. When the Mn:Co ratio was below 3:1 or the ZrO2 content exceeded 40 wt%, the uniformity and stability of the film color development decreased significantly. Therefore, the above ratio range was determined to be the optimal condition for achieving high contrast and long-term stable color development. Technical solution

[0004] To address the aforementioned problems, this invention provides a fully inorganic colorimetric system. This material is composed of manganese oxide (MnO2), cobalt oxide (Co3O4), and zirconium oxide (ZrO2), wherein the Mn:Co molar ratio is 3–7:1, and the ZrO2 content is 10–40 wt%. Under plasma irradiation, Mn… 4 The ⁺→Mn³⁺ and Co³⁺→Co²⁺ undergo a concerted valence transition, accompanied by the generation of oxygen vacancies, changing the material color from light gray to bluish-gray or dark bluish-gray, with ΔE ≥ 30. ZrO2, as a lattice-stabilizing phase and an oxygen vacancy buffer phase, significantly improves structural integrity and color retention at high temperatures.

[0005] Preparation process This invention can be prepared using the following two main process routes: 1. Sol-gel method: MnO2, Co3O4, and ZrO2 are mixed in a certain proportion, and ethanol and acetic acid (volume ratio 3:1) are added to form a 0.2 mol / L dispersion sol; the mixed solution is magnetically stirred for 15–30 min to ensure uniform dispersion; after ultrasonic dispersion for 30 min, it is spin-coated onto the surface of a glass or PI substrate (3000 rpm, 30 s) and cured at 150–200 ℃ to form a uniform film layer; 2. Physical vapor deposition (PVD or PE-ALD): Manganese acetylacetonate and cobalt acetylacetonate are used as precursors, O2 / N2 mixed atmosphere (1:1), reaction temperature is 200 ℃, and film thickness is controlled at 50-200 nm. Both process routes can produce Mn / Co / ZrO2 composite colorimetric materials with stable color development and uniform film layer.

[0006] Structural design Preferably, the color-developing layer is disposed on a glass, polyimide (PI) or ceramic substrate; ZrO2 is nanoparticles with a particle size of 10-50 nm to improve lattice stability and color retention performance; Furthermore, its surface is covered with a SiO2 protective layer to enhance scratch resistance and optical contrast; Furthermore, its surface is covered with a SiO2 protective layer to enhance scratch resistance and optical contrast; Furthermore, a high-temperature resistant double-sided adhesive layer can be applied to the back of the color development layer to facilitate quick application and removal within the plasma chamber.

[0007] Working characteristics Under O2, N2, or Ar plasma conditions (power 100–200 W, reaction time 1–3 min, temperature 300–400℃), the composite color-developing layer gradually changes from light gray to blue-gray or dark blue-gray, with a ΔE value of 30–35 and a color retention rate ≥ 90%. Tests showed that the color-developing film exhibited significant color differences under different atmospheres and a response time of less than 2 minutes.

[0008] Further verification showed that when the Mn:Co molar ratio was between 3:1 and 7:1 and the ZrO2 content was between 10 and 40 wt%, the ΔE of the color development layer reached over 30, and the structure was stable with irreversible color development. When the Mn:Co ratio was below 3:1 or the ZrO2 content exceeded 40 wt%, the uniformity and stability of the film color development decreased significantly. Therefore, the above ratio range was determined to be the optimal condition for achieving high contrast and long-term stable color development.

[0009] Beneficial effects 1. The color development reaction is irreversible and has high contrast. A color development effect with ΔE ≥ 30 is achieved through the synergistic valence state transition of Mn / Co, resulting in obvious color changes that can be directly identified by the naked eye as the plasma processing completion status. 2. Excellent high-temperature stability. ZrO2, as a lattice-stabilizing phase, ensures that the material maintains its structural integrity even under continuous heating at 300–400 °C, and the ΔE decay is less than 10% after 30 thermal cycles; 3. Clean and pollution-free. A completely inorganic system, containing no organic binders and releasing no volatile gases or particulate matter; 4. The preparation process is simple and controllable. Both the sol-gel method and PVD process are suitable for mass production; 5. High applicability. Suitable for visual monitoring of high-cleanliness processes such as semiconductors, medical sterilization, and electronic component manufacturing. Attached Figure Description

[0010] Figure 1 Schematic diagram of the color development layer structure; Figure 2 Flowchart of the Mn / Co / ZrO2 valence state synergistic color development mechanism; Figure 3 Schematic diagram of color development effect under different plasma atmospheres. Detailed Implementation

[0011] Example 1: Mn:Co = 5:1, ZrO2 = 20 wt%, ethanol:acetic acid = 3:1, solution concentration 0.2 mol / L. Spin coating parameters: 3000 rpm, 30 s; curing temperature: 180 ℃. After O2 plasma treatment (13.56 MHz, 150 W, 2 min), the color changed from light gray to dark blue-gray, ΔE = 32. After 30 thermal cycles at 350 ℃, ΔE decreased by 8.5%. Example 2 (Comparative): The ZrO2 content is 5 wt%, the color development ΔE is 14, and the color fades significantly after 5 thermal cycles; Example 3 (PVD method): O2 / N2 atmosphere (1:1), power 200 W, film thickness 100 nm, ΔE=30, after being heated at 400 ℃ for 1 h, the color retention rate was 92%. XRD analysis showed that no new phase peaks appeared after the sample was treated at 400 ℃, indicating that the crystal structure remained stable. Example 4 (Mn:Co = 3:1 Boundary Verification) This example was used to verify the color development performance at a lower manganese:cobalt ratio. Manganese oxide (MnO2) and cobalt oxide (Co3O4) were mixed in a molar ratio of 3:1, and 20 wt% zirconium oxide (ZrO2) powder was added. The solvent system was ethanol:acetic acid = 3:1, with a solution concentration of 0.2 mol / L. After ultrasonic dispersion for 30 min, the mixture was spin-coated onto the surface of a polyimide (PI) substrate (3000 rpm, 30 s) and cured at 180 ℃ for 10 min to form a color development film. After treatment with O2 plasma (150 W, 2 min), the film color changed from light gray to bluish-gray, with a color development contrast ΔE = 31. After 30 thermal cycles at 300 ℃, ΔE decreased by 9%, indicating that the color development reaction remained stable and irreversible at Mn:Co = 3:1. Example 5 (Mn:Co = 7:1 Boundary Verification) This example verifies the color development stability under high manganese ratio conditions. MnO2 and Co3O4 were mixed in a molar ratio of 7:1, with a ZrO2 content of 20 wt%, and the preparation process was the same as in Example 4. After O2 plasma treatment, the color development ΔE = 30, and after being kept at 350 ℃ for 1 h, the retention rate was 90%, with no cracks or granulation appearing in the film. This indicates that good color contrast and structural stability can still be maintained under high manganese ratio conditions. Comparative Example 2′ (Verification of the Upper Limit of ZrO2 Content) To verify the rationality of the upper limit of ZrO2 content, the same preparation process as in Example 1 was used, except that the ZrO2 content was increased to 50 wt%. After O2 plasma treatment, the colorimetric layer showed ΔE = 18, indicating uneven color development and localized particle aggregation. After 10 cycles of thermal cycling at 300 °C, microcracks appeared on the film surface, and the color retention rate was less than 80%. The results indicate that when the ZrO2 content exceeds 40 wt%, the system dispersibility decreases, and the color development performance deteriorates significantly. Therefore, a ZrO2 content of 10–40 wt% is determined to be the preferred range of this invention.

Claims

1. A manganese (Mn) cobalt (Co) oxide and zirconium oxide (Zr02) composite plasmonic colorimetric material, characterized in that, The material is composed of manganese oxide (MnO2), cobalt oxide (Co3O4) and zirconium oxide (ZrO2), the molar ratio of Mn:Co is 3-7:1, and the mass fraction of ZrO2 is 10-40 wt%; under the action of plasma, the material undergoes the cooperative valence transformation of Mn 4 ⁺→Mn³⁺ and Co³⁺→Co²⁺, accompanied by the generation of oxygen vacancies, thereby producing irreversible color change, color contrast ΔE≥30, and maintaining structural and color stability under continuous heating conditions of 300-400 ℃.

2. The color-developing material according to claim 1, characterized by, The zirconium oxide (ZrO2) is a nano-sized particle, which is used to provide lattice stability and oxygen vacancy buffering to prevent phase decomposition of the color layer under high temperature conditions.

3. The developer according to claim 1 or 2, characterized by The color layer is arranged on the surface of a glass, polyimide (PI) or ceramic substrate, and a SiO2 protective film is arranged on the color layer to enhance the scratch resistance and optical contrast.

4. A spin coating method for preparing the color-developing material according to any one of claims 1 to 3, characterized by, The method comprises the following steps: (1) MnO2, Co3O4, and ZrO2 nano-powders are added into a mixed solvent of ethanol and acetic acid (volume ratio 3:1) in a certain proportion to form a 0.2 mol / L sol; (2) After ultrasonic dispersion for 30 min, the sol is spin-coated on the surface of the substrate at 3000 rpm for 30 s; (3) The sol is cured at 150-200 ℃ to form a uniform and dense color layer, and the color layer has a color contrast ΔE≥30 under a 300-400 ℃ environment, and the ΔE attenuation is less than 10% after 30 thermal cycles.

5. A physical vapor deposition (PVD) process for preparing the color-developing material according to any one of claims 1 to 3, characterized in that, A Mn / Co / ZrO2 composite thin film is deposited by using a manganese / cobalt metal or oxide target under an O2 / N2 mixed atmosphere at 150-300 ℃, and the film thickness is 50-200 nm; wherein the thin film has a color contrast ΔE≥30 under the action of plasma, and remains stable in structure and color under continuous heating at 300-400 ℃.

6. The developer according to any one of claims 1 to 3, characterized by The material is used for visual indication of plasma processing state, process completion, or cleanliness change.

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