Tin-oxide-based thin film and preparation method therefor

Abstract

A tin-oxide-based thin film. The tin-oxide-based thin film comprises an amorphous structure material having the following chemical general formula: MxSn1-xO2(1-y)F2y, wherein 0.001≤x≤0.2, 0≤y≤0.1, and M is a doped metal element having an ion radius of less than or equal to 120 pm. Compared with a traditional tin oxide thin film, the tin-oxide-based thin film has better electrical properties.

Description

Tin oxide-based film and preparation method thereof

[0001] This application claims priority to the Chinese patent application filed with the China Patent Office on August 23, 2023, with application number 202311065686.8 and invention name “Tin oxide-based film and preparation method thereof”, the entire contents of which are incorporated by reference into this application. Technical Field

[0002] The present application relates to the technical field of conductive films, and in particular to a tin oxide-based film and a preparation method thereof. Background Art

[0003] Indium oxide (In2O3)-based transparent conductive materials are currently the most commonly used transparent conductive oxides (TCOs) in industry. However, indium metal is relatively rare, and In2O3 is unstable in reducing atmospheres and relatively high humidity environments. In recent years, tin oxide-based TCO films have been developed as an alternative to In2O3 films and are widely used in technologies such as solar cells, touch screens, thin-film transistors, and semiconductor lasers. However, traditional tin oxide-based films have poor electrical properties.

[0004] Summary of the Invention

[0005] Based on this, it is necessary to provide a tin oxide-based thin film and a preparation method thereof. The tin oxide-based thin film of the present application has good electrical properties.

[0006] In a first aspect, the present application provides a tin oxide-based thin film, comprising an amorphous material having the following general chemical formula:

[0007] M x Sn 1-x O 2(1-y) F 2y , where 0.001≤x≤0.2, 0≤y≤0.1, and M is a doping metal element with an ion radius less than or equal to 120 pm.

[0008] In some embodiments, M includes at least one of an alkali metal element, an alkaline earth metal element, a lanthanide metal element, Y, Ti, Mn, Fe, Co, Ni, Cu, Zn, Nd, Ta, Nb, Sb, W, Mo, and Cd.

[0009] In some embodiments, M comprises Li and one or more of Zn, Mg, Ca, Ba, Y, and La, and the work function of the tin oxide-based thin film is greater than 3.4 eV and less than 4.5 eV.

[0010] In some embodiments, M is Li and y=0, and the work function of the tin oxide-based thin film is greater than 3.4 eV and less than 3.66 eV.

[0011] In some embodiments, M is one or more of Zn, Mg, Ca, Ba, Y, and La, and the work function of the tin oxide-based thin film is greater than 3.66 eV and less than 4.5 eV.

[0012] In some embodiments, the tin oxide-based film has a thickness of 1 nm to 200 nm.

[0013] In a second aspect, the present application provides a method for preparing any of the above-mentioned tin oxide-based thin films, comprising:

[0014] A tin oxide-based thin film is prepared on a substrate, wherein the tin oxide-based thin film comprises an amorphous material having the following chemical formula: x Sn 1-x O 2(1-y) F 2y , where 0.001≤x≤0.2, 0≤y≤0.1, and M is a doping metal element with an ion radius less than or equal to 120 pm.

[0015] In some embodiments, forming a tin oxide-based thin film on a substrate includes:

[0016] The tin oxide-based thin film is deposited using a tin oxide target containing a doped metal element M, or using a tin oxide target containing a doped metal element M and a fluorine element.

[0017] In some embodiments, M includes at least one of an alkali metal element, an alkaline earth metal element, a lanthanide metal element, Y, Ti, Mn, Fe, Co, Ni, Cu, Zn, Nd, Ta, Nb, Sb, W, Mo, and Cd.

[0018] In some embodiments, the deposition temperature is 20°C to 300°C.

[0019] In some embodiments, the deposition time is 2 min to 100 min.

[0020] In some embodiments, the deposition power is 0.2 W / cm 2 ~3W / cm 2 .

[0021] The tin oxide-based film comprises an amorphous material having the following chemical formula: x Sn 1-x O 2(1-y) F 2y, where 0.001≤x≤0.2, 0≤y≤0.1, and M is a doping metal element with an ion radius less than or equal to 120pm. Compared to substitutional doping in traditional semiconductor materials, the tin oxide-based film of the present application uses metal elements with an ion radius less than or equal to 120pm for doping, and the interstitial defect formation energy of the amorphous structure material is low, and mainly exists in the film as interstitial defects, which can reduce the structural defects in the tin oxide-based film to improve the electrical properties of the tin oxide-based film. At the same time, the doping metal elements in the interstitial position act as shallow donors in the film, which can further improve the electrical properties of the film. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] Figure 1 shows the Li prepared in Example 1 and Comparative Example 1 of the present application. 0.12 Sn 0.88 O XRD pattern of tin oxide-based films;

[0023] Figure 2 shows the Mg prepared in Example 2 and Comparative Example 2 of the present application. 0.05 Sn 0.95 O XRD pattern of tin oxide-based films;

[0024] Figure 3 shows the Zn prepared in Example 3 and Comparative Example 3 of the present application. 0.08 Sn 0.92 O XRD pattern of tin oxide-based films;

[0025] FIG4 is a diagram of Y prepared in Example 4 and Comparative Example 4 of the present application. 0.03 Sn 0.97 O XRD pattern of tin oxide-based films;

[0026] Figure 5 shows the La prepared in Example 5 and Comparative Example 5 of the present application. 0.04 Sn 0.96 O XRD pattern of tin oxide-based films;

[0027] Figure 6 shows the Li prepared in Example 7 of this application. 0.01 Zn 0.01 Sn 0.98 O XRD pattern of tin oxide-based films;

[0028] Figure 7 shows the Li prepared in Example 1 of this application. 0.12 Sn 0.88 UPS diagram of tin oxide-based films;

[0029] Figure 8 shows the Mg prepared in Example 2 of this application. 0.05 Sn 0.95 UPS diagram of tin oxide-based films;

[0030] Figure 9 shows the Zn prepared in Example 3 of this application. 0.08 Sn0.92 UPS diagram of tin oxide-based films;

[0031] Figure 10 is the Y prepared in Example 4 of the present application 0.03 Sn 0.97 UPS diagram of tin oxide-based films;

[0032] Figure 11 shows the Li prepared in Example 7 of this application. 0.01 Zn 0.01 Sn 0.98 UPS diagram of tin oxide-based films;

[0033] Figure 12 is the control group SnO provided by this application 0.98 F 0.02 UPS diagram of tin oxide-based films. DETAILED DESCRIPTION

[0034] To make the above-mentioned objects, features, and advantages of the present application more clearly understood, the specific embodiments of the present application are described in detail below with reference to the accompanying drawings. The following description sets forth many specific details to facilitate a full understanding of the present application. However, the present application can be implemented in many other ways than those described herein, and those skilled in the art can make similar improvements without violating the scope of the present application. Therefore, the present application is not limited to the specific embodiments disclosed below.

[0035] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the art to which this application pertains. The terms used herein in the specification of this application are for the purpose of describing specific embodiments only and are not intended to limit this application. The term "and / or" as used herein includes any and all combinations of one or more of the associated listed items.

[0036] An embodiment of the present application provides a tin oxide-based thin film, including an amorphous material having the following chemical formula: x Sn 1-x O 2(1-y) F 2y , where 0.001≤x≤0.2, 0≤y≤0.1, and M is a doping metal element with an ion radius less than or equal to 120 pm.

[0037] The tin oxide-based film comprises an amorphous material having the following chemical formula: x Sn 1-x O 2(1-y) F 2y, wherein 0.001≤x≤0.2, 0≤y≤0.1, and M is a doping metal element with an ion radius less than or equal to 120pm. Compared with substitutional doping in traditional semiconductor materials, the tin oxide-based film in the present application is doped with metal elements with an ion radius less than or equal to 120pm, and the interstitial defect formation energy of the amorphous structure material is low, and it mainly exists in the form of interstitial defects in the film, which can reduce the structural defects in the tin oxide-based film to improve the electrical properties of the tin oxide-based film. At the same time, the doped metal elements in the interstitial position act as shallow donors in the film, which can further improve the electrical properties of the film. The tin oxide-based film of the present application has better electrical properties than traditional tin oxide films.

[0038] Alternatively, x is 0.001, 0.002, 0.003, 0.004, 0.005, 0.008, 0.01, 0.015, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.11, 0.12, 0.13, 0.14, 0.15, 0.16, 0.17, 0.18, 0.19, 0.195 or 0.2.

[0039] Optionally, y is 0, 0.0001, 0.001, 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.091, 0.092, 0.093, 0.094, 0.095, 0.099, 0.0999 or 0.1.

[0040] Alternatively, the ionic radius of 50 pm ≤ M is ≤ 120 pm. Further optionally, the ionic radius of M is 50 pm, 52 pm, 54 pm, 56 pm, 58 pm, 60 pm, 62 pm, 64 pm, 66 pm, 68 pm, 70 pm, 72 pm, 74 pm, 76 pm, 78 pm, 80 pm, 82 pm, 84 pm, 86 pm, 88 pm, 90 pm, 92 pm, 94 pm, 96 pm, 98 pm, 100 pm, 102 pm, 104 pm, 106 pm, 108 pm, 110 pm, 112 pm, 114 pm, 116 pm, 118 pm or 120 pm.

[0041] In some embodiments, the component of the tin oxide-based film is an amorphous material having the following chemical formula: x Sn 1-x O 2(1-y) F 2y , where 0.001≤x≤0.2, 0≤y≤0.1, and M is a doping metal element with an ion radius less than or equal to 120 pm.

[0042] In some embodiments, the tin oxide-based film has an amorphous structure. Based on the tin oxide-based films of the aforementioned compositions, the amorphous tin oxide-based film has superior electrical properties compared to single-crystal or polycrystalline tin oxide-based films. Compared to polycrystalline or single-crystal structures, the amorphous structure of the tin oxide-based film is more conducive to the relaxation of strain caused by interstitial impurities, thereby achieving a higher interstitial impurity concentration, significantly increasing the carrier concentration of the film and reducing the resistivity of the film, resulting in the tin oxide-based film having an amorphous structure having superior electrical conductivity.

[0043] In some embodiments, M comprises at least one of an alkali metal element, an alkaline earth metal element, a lanthanide metal element, Y, Ti, Mn, Fe, Co, Ni, Cu, Zn, Nd, Ta, Nb, Sb, W, Mo, and Cd. Alternatively, M comprises at least one of Li, Mg, Sc, Ti, Cr, Mn, Fe, Co, Ni, Cu, Zn, Sb, Y, La, and Ta.

[0044] In some embodiments, M comprises Li and one or more of Zn, Mg, Ca, Ba, Y, and La, and the work function of the tin oxide-based film is greater than 3.4 eV and less than 4.5 eV. When tin oxide is co-doped with Li and one or more of Zn, Mg, Ca, Ba, Y, and La, a tin oxide-based film with a work function adjustable over a wide range can be obtained.

[0045] In some embodiments, M is Li and y=0, and the work function of the tin oxide-based film is greater than 3.4 eV and less than 3.66 eV. When M is Li and y=0, a work function greater than that of the conventional SnO 0.98 F 0.02 Tin oxide based film (FTO) with low tin oxide based film.

[0046] In some embodiments, M is one or more of Zn, Mg, Ca, Ba, Y, and La, and the work function of the tin oxide-based film is greater than 3.66 eV and less than 4.5 eV. When tin oxide is doped with one or more of Zn, Mg, Ca, Ba, Y, and La, a tin oxide-based film having a higher work function than that of the FTO film can be obtained.

[0047] Using metal elements as dopants, the structure and radius of the metal ions can have varying effects on the work function of the film. Doping with Li can reduce the work function of tin oxide-based films, while doping with Zn, Mg, Ca, Ba, Y, or La can increase it. This allows the work function of tin oxide-based films to be tunable within a certain range, potentially expanding their application.

[0048] In some embodiments, the thickness of the tin oxide-based film is 1 nm to 200 nm. Within the thickness range of the tin oxide-based film, M x Sn 1-x O 2(1-y) F 2y The material has a better effect of maintaining an amorphous structure. When the thickness of the tin oxide-based film is too large, M x Sn 1-x O 2(1-y) F 2y The material may crystallize, resulting in reduced electrical properties of the film. Optionally, the thickness of the tin oxide-based film is 1 nm, 2 nm, 3 nm, 5 nm, 7 nm, 9 nm, 10 nm, 20 nm, 30 nm, 40 nm, 50 nm, 60 nm, 70 nm, 80 nm, 90 nm, 100 nm, 110 nm, 120 nm, 130 nm, 140 nm, 150 nm, 160 nm, 170 nm, 180 nm, 190 nm, or 200 nm.

[0049] Another embodiment of the present application provides a method for preparing any of the above-mentioned tin oxide-based thin films, comprising: preparing a tin oxide-based thin film on a substrate, wherein the tin oxide-based thin film comprises an amorphous material having the following chemical formula: x Sn 1-x O 2(1-y) F 2y , where 0.001≤x≤0.2, 0≤y≤0.1, and M is a doping metal element with an ion radius less than or equal to 120 pm.

[0050] In some embodiments, preparing a tin oxide-based thin film on a substrate includes: depositing the tin oxide-based thin film using a tin oxide target containing a doped metal element M, or depositing the tin oxide-based thin film using a tin oxide target containing a doped metal element M and a fluorine element.

[0051] In some embodiments, M comprises at least one of an alkali metal element, an alkaline earth metal element, a lanthanide metal element, Y, Ti, Mn, Fe, Co, Ni, Cu, Zn, Nd, Ta, Nb, Sb, W, Mo, and Cd. Alternatively, M comprises at least one of Li, Mg, Sc, Ti, Cr, Mn, Fe, Co, Ni, Cu, Zn, Sb, Y, La, and Ta.

[0052] In some embodiments, the deposition temperature is 20°C to 300°C. The crystallization temperature of the tin oxide-based film is above 400°C. The amorphous structure of the tin oxide-based film is more conducive to the relaxation of strain caused by interstitial impurities than polycrystalline or single crystal structures. Therefore, a higher interstitial impurity concentration can be obtained, which greatly increases the carrier concentration of the film and reduces the resistivity of the film. As a result, the tin oxide-based film with an amorphous structure has better conductivity. Tin oxide-based films with an amorphous structure can be prepared within this temperature range. Optionally, the deposition temperature is 20°C, 25°C, 30°C, 35°C, 40°C, 45°C, 50°C, 55°C, 60°C, 65°C, 70°C, 75°C, 80°C, 85°C, 90°C, 95°C, 100°C, 110°C, 120°C, 130°C, 150°C, 160°C, 180°C, 200°C, 210°C, 220°C, 230°C, 250°C, 260°C, 280°C, 290°C or 300°C.

[0053] In some embodiments, the deposition time is 2 min to 100 min. By controlling the deposition time, the thickness of the tin oxide-based film can be controlled. Within the deposition time range, a tin oxide-based film of suitable thickness can be obtained, so that the tin oxide-based film has both good conductive properties and transparent properties. Optionally, the deposition time is 2 min, 3 min, 4 min, 5 min, 6 min, 7 min, 8 min, 9 min, 10 min, 12 min, 15 min, 18 min, 20 min, 22 min, 25 min, 28 min, 30 min, 35 min, 40 min, 45 min, 50 min, 55 min, 60 min, 65 min, 70 min, 72 min, 75 min, 78 min, 80 min, 82 min, 85 min, 88 min, 90 min, 92 min, 95 min, 98 min, 99 min or 100 min.

[0054] In some embodiments, the deposition power is 0.2 W / cm 2 ~3W / cm 2 It is understood that the deposition power represents the power of the deposition equipment corresponding to the target material per unit area. Within the range of the deposition power, a tin oxide-based thin film with a good film forming effect can be obtained. Optionally, the deposition power is 0.2W / cm 2 , 0.3W / cm 2 , 0.4W / cm 2 , 0.5W / cm 2 , 0.6W / cm 2 , 0.7W / cm 2 , 0.8W / cm 2 , 0.9W / cm2 , 1W / cm 2 , 1.1W / cm 2 , 1.2W / cm 2 , 1.3W / cm 2 , 1.4W / cm 2 , 1.5W / cm 2 , 1.6W / cm 2 , 1.7W / cm 2 , 1.8W / cm 2 , 1.9W / cm 2 , 2W / cm 2 , 2.1W / cm 2 , 2.2W / cm 2 , 2.3W / cm 2 , 2.4W / cm 2 , 2.5W / cm 2 , 2.6W / cm 2 , 2.7W / cm 2 , 2.8W / cm 2 , 2.9W / cm 2 or 3W / cm 2 .

[0055] In some embodiments, the tin oxide-based thin film is prepared by magnetron sputtering or reactive plasma deposition.

[0056] In some embodiments, the gas atmosphere of magnetron sputtering or reactive plasma deposition is a mixture of an inert gas and an oxidizing gas.

[0057] In some embodiments, the oxidizing gas includes oxygen.

[0058] In some embodiments, the inert gas includes at least one of helium, neon, argon, krypton, and xenon.

[0059] In some embodiments, the gas pressure of the mixed gas during the deposition process is 0.1 Pa to 10 Pa. Alternatively, the gas pressure of the mixed gas is 0.1 Pa, 0.2 Pa, 0.5 Pa, 1 Pa, 1.5 Pa, 2 Pa, 2.5 Pa, 3 Pa, 3.5 Pa, 4 Pa, 4.5 Pa, 5 Pa, 5.5 Pa, 6 Pa, 6.5 Pa, 7 Pa, 7.5 Pa, 8 Pa, 8.5 Pa, 9 Pa, 9.5 Pa, or 10 Pa.

[0060] In some embodiments, the flow ratio of the inert gas to the oxidizing gas is (1-30): 1. Alternatively, the flow ratio of the inert gas to the oxidizing gas is 1:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, 10:1, 11:1, 12:1, 13:1, 14:1, 15:1, 16:1, 17:1, 18:1, 19:1, 20:1, 21:1, 22:1, 23:1, 24:1, 25:1, 26:1, 27:1, 28:1, 29:1, or 30:1.

[0061] The following are specific embodiments

[0062] Example 1

[0063] The components of the tin oxide-based film prepared in this embodiment are Li 0.12 Sn 0.88 O.

[0064] The preparation method of the tin oxide-based film in this embodiment is as follows:

[0065] (1) A tin oxide-based thin film was deposited using a magnetron sputtering device. The target material of the magnetron sputtering was Li-doped tin oxide ceramic. The substrate was placed in a reaction chamber of the magnetron sputtering device, the reaction chamber was evacuated, and the temperature of the substrate was controlled to 180°C.

[0066] (2) Argon and oxygen were introduced into the reaction chamber to make the gas pressure in the reaction chamber 0.4 Pa, and the power of magnetron sputtering was controlled to 1.48 W / cm 2 , the deposition of tin oxide-based thin film was carried out, and the deposition time was 27 minutes.

[0067] Example 2

[0068] The components of the tin oxide-based film prepared in this embodiment are Mg 0.05 Sn 0.95 O.

[0069] The preparation method of the tin oxide-based film in this embodiment is as follows:

[0070] (1) A tin oxide-based thin film was deposited using a magnetron sputtering device. The target material of the magnetron sputtering was Mg-doped tin oxide ceramic. The substrate was placed in a reaction chamber of the magnetron sputtering device, the reaction chamber was evacuated, and the temperature of the substrate was controlled to 180°C.

[0071] (2) Argon and oxygen were introduced into the reaction chamber to make the gas pressure in the reaction chamber 0.4 Pa, and the power of magnetron sputtering was controlled to 1.48 W / cm 2 , the deposition of tin oxide-based thin film was carried out, and the deposition time was 27 minutes.

[0072] Example 3

[0073] The components of the tin oxide-based film prepared in this embodiment are Zn 0.08 Sn 0.92 O.

[0074] The preparation method of the tin oxide-based film in this embodiment is as follows:

[0075] (1) A magnetron sputtering device is used to deposit a tin oxide-based thin film. The target material of the magnetron sputtering is Zn-doped tin oxide ceramic. The substrate is placed in a reaction chamber of the magnetron sputtering device, the reaction chamber is evacuated, and the temperature of the substrate is controlled to 180°C.

[0076] (2) Argon and oxygen were introduced into the reaction chamber to make the gas pressure in the reaction chamber 0.4 Pa, and the power of magnetron sputtering was controlled to 1.48 W / cm 2 , the deposition of tin oxide-based thin film was carried out, and the deposition time was 27 minutes.

[0077] Example 4

[0078] The components of the tin oxide-based film prepared in this embodiment are Y 0.03 Sn 0.97 O.

[0079] The preparation method of the tin oxide-based film in this embodiment is as follows:

[0080] (1) A magnetron sputtering device is used to deposit a tin oxide-based thin film. The target material of the magnetron sputtering is Y-doped tin oxide ceramic. The substrate is placed in the reaction chamber of the magnetron sputtering device, the reaction chamber is evacuated, and the temperature of the substrate is controlled to 180°C.

[0081] (2) Argon and oxygen were introduced into the reaction chamber to make the gas pressure in the reaction chamber 0.4 Pa, and the power of magnetron sputtering was controlled to 1.48 W / cm 2 , the deposition of tin oxide-based thin film was carried out, and the deposition time was 27 minutes.

[0082] Example 5

[0083] The components of the tin oxide-based film prepared in this embodiment are La 0.04 Sn 0.96 O.

[0084] The preparation method of the tin oxide-based film in this embodiment is as follows:

[0085] (1) A tin oxide-based thin film was deposited using a magnetron sputtering device. The target material of the magnetron sputtering was La-doped tin oxide ceramic. The substrate was placed in a reaction chamber of the magnetron sputtering device, the reaction chamber was evacuated, and the temperature of the substrate was controlled to 180°C.

[0086] (2) Argon and oxygen were introduced into the reaction chamber to make the gas pressure in the reaction chamber 0.4 Pa, and the power of magnetron sputtering was controlled to 1.48 W / cm 2 , the deposition of tin oxide-based thin film was carried out, and the deposition time was 27 minutes.

[0087] Example 6

[0088] The components of the tin oxide-based film prepared in this embodiment are Li 0.03 Sn 0.97 O 1.9 F 0.1 .

[0089] The preparation method of the tin oxide-based film in this embodiment is as follows:

[0090] (1) A tin oxide-based thin film was deposited using a magnetron sputtering device. The target material of the magnetron sputtering was La-doped tin oxide ceramic. The substrate was placed in a reaction chamber of the magnetron sputtering device, the reaction chamber was evacuated, and the temperature of the substrate was controlled to 180°C.

[0091] (2) Argon and oxygen were introduced into the reaction chamber to make the gas pressure in the reaction chamber 0.4 Pa, and the power of magnetron sputtering was controlled to 1.48 W / cm 2 , the deposition of tin oxide-based thin film was carried out, and the deposition time was 27 minutes.

[0092] Example 7

[0093] The components of the tin oxide-based film prepared in this embodiment are Li 0.01 Zn 0.01 Sn 0.98 O.

[0094] The preparation method of the tin oxide-based film in this embodiment is as follows:

[0095] (1) A tin oxide-based thin film was deposited using a magnetron sputtering device. The target material of the magnetron sputtering was a tin oxide ceramic co-doped with Li and Zn. The substrate was placed in a reaction chamber of the magnetron sputtering device, the reaction chamber was evacuated, and the temperature of the substrate was controlled to 180°C.

[0096] (2) Argon and oxygen were introduced into the reaction chamber to make the gas pressure in the reaction chamber 0.4 Pa, and the power of magnetron sputtering was controlled to 1.48 W / cm 2 , the deposition of tin oxide-based thin film was carried out, and the deposition time was 27 minutes.

[0097] Comparative Example 1

[0098] The components of the tin oxide-based film prepared in this comparative example are Li 0.12 Sn 0.88 O.

[0099] The preparation method of the tin oxide-based film in this comparative example is:

[0100] (1) A tin oxide-based thin film was deposited using a magnetron sputtering device. The target material of the magnetron sputtering was Li-doped tin oxide ceramic. The substrate was placed in a reaction chamber of the magnetron sputtering device, the reaction chamber was evacuated, and the temperature of the substrate was controlled to 400°C.

[0101] (2) Argon and oxygen were introduced into the reaction chamber to make the gas pressure in the reaction chamber 0.4 Pa, and the power of magnetron sputtering was controlled to 1.48 W / cm 2 , the deposition of tin oxide-based thin film was carried out, and the deposition time was 27 minutes.

[0102] Comparative Example 2

[0103] The components of the tin oxide-based film prepared in this comparative example are Mg 0.05 Sn 0.95 O.

[0104] The preparation method of the tin oxide-based film in this comparative example is:

[0105] (1) A tin oxide-based thin film was deposited using a magnetron sputtering device. The target material of the magnetron sputtering was Mg-doped tin oxide ceramic. The substrate was placed in a reaction chamber of the magnetron sputtering device, the reaction chamber was evacuated, and the temperature of the substrate was controlled to 400°C.

[0106] (2) Argon and oxygen were introduced into the reaction chamber to make the gas pressure in the reaction chamber 0.4 Pa, and the power of magnetron sputtering was controlled to 1.48 W / cm 2 , the deposition of tin oxide-based thin film was carried out, and the deposition time was 27 minutes.

[0107] Comparative Example 3

[0108] The components of the tin oxide-based film prepared in this comparative example are Zn 0.08 Sn 0.92 O.

[0109] The preparation method of the tin oxide-based film in this comparative example is:

[0110] (1) A tin oxide-based thin film was deposited using a magnetron sputtering device. The target material of the magnetron sputtering was Zn-doped tin oxide ceramic. The substrate was placed in a reaction chamber of the magnetron sputtering device, the reaction chamber was evacuated, and the temperature of the substrate was controlled to 400°C.

[0111] (2) Argon and oxygen were introduced into the reaction chamber to make the gas pressure in the reaction chamber 0.4 Pa, and the power of magnetron sputtering was controlled to 1.48 W / cm 2 , the deposition of tin oxide-based thin film was carried out, and the deposition time was 27 minutes.

[0112] Comparative Example 4

[0113] The components of the tin oxide-based film prepared in this comparative example are Y 0.03 Sn 0.97 O.

[0114] The preparation method of the tin oxide-based film in this comparative example is:

[0115] (1) A tin oxide-based thin film was deposited using a magnetron sputtering device. The target material of the magnetron sputtering was Y-doped tin oxide ceramic. The substrate was placed in a reaction chamber of the magnetron sputtering device, the reaction chamber was evacuated, and the temperature of the substrate was controlled to 600°C.

[0116] (2) Argon and oxygen were introduced into the reaction chamber to make the gas pressure in the reaction chamber 0.4 Pa, and the power of magnetron sputtering was controlled to 1.48 W / cm 2 , the deposition of tin oxide-based thin film was carried out, and the deposition time was 27 minutes.

[0117] Comparative Example 5

[0118] The components of the tin oxide-based film prepared in this comparative example are La 0.04 Sn 0.96 O.

[0119] The preparation method of the tin oxide-based film in this comparative example is:

[0120] (1) A tin oxide-based thin film was deposited using a magnetron sputtering device. The target material of the magnetron sputtering was La-doped tin oxide ceramic. The substrate was placed in a reaction chamber of the magnetron sputtering device, the reaction chamber was evacuated, and the temperature of the substrate was controlled to 500°C.

[0121] (2) Argon and oxygen were introduced into the reaction chamber to make the gas pressure in the reaction chamber 0.4 Pa, and the power of magnetron sputtering was controlled to 1.48 W / cm 2 , the deposition of tin oxide-based thin film was carried out, and the deposition time was 27 minutes.

[0122] Comparative Example 6

[0123] The components of the tin oxide-based film prepared in this comparative example are Ba 0.1 Sn 0.9 O, where Ba 2+ The radius is 135pm.

[0124] The preparation method of the tin oxide-based film in this comparative example is:

[0125] (1) A tin oxide-based thin film was deposited using a magnetron sputtering device. The target material of the magnetron sputtering was Ba-doped tin oxide ceramic. The substrate was placed in a reaction chamber of the magnetron sputtering device, the reaction chamber was evacuated, and the temperature of the substrate was controlled to 180°C.

[0126] (2) Argon and oxygen were introduced into the reaction chamber to make the gas pressure in the reaction chamber 0.4 Pa, and the power of magnetron sputtering was controlled to 1.48 W / cm 2 , the deposition of tin oxide-based thin film was carried out, and the deposition time was 27 minutes.

[0127] The components of the tin oxide-based films prepared in Examples 1 to 7 and Comparative Examples 1 to 6, as well as the temperature, pressure, power, and time of magnetron sputtering in the preparation process are shown in Table 1 below:

[0128] Table 1

[0129] 1 to 6, the electrical properties of the tin oxide-based films prepared in Examples 1 to 7 and Comparative Examples 1 to 6 were tested. Figures 1 to 6 are XRD patterns of the tin oxide-based films prepared in Examples 1 to 5, 7 and Comparative Examples 1 to 5. 20 / cm 3 ), mobility μ(cm 2 / Vs), resistivityρ(10 -3 Ωcm), and the transmittance T (%) and absorptivity A (%) were also tested. Referring to Figures 7 to 12, the tin oxide-based films prepared in Examples 1 to 4 and 7 and the SnO 0.98 F 0.02 The work function of the tin oxide-based film was tested. Figures 7 to 12 are UPS diagrams of the above tin oxide-based films respectively. The test results are shown in Table 2 below:

[0130] Table 2

[0131] As can be seen from Table 2 above, the tin oxide-based films prepared in Examples 1-7 all have higher carrier concentrations n, higher mobilities μ, significantly lower resistivities, higher transmittances T, and lower absorptivity A than the tin oxide-based films prepared in Comparative Examples 1-6. In Examples 1-6, the deposition temperature was controlled at 180°C, i.e., within the range of 20°C to 300°C, to obtain amorphous tin oxide-based films. In contrast, the deposition temperatures in Comparative Examples 1-6 were all above 400°C, resulting in crystallization of the tin oxide-based films. Specifically, when the doping element M is a doping metal element with an ionic radius of less than or equal to 120 μm, and the material of the tin oxide-based film is amorphous, tin oxide-based films with superior electrical properties can be obtained.

[0132] At the same time, the components are SnO 0.98 F 0.02 The tin oxide-based film prepared in Example 1 is composed of Li 0.12 Sn 0.88 O, its work function is 3.58eV, which is smaller than the work function of the control film, that is, when M is Li and y=0, a tin oxide-based film with a reduced work function can be obtained. The work function of the films prepared in Examples 2 to 4 is greater than that of the control film, that is, when M is at least Mg, Zn, and Y, a tin oxide-based film with an increased work function can be obtained. The component of the film prepared in Example 7 is Li 0.01 Zn 0.01 Sn 0.98 O, that is, M includes Li and Zn, and the work function is 3.71eV. In this application, the work function of the tin oxide-based film can be regulated by doping with different elements, so that the film has a wider range of applications in the fields of solar cells and flexible devices.

[0133] The technical features of the above-mentioned embodiments can be combined arbitrarily. In order to make the description concise, not all possible combinations of the technical features in the above-mentioned embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0134] The above-described embodiments merely represent several implementation methods of the present application. While the descriptions are relatively specific and detailed, they should not be construed as limiting the scope of the patent. It should be noted that a person skilled in the art could make several modifications and improvements without departing from the spirit of the present application, all of which fall within the scope of protection of the present application. Therefore, the scope of protection of the patent in this application shall be based on the appended claims, and the specification and drawings may be used to interpret the claims.

Claims

1. A tin oxide-based film comprising an amorphous material having the following general chemical formula: M x Sn 1-x O 2(1-y) F 2y ,in, 0.001≤x≤0.2, 0≤y≤0.1, M is a doping metal element having an ion radius less than or equal to 120 pm.

2. The tin oxide-based thin film according to claim 1, wherein M includes at least one of alkali metal elements, alkaline earth metal elements, lanthanide metal elements, Y, Ti, Mn, Fe, Co, Ni, Cu, Zn, Nd, Ta, Nb, Sb, W, Mo and Cd.

3. The tin oxide-based thin film according to claim 2, wherein M includes Li and one or more of Zn, Mg, Ca, Ba, Y and La, and a work function of the tin oxide-based thin film is greater than 3.4 eV and less than 4.5 eV.

4. The tin oxide-based film according to any one of claims 2 to 3, wherein: M is Li and y=0, and the work function of the tin oxide-based film is greater than 3.4 eV and less than 3.66 eV.

5. The tin oxide-based film according to any one of claims 2 to 4, wherein: M is one or more of Zn, Mg, Ca, Ba, Y and La, and the work function of the tin oxide-based film is greater than 3.66 eV and less than 4.5 eV.

6. The tin oxide-based thin film according to any one of claims 1 to 5, wherein The thickness of the tin oxide-based film is 1 nm to 200 nm.

7. A method for preparing the tin oxide-based thin film according to any one of claims 1 to 6, comprising: A tin oxide-based thin film is prepared on a substrate, wherein the tin oxide-based thin film includes an amorphous structure material having the following chemical formula: x Sn 1-x O 2(1-y) F 2y , wherein 0.001≤x≤0.2, 0≤y≤0.1, and M is a doping metal element having an ion radius less than or equal to 120 pm.

8. The method for preparing a tin oxide-based thin film according to claim 7, wherein: The preparation of a tin oxide-based thin film on a substrate includes: The tin oxide-based thin film is deposited using a tin oxide target containing a doped metal element M, or the tin oxide-based thin film is deposited using a tin oxide target containing a doped metal element M and a fluorine element.

9. The method for preparing a tin oxide-based thin film according to claim 8, wherein: M includes at least one of alkali metal elements, alkaline earth metal elements, lanthanide metal elements, Y, Ti, Mn, Fe, Co, Ni, Cu, Zn, Nd, Ta, Nb, Sb, W, Mo and Cd.

10. The method for preparing a tin oxide-based thin film according to any one of claims 8 to 9, wherein: The deposition temperature is 20°C to 300°C.

11. The method for preparing a tin oxide-based thin film according to any one of claims 8 to 10, wherein: The deposition time is 2 min to 100 min.

12. The method for preparing a tin oxide-based thin film according to any one of claims 8 to 11, wherein: The deposition power is 0.2 W / cm 2 ~3W / cm 2 .

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