Composite ink and preparation method and application thereof, and composite semiconductor film and preparation method and application thereof

Abstract

The invention belongs to the technical field of semiconductor materials, and particularly relates to composite ink and a preparation method and application thereof, and a composite semiconductor film and a preparation method and application thereof. According to the invention, the polyacrylamide is doped with the metal oxide, the polyacrylamide is used as a linear polymer, the chain flexibility is good, the polyacrylamide molecule promotes the formation of an indium oxide ordered structure in a local area, the efficient transmission of a current carrier is facilitated, and the composite semiconductor film prepared from the polyacrylamide has excellent electrical properties and can be applied to the field of semiconductor devices. And the cable has good mechanical properties, such as good bending resistance. The composite ink provided by the invention is a sol system based on a sol-gel principle, the mixing uniformity of organic and inorganic components can reach a molecular level, and the component uniformity is very high. In addition, as water-based ink, the composite ink provided by the invention has the characteristic of environmental friendliness.

Description

Technical Field

[0001] The present invention belongs to the technical field of semiconductor materials, and in particular relates to a composite ink and a preparation method and application thereof, and a composite semiconductor film and a preparation method and application thereof. Background Art

[0002] Currently, in the field of flat panel displays, metal oxides are considered to be the most promising TFT array active layer materials, with advantages such as high mobility, high optical transmittance and high stability. Compared with traditional α-Si thin film transistors, metal oxide thin film transistors have significant advantages in performance, especially in high refresh rate, high resolution and low power consumption.

[0003] However, with the rapid development of the display field, the electrical properties of metal oxide films can no longer fully meet the requirements of the industry. Summary of the invention

[0004] The purpose of the present invention is to provide a composite ink and a preparation method and application thereof, and a composite semiconductor film and a preparation method and application thereof. The composite semiconductor film prepared by the composite ink provided by the present invention has excellent electrical properties.

[0005] In order to achieve the above object, the present invention provides the following technical solutions:

[0006] The invention provides a composite ink, comprising indium salt, polyacrylamide, surfactant and water; the concentration of indium salt in the composite ink is 0.1-0.5 mol / L; the mass fraction of surfactant in the composite ink is 0.05-0.3%; the mass ratio of indium oxide with equal indium molar number of the indium salt to polyacrylamide is 100:1-5.

[0007] Preferably, the indium salt includes one or both of indium nitrate and hydrated indium nitrate; and the purity of the indium salt is not less than 99.0%.

[0008] Preferably, the weight average molecular weight of the polyacrylamide is 40,000-5,000,000.

[0009] The present invention also provides a method for preparing the composite ink described in the above scheme, comprising the following steps:

[0010] Indium salt, polyacrylamide, a surfactant and water are mixed to obtain the composite ink.

[0011] The present invention also provides the use of the composite ink described in the above scheme or the composite ink obtained by the preparation method described in the above scheme in the preparation of a composite semiconductor film.

[0012] The present invention also provides a composite semiconductor film, which comprises indium oxide and polyacrylamide; the indium oxide is connected to the polyacrylamide through hydrogen bonds and covalent bonds.

[0013] Preferably, the thickness of the composite semiconductor film is 5 to 40 nm.

[0014] The present invention also provides a method for preparing the composite semiconductor film described in the above scheme, comprising the following steps:

[0015] The composite ink is coated on a substrate and then heated and cured to obtain a composite semiconductor film.

[0016] Preferably, the heating temperature is 200-250° C., and the insulation time is 30-60 min.

[0017] The present invention also provides the application of the composite semiconductor film described in the above scheme or the composite semiconductor film obtained by the preparation method described in the above scheme in the field of electronic display.

[0018] The present invention provides a composite ink. In the present invention, polyacrylamide is doped with metal oxides, and the polyacrylamide molecules promote the formation of an ordered structure of indium oxide in a local area, which is beneficial to the efficient transmission of carriers and gives the composite semiconductor film excellent electrical properties; polyacrylamide, as a linear polymer, has good chain flexibility, and the composite semiconductor film prepared by using it improves the mechanical properties of the material without affecting its electrical properties, especially good bending resistance. The composite ink provided by the present invention is a sol system based on the sol-gel principle, and the mixing uniformity of organic and inorganic components can reach the molecular level, and the component uniformity is very high. In addition, the composite ink provided by the present invention is a water-based ink and has environmentally friendly characteristics.

[0019] The present invention also provides a method for preparing the composite ink of the above scheme. The preparation method provided by the present invention has simple steps, is safe and environmentally friendly, and has readily available raw materials.

[0020] The present invention also provides the use of the composite ink described in the above scheme or the composite ink obtained by the preparation method described in the above scheme in preparing a composite semiconductor film. The composite ink provided by the present invention can be used to prepare a composite semiconductor film, and the obtained composite semiconductor film has excellent electrical properties and good mechanical properties, making the composite semiconductor film more suitable for electronic products and having broad prospects.

[0021] The present invention also provides a composite semiconductor film. The composite semiconductor film provided by the present invention adopts the composite ink of the above scheme, and the polyacrylamide molecules promote the formation of an ordered structure of indium oxide in a local area, which is conducive to the efficient transmission of carriers and gives the composite semiconductor film good electrical properties. In addition, the composite semiconductor film provided by the present invention has good mechanical properties and good bending resistance. In addition, the excellent component uniformity of the composite ink gives the composite semiconductor film excellent component uniformity.

[0022] The present invention also provides a method for preparing the composite semiconductor film of the above scheme. The preparation method provided by the present invention is easy to operate, has good feasibility, low cost, and is suitable for industrial production.

[0023] The present invention also provides the application of the composite semiconductor film described in the above scheme or the composite semiconductor film obtained by the preparation method described in the above scheme in the field of electronic display. The composite semiconductor film provided by the present invention has excellent electrical properties, mechanical properties, good bending resistance, and can be used in the field of electronic display, especially in the field of flexible display. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0025] Figure 1 Mobility graphs of thin film transistors prepared using the composite inks of Examples 1 to 5 and the ink of the control example;

[0026] Figure 2 This is a transfer characteristic curve of the thin film transistor prepared with the composite ink of Example 1. DETAILED DESCRIPTION

[0027] The invention provides a composite ink, comprising an indium salt, polyacrylamide, a surfactant and water; the concentration of the indium salt in the composite ink is 0.1-0.5 mol / L; the mass fraction of the surfactant in the composite ink is 0.3-0.5%; and the mass ratio of indium oxide with equal indium molar number of the indium salt to polyacrylamide is 100:1-5.

[0028] The composite ink provided by the present invention includes an indium salt; the indium salt preferably includes one or both of indium nitrate and hydrated indium nitrate; the purity of the indium salt is preferably not less than 99.0%, specifically 99.0%, 99.5% or 99.99% (analytical purity).

[0029] In the present invention, the concentration of the indium salt in the composite ink is preferably 0.1-0.3 mol / L, specifically 0.1 mol / L, 0.15 mol / L, 0.2 mol / L, 0.25 mol / L or 0.3 mol / L.

[0030] The composite ink provided by the present invention includes polyacrylamide; the weight average molecular weight of the polyacrylamide is preferably 40,000-5,000,000, and specifically can be 40,000, 80,000, 12,000, 150,000, 200,000, 350,000 or 5,000,000.

[0031] In the present invention, the mass ratio of indium oxide and polyacrylamide of the indium salt or the like indium mole number is preferably 100:1-4, and can be specifically 100:1, 100:2, 100:3 or 100:4. The present invention defines the usage relationship of indium salt and polyacrylamide by means of indium oxide: on the one hand, the mole number of indium ions in indium oxide is equal to the mole number of indium ions in indium salt, and on the other hand, the mass ratio of indium oxide to polyacrylamide is 100:1-4.

[0032] The composite ink provided by the present invention comprises a surfactant; the surfactant is preferably a fluorocarbon surfactant; the fluorocarbon surfactant is preferably a non-ionic fluorocarbon surfactant; the non-ionic fluorocarbon surfactant is preferably commercially available FSO.

[0033] In the present invention, the mass fraction of the surfactant in the composite ink is preferably 0.05-0.3%, specifically 0.05%, 0.1%, 0.15%, 0.2%, 0.25% or 0.3%.

[0034] The composite ink provided by the present invention comprises water; the water is preferably deionized water.

[0035] The present invention also provides a method for preparing the composite ink described in the above scheme, comprising the following steps:

[0036] Indium salt, polyacrylamide, a surfactant and water are mixed to obtain the composite ink.

[0037] The present invention mixes indium salt, polyacrylamide, surfactant and water (referred to as the first mixing) to obtain the composite ink. In the present invention, the first mixing is preferably: mixing water and polyacrylamide (referred to as mixing A) to obtain a mixed solution A, then mixing the mixed solution A with indium salt (referred to as mixing B) to obtain a mixed solution B, and then mixing the mixed solution B with a surfactant (referred to as mixing C).

[0038] In the present invention, the temperature of the mixture A is preferably 30-50°C, specifically 35°C or 45°C, the mixing time is preferably not less than 3h, specifically 3h, 4h, 5h, 7h, 10h, 15h, 20h or 50h; the mixture A is preferably stirred mixing; the stirring mixing speed is preferably 100-2000rpm, specifically 100rpm, 300rpm, 600rpm, 900rpm, 1200rpm, 1500rpm, 1800rpm, or 2000rpm.

[0039] In the present invention, the temperature of the mixture B is preferably 30-50°C, specifically 35°C or 45°C, and the mixing time is preferably 3-5h, specifically 4h; the mixture B is preferably magnetically stirred; the rotation speed of the magnetic stirring is preferably 2000-6000rpm, specifically 2000rpm, 3000rpm, 4000rpm, 5000rpm or 6000rpm.

[0040] In the present invention, the temperature of the mixture C is preferably 30-50°C, specifically 35°C or 45°C, and the mixing time is preferably 3-5h, specifically 3h; the mixture C is preferably magnetically stirred; the rotation speed of the magnetic stirring is preferably 2000-6000rpm, specifically 2000rpm, 3000rpm, 4000rpm, 5000rpm or 6000rpm.

[0041] The present invention also provides the use of the composite ink described in the above scheme or the composite ink obtained by the preparation method described in the above scheme in the preparation of a composite semiconductor film.

[0042] The composite ink provided by the present invention can be used to prepare a composite semiconductor film. The obtained composite semiconductor film has both mechanical and electrical properties, making the composite semiconductor film more suitable for flexible electronic products and having broad prospects.

[0043] The present invention also provides a composite semiconductor film, which comprises indium oxide and polyacrylamide; the indium oxide is connected to the polyacrylamide through hydrogen bonds and covalent bonds.

[0044] In the present invention, the thickness of the composite semiconductor film is preferably 5 to 40 nm, and specifically may be 5 nm, 10 nm, 20 nm, 30 nm or 40 nm.

[0045] The present invention also provides a method for preparing the composite semiconductor film described in the above scheme, comprising the following steps:

[0046] The composite ink is coated on a substrate and then heated and cured to obtain a composite semiconductor film.

[0047] The present invention coats the composite ink on the substrate and then heats and solidifies it to obtain a composite semiconductor film. In the present invention, the substrate is preferably a glass sheet; the surface of the glass sheet is preferably covered with a Mo film and a SiO film in sequence from the inside to the outside. x / SiN x Composite dielectric film; the size of the substrate is preferably 10mm*10mm.

[0048] In the present invention, the substrate is preferably cleaned before use; the cleaning is preferably: the substrate is sequentially subjected to alkaline washing, water washing, alcohol washing and drying; the reagent used for the alkaline washing is preferably a commercially available IPO glass-specific cleaning solution; the alkaline washing is preferably ultrasonic washing; the time for the alkaline washing is preferably 15 minutes; the water used for the water washing is preferably deionized water; the water washing is preferably ultrasonic washing; the water washing time is preferably 15 minutes; the alcohol used for the alcohol washing is preferably ethanol; the alcohol washing is preferably ultrasonic washing; the alcohol washing time is preferably 15 minutes.

[0049] In the present invention, the coating is preferably spin coating; the spin coating rotation speed is preferably 2000-6000rpm, specifically 2000rpm, 3000rpm, 4000rpm, 5000rpm or 6000rpm, and the spin coating time is preferably 20-60s, specifically 20s, 30s, 40s, 50s or 60s.

[0050] In the present invention, the heating is preferably: placing the substrate on a hot table for heating; the heating temperature is preferably 200-250°C, specifically 200°C, 205°C, 215°C, 225°C, 235°C, 245°C or 250°C, and the insulation time is preferably 30-60min, specifically 30min, 40min, 50min or 60min.

[0051] The present invention also provides the application of the composite semiconductor film described in the above scheme or the composite semiconductor film obtained by the preparation method described in the above scheme in the field of electronic display.

[0052] The composite semiconductor film provided by the present invention has excellent electrical properties, takes into account mechanical properties, and especially has good bending resistance. It can be used in the field of electronic display and the field of flexible display, and specifically can be used in products such as thin film transistor devices.

[0053] In order to further illustrate the present invention, the scheme of the present invention is described in detail below in conjunction with the accompanying drawings and embodiments, but they should not be understood as limiting the protection scope of the present invention.

[0054] Example

[0055] (1) Preparation of drugs and reagents

[0056] Hydrated indium nitrate, analytical grade; polyacrylamide, weight average molecular weight 150,000; deionized water; fluorocarbon surfactant FSO.

[0057] (2) Cleaning of finger bottles and magnetic rotors

[0058] Remove the cap of the finger vial to be washed, sink it into a large beaker filled with deionized water, and put the cap and magnetic rotor in together, so that the finger vial is completely filled with deionized water without bubbles, then ultrasonically clean it for 15 minutes, and then ultrasonically clean it with anhydrous ethanol for 15 minutes; when using tweezers to transfer the finger vial, avoid the tweezers touching the inner wall of the finger vial; after cleaning, put the finger vial and magnetic rotor in an oven to dry.

[0059] (3) Substrate cleaning

[0060] The substrate is a 10mm*10mm glass sheet with a prefabricated Mo film and SiO x / SiN x Composite dielectric film; the substrate to be cleaned is sequentially placed in a beaker containing IPO glass special cleaning solution, deionized water and ethanol for ultrasonic cleaning, each ultrasonic cleaning lasts for 15 minutes, and after cleaning, it is placed in an oven for drying.

[0061] (4) Composite ink preparation

[0062] Deionized water was used as the solvent, and polyacrylamide with a mass fraction of hydrated indium nitrate of 0% (control example), 1% (example 1), 2% (example 2), 3% (example 3), 4% (example 4) or 5% (example 5) was added, stirred at 35° C. for 3 h to dissolve it, and then hydrated indium nitrate with a molar concentration of 0.1 mol / L was added, and magnetic stirring was performed to dissolve it; subsequently, a fluorocarbon surfactant FSO with a solution mass fraction of 0.1% was added, and magnetic stirring was performed to obtain a composite ink.

[0063] (5) Preparation of composite semiconductor films and devices

[0064] The prepared composite ink was spin-coated on the cleaned substrate, the spin-coating speed was set to 5000 rpm, and the spin-coating time was 30 s; after the spin-coating was completed, the substrate was placed on a hot stage and heated at 215°C for 30 minutes to completely solidify the film; a pair of electrodes were prepared on the substrate using a vacuum sputtering device to obtain a thin film transistor device.

[0065] (6) Performance testing

[0066] Use semiconductor parameter analyzer to test the output characteristics and transfer characteristics of thin film transistor devices. The results are as follows Figure 1 and Figure 2 shown.

[0067] according to Figure 1 and Figure 2 It can be seen that the composite semiconductor film provided by the present invention has good electrical properties. This is because the polyacrylamide molecules promote the formation of an ordered structure of indium oxide in a local area, which is beneficial to the efficient transmission of carriers. However, as the amount of polyacrylamide doping increases, the blocking effect of its molecular chain on the oxide structure becomes more obvious, and the device performance gradually decreases. When the polyacrylamide doping concentration is 1%, the film electrical performance is optimal, and the mobility of the thin film transistor device is 5.78cm 2 / V·s, the on / off ratio is 10 7 .

[0068] It can be seen from the above embodiments that the composite ink provided by the present invention can be used to prepare a composite semiconductor film. The obtained composite semiconductor film has excellent electrical properties while taking into account mechanical properties, especially bending resistance, making the composite semiconductor film of the present invention more suitable for electronic products.

[0069] Although the above embodiment describes the present invention in detail, it is only a part of the embodiments of the present invention, not all of the embodiments. Other embodiments can be obtained based on this embodiment without creativity, and these embodiments all fall within the protection scope of the present invention.

Claims

1. A composite ink, characterized in that: including indium salt, polyacrylamide, surfactant and water; The concentration of indium salt in the composite ink is 0.1-0.5 mol / L; The mass fraction of the surfactant in the composite ink is 0.05-0.3%; The mass ratio of indium oxide with the same indium mole number as the indium salt to polyacrylamide is 100:1-5.

2. The composite ink according to claim 1, characterized in that: The indium salt includes one or both of indium nitrate and hydrated indium nitrate; The purity of the indium salt is not less than 99.0%.

3. The composite ink according to claim 1 or 2, characterized in that: The weight average molecular weight of the polyacrylamide is 40,000-5,000,000.

4. The method for preparing the composite ink according to any one of claims 1 to 3, characterized in that: The following steps are involved: Indium salt, polyacrylamide, a surfactant and water are mixed to obtain the composite ink.

5. Use of the composite ink according to any one of claims 1 to 3 or the composite ink obtained by the preparation method according to claim 4 in the preparation of a composite semiconductor film.

6. A composite semiconductor film, characterized in that: The composite semiconductor film includes indium oxide and polyacrylamide; the indium oxide is connected to the polyacrylamide through hydrogen bonds and covalent bonds.

7. The composite semiconductor film according to claim 6, characterized in that The thickness of the composite semiconductor film is 5 to 40 nm.

8. The method for preparing a composite semiconductor film according to any one of claims 6 to 7, characterized in that: The following steps are involved: The composite ink is coated on a substrate and then heated and cured to obtain a composite semiconductor film.

9. The preparation method according to claim 8, characterized in that: The heating temperature is 200-250° C., and the heat preservation time is 30-60 minutes.

10. Use of the composite semiconductor film according to any one of claims 6 to 7 or the composite semiconductor film obtained by the preparation method according to any one of claims 8 to 9 in the field of electronic display.

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